KR19990022376A - Method and apparatus for preparing intermediate product by controlling conversion and temperature in sprayed liquid - Google Patents

Abstract

A method and apparatus for preparing intermediate oxidation products by spraying a first liquid containing reactants into a gas containing an oxidant in such a way as to form intermediate oxidation products other than carbon monoxide and / or carbon dioxide. The oxidation reaction is controlled by monitoring and adjusting the temperature and conversion rates in one or more different reaction steps. The oxidation reaction also monitors the temporal conversion rate (the conversion rate between the time the droplet is formed and the time they are in the liquid mass) before coalescence when the first reactant is converted to the oxidation product just before the droplets coalesce into the second liquid mass. Temperature before the coalescence (the temperature of the droplets just before the droplets coalesce into the liquid mass), or the temporal temperature difference (the difference between the temperature before deposition and the droplet temperature just before spraying), or the temporal fine temperature difference (two in the reaction zone). Temperature difference between locations), or a combination thereof. The present invention, among other advantages, minimizes waste and provides significant environmental benefits.

Description

Method and apparatus for preparing intermediate oxidation product by controlling conversion and temperature in sprayed liquid

The reaction of reacting a first reactant dissolved in a liquid with a second reactant contained in a gas under increased surface area conditions is known in the art. This reaction is carried out in a device such as a gas scrubber, burner, reaction vessel, or the like.

The technique of spraying a liquid into a gaseous atmosphere is one of the aforementioned techniques disclosed in the art. Spray techniques for carrying out the reactions so far disclosed in the art are directed to the desired reaction product, yield, conversion and conversion rate, temperature profile in the reaction zone, average droplet size or diameter, evaporation rate, etc., if the reaction product is an intermediate. There is some immaturity and lack of innovation in controlling the response. Indeed, in most but not all cases, the reaction product is substantially the final product expected under the initial overall reaction conditions. For example, in the case of a burner that sprays fuel in the atmosphere of an oxygen containing gas such as air, the final product of the reaction is carbon dioxide and carbon monoxide and nitrogen oxides are preferably minimized as much as possible. As another example, a gas scrubber for removing acidic compounds from a gas may use sprayed liquids containing alkali or alkaline earth metal compounds that react with acidic compounds in the gas to form corresponding salts. As another example, ammonia and phosphoric acid are reacted under spray conditions to form the final reaction product, ammonium orthophosphate.

On the other hand, in the case of oxidation, in particular, the reaction for preparing the intermediate product is not carried out under spraying conditions because atomization promotes the completion of the reaction and thus the formation of the final product. For example, it has not been reported that the oxidation of cyclohexane to adipic acid, or the oxidation of p-xylene to terephthalic acid under spray conditions, is expected to burn cyclohexane to produce carbon dioxide under these conditions. Therefore, there is no advantage in doing this in the art. However, we are able to obtain intermediate reactions or oxidation products such as, for example, adipic acid, phthalic acid, isophthalic acid and terephthalic acid, advantageously under spray conditions, in the presence of the unexpected complex and critical adjustments and requirements of the present invention. I found out.

In particular, the following references disclose processes which are carried out in liquids which are mixed with each other with gaseous substances under mostly increased surface area conditions.

U.S. Pat.Nos. 5,399,750 (Brun et al.), 5,396,850 (Conochie et al.), 5,312,567 (Kozma et al.), 5,244,603 (Davis), 5,270,019 (Melton et al.), 5,170,727 (Nielsen), 5,123,936 (Stone et al.), 5,061,453 (Krippl et al.), 4,423,018 (Lester, Jr. et al.), 4,370,304 (Hendriks et al.), 4,361,965 (Goumondy et al.), 4,308,037 (Meissner et al.) 4,065,527 (Graber), 4,039,304 (Bechthold, etc.), 3,928,005 (Lasio), 3,677,696 (Helsinki et al.), 3,613,333 (Gardenier), 2,980,523 (Dille et al.), 2,301,240 (Baumann et al. ), 2,014,044 (Haswell) and 1,121,532 (Newberry).

Currently, oxidation reactions for the preparation of organic acids, including but not limited to adipic acid, are carried out in a liquid phase reactor while sparging the reaction gas. In this case the reaction gas is typically air but may be oxygen. Sufficient reaction gas—at a relatively high rate—with or without an unreactive diluent (eg nitrogen) is sprayed to maximize the aeration of the liquid reaction medium (typically 15-25% aeration rate). Relatively high sparging rates of reactants containing a gaseous feed (hereinafter referred to as reactant gas) associated with this conventional method have some disadvantages of ness:

Expensive reactive gas feed compressors are needed to compress the spraying reaction gases. This is expensive to install and operate (consuming a lot of electricity or steam) and has a number of practical problems resulting in excessive factory downtime.

It is very difficult to control the oxygen content in the reactor to a low concentration because of the high gas velocity required (due to the high reactor gas rotational speed).

It is very difficult to control the reaction temperature at low production rates (ie high conveying rates) for reactor systems of a given size because of the high gas velocity required. This occurs because the gas used for sparging takes energy away from the reaction system by volatilizing the reaction liquid and liquid solvent-this volatilization effect is usually very important in oxidation reactions that require and require relatively high temperatures. Unless carefully balanced by the heat of reaction released, the volatilization will act to substantially reduce the temperature of the reactor liquid. Thus, it is possible to devise a suitably sparged system for good temperature control at medium to high production rates, but at significant conveying speeds a loss of temperature and loss of temperature control will result.

High reaction gas feed rates result in relatively high reactor non-condensable off-gas ratios. Non-condensable off-gases are all released to the atmosphere, or if the oxygen content is high-some are removed and some are recycled to the reactor. The use of air as the reactant gas feed is disadvantageous because it increases the rate of release to the atmosphere-which is desirable because the effluent must first be washed with a very expensive off-gas scrubber to meet very stringent environmental requirements. Not. Using a gaseous feed of oxygen alone in the reactor results in high sparging requirements that lower the oxygen conversion rate in the reactor and lower conversion rates increase the oxygen concentration in the reactor, while higher oxygen concentrations in the reactor increase the chemical yield loss while simultaneously providing liquid reactants and liquids. It may not be desirable because it results in excessive peroxidation of the solvent (ie, their combustion with carbon monoxide and carbon dioxide). Dilution of oxygen in the reactor with recycle nitrogen or gaseous recycle inert materials increases the capital and cost of recompression and creates practical problems of recompression.

Current technology also has a relatively low gas-liquid surface area ratio to liquid reactant. Currently available technologies do not maximize this ratio. In contrast, the present invention speeds up the reaction by increasing the rate of migration of gaseous reactants (oxygen) to the liquid reaction site and maximizes the ratio to enable economical manipulation at relatively low oxygen concentrations in the gas phase.

Operation at lower oxygen concentrations with acceptable conversion rates in the reactor improves yield by reducing peroxidation reactions and eliminates safety (explosion) problems associated with operation in explosive oxygen / fuel cysts. In the current art, reducing the oxygen content below the typical level results in an uneconomical decrease in reaction rate. However, a significant increase in the above-mentioned ratios offsets this rate reduction relative to current levels, thereby enabling economical operation at reduced oxygen concentrations in the reactor.

Another problem with the current technology is that large aggregates of insoluble oxidation products are often formed in the reactor. They are formed on the reactor walls to reduce the available reaction volume, and in an oxygen deficient microreactor environment these deposits are overexposed to reaction conditions (eg high temperature) resulting in the formation of unwanted byproducts. They can also form heavy solids in the reactor that can damage expensive reactor stirrer shafts and stirrer seals, resulting in expensive repair costs and high practical wear problems. Finally, current technology often requires expensive stirring shafts and seals that can withstand chemical corrosion and can accommodate the high pressure of the system.

The use of gas phase reaction systems instead of liquid phase reactors presents a new problem, of which important is the difficulty of identifying inexpensive, efficient, non-clogging and long-lived catalyst systems. Liquid catalyst systems are well developed and well understood. Unfortunately, they are nonvolatile. When a nonvolatile catalyst is used in a gas phase reaction system, most organic acids obtained from the oxidation reaction are often nonvolatile solids unless dissolved in a liquid reaction medium, which often leads to some clogging problems.

There are a number of references dealing with the oxidation reactions of organic compounds, for example for producing acids such as adipic acid.

Among other things, US Pat. Nos. 5,321,157 (Kollar), 5,221,800 (Park et al.), And 5,463,119 (Kollar) are believed to relate to representative oxidation methods associated with the production of diacids.

Among other things, US Pat. Nos. 3,987,100 (Barnette et al.), 3,957,876 (Rapoport et al.) And 3,530,185 (Pugi) disclose oxidation processes performed in multistage and multi-plate systems.

Any of the above documents or any other document known to the inventors is subject to oxidation reactions to obtain intermediate oxidation products or other products under spraying conditions that require complex and critical control and requirements of the invention as described and claimed herein. Or do not disclose, suggest, or suggest other forms of reaction alone or in combination.

The present invention relates to a process and apparatus for producing a reaction product, in particular an intermediate oxidation product, in which a first reactant introduced into a sprayed liquid is reacted with a gas, in particular an oxidant, containing a second reactant under controlled conditions.

The following detailed description in conjunction with the accompanying drawings enhances the understanding of the present invention.

1 is a schematic diagram of a preferred embodiment of the present invention in which the temporary conversion rate prior to coalescence is controlled by varying the spray distance through the movement of the atomizer;

1A is a schematic diagram of a preferred embodiment of the present invention in which the pre-adhesion temperature and / or the temporary conversion rate before pre-adhesion is adjusted by varying the spray distance through the movement of the atomizer,

2 is a schematic diagram of another preferred embodiment of the present invention in which the temporal conversion rate before coalescence is adjusted by varying the spray temperature;

2A is a schematic diagram of another preferred embodiment of the present invention in which the pre-adhesion temperature and / or the temporary temperature difference is adjusted by varying the spray temperature;

3 is a schematic diagram of another preferred embodiment of the present invention in which the temporal conversion prior to coalescence is controlled by varying the pressure in the reaction chamber, by varying the second flow rate, or by varying the second content,

3A is a schematic diagram of another preferred embodiment of the present invention in which the temperature before the coalescence and / or the temporal temperature difference is adjusted by changing the pressure in the reaction chamber, changing the second flow rate, or changing the second content,

4 is a schematic diagram of another preferred embodiment of the present invention for adjusting the temporary conversion rate before coalescence by varying the first content,

4A is a schematic diagram of another preferred embodiment of the present invention in which the temperature before coalescence is adjusted by varying the first content,

5 is a schematic diagram of another preferred embodiment of the present invention that controls the temporal conversion prior to coalescence by varying droplet size or diameter,

5A is a schematic diagram of another preferred embodiment of the present invention in which the temperature before coalescence is adjusted by varying droplet size or diameter;

6 is a schematic diagram of another preferred embodiment of the present invention for adjusting the temporary conversion rate before coalescence by varying the first flow rate,

6A is a schematic diagram of another preferred embodiment of the present invention in which the pre-adhesion temperature and / or temporary temperature difference is adjusted by varying the first flow rate,

7 is a schematic diagram of another preferred embodiment of the present invention for adjusting the temporal conversion rate before coalescence by varying the volatilization rate,

FIG. 7A is a schematic diagram of another preferred embodiment of the present invention in which the pre-adhesion temperature and / or temporary temperature difference is adjusted by varying the volatilization rate;

FIG. 8 is a schematic diagram of another preferred embodiment of the present invention in which the temporal conversion rate before coalescence or the temperature before coalescence is controlled by changing the spray distance by moving the surface height of the second liquid,

9 is a schematic diagram of a sample collector used in the embodiment of FIG. 8;

10 is a schematic view of a filter arrangement mounted in a separator according to another preferred embodiment of the present invention,

11 illustrates the use of an exhauster to recycle non-condensable off-gas, a condenser to condense the condensable material, and condensation into a reaction chamber with thick membranes or curtains to prevent solids from forming on the septum. Is a schematic representation of another preferred embodiment of the present invention for recovering a portion of a sex material,

Figure 12 uses a pump to recycle non-condensable off-gas, a condenser to condense the condensable material, and condenses into a reaction chamber with a thick membrane or curtain to prevent solids from forming on the septum. Is a schematic representation of another preferred embodiment of the present invention for recovering a portion of a sex material,

FIG. 13 is a schematic diagram of another preferred embodiment of the present invention in which both condensable and non-condensable materials exit the reactor through the bottom end,

14 is a schematic representation of another preferred embodiment of the present invention in which a cooling membrane surrounds the reaction chamber,

15 is a schematic diagram of another preferred embodiment of the present invention in which a cooling coil performs a condensation reaction in a reaction chamber,

FIG. 16 is a schematic diagram of another preferred embodiment of the present invention in which a condensation reaction in a reactor is carried out by spraying a cooling liquid while spraying a first liquid,

FIG. 17 is a schematic diagram of another preferred embodiment of the present invention in which the condensation reaction in the reactor is carried out by spraying cooling liquid toward the septum of the reaction chamber, FIG.

18 is a schematic diagram of a reaction chamber having a thermocouple for measuring a temporary temperature difference,

FIG. 19 is a schematic diagram of another preferred embodiment of the present invention for controlling the rate of oxidation of a reaction in a reaction chamber by adjusting the temperature and / or conversion of the first reactants to intermediate oxidation products at different locations in the system.

As mentioned above, the present invention relates to a method and apparatus for preparing intermediate oxidation products, wherein a first reactant introduced into a sprayed liquid is reacted with a gas containing an oxidant under controlled conditions. More specifically, the present invention

(A) spraying a first liquid at a spray temperature and a spray distance from the second liquid mass to form a plurality of gaseous droplets,

(B) causing a substantially non-degradable oxidation reaction between the first reactant and the oxidant at an oxidation pressure to form an intermediate oxidation product, (b)

Adhering the droplet to the second liquid mass (c) and

Before the droplets coalesce into the second liquid, each of the parameters or determinants selected from the group consisting of pre- coalescence temperature of the droplets, temporal temperature difference of the droplets, temporal fine temperature difference of the droplets, temporal conversion before coalescence, and combinations thereof And a method for producing an intermediate oxidation product from a first liquid containing a first reactant and a gas containing an oxidant, comprising adjusting to within a predetermined range of.

The intermediate oxidation product can then be separated from the second liquid.

The temperature before coalescence is the temperature of the droplet just before it is coalesced into the second liquid.

The temporary temperature difference is the difference in droplet temperature between the pre-adhesion temperature and the spray temperature. The spray temperature is the temperature of the first liquid in the nebulizer just before the first liquid is sprayed.

The spray distance is the distance between the nebulizer and the second liquid mass.

According to the invention, the temporary fine temperature difference is the difference in the droplet temperature between the point on the spray position side and the point on the second liquid position side in the passage through which the droplet flows. Temporary fine temperature differences are useful because they provide information about the temperature profile in the reaction chamber and additional data about the reaction progress. Their use is within the scope of the present invention. In addition, according to the invention, the temporary fine temperature difference between the point close to the atomizer and the point close to the second liquid can be used instead of the temporary temperature difference as defined above.

The transient conversion rate before coalescence is the conversion rate that occurs from the point where the first liquid is sprayed to form the first droplet, as described herein, to the point just before the first droplet coalesces into the liquid mass. This occurs in only one cycle of droplet formation and droplet coalescence. The term conversion refers to the conversion of reactants into reaction products. Thus, at any point during the reaction, the conversion rate is the ratio of the number of moles of reaction product formed during the reaction to the total number of moles of reactants in the feedstock, theoretically determined when one mole of reactant is completely converted to the reaction product. It means the value multiplied by the inverse of the number of moles of the product.

The temperature before the coalescence of the droplets, the temporal temperature difference of the droplets, the temporary fine temperature difference of the droplets, and the temporal conversion before the coalescence are called determinants because they determine the parameters relating to the control of the oxidation reaction. Thus, the oxidation reaction is carried out in such a way that one or more of the following occur by different variables, as described in detail below: The pre-sink temperature reaches a value within the pre-splung temperature range and the temporal temperature difference is predetermined. A value within the range of the temporary temperature difference is reached, the temporary fine temperature difference reaches a value within the range of the predetermined temporary fine temperature difference, and the conversion rate reaches a value within the temporary conversion rate range before the predetermined coalescence.

Techniques well known in the art, including measurements and calculations, should be calibrated for different factors that may affect the temporal temperature difference in any way. Since the change in temporal temperature difference can be more important than its absolute value, in most cases high accuracy is not required for measurements and calculations. Similar corrections and techniques can be used for the remaining determinants.

It is desirable to prioritize determinants outside each predetermined range and further beyond each most desirable set point and prevail this. This means that computerized regulators, such as those described in the embodiments below, assign lower priority to data from other determinants and treat the received data first with respect to the predominant determinant. After bringing the predominant determinant closer to its respective most desirable set point than the other determinants, the other determinant is prioritized or predominantly. In this way, after all the determinants have a value within their respective predetermined range, the determinants are further prioritized or predominantly deviated from each most desirable setpoint until all determinants have reached their most desirable setpoint. . At this point, no variables change until one determinant is displaced (in this point the order described above is restarted), thus keeping all determinants as close as possible to their respective desired setpoints. This sequence continues for the purpose of keeping all the determinants always within their respective predetermined ranges and ensuring that each determinant is always the most desirable set point. When it is necessary to select a determinant to give priority to another determinant, whether or not the same or different units are divided, each predetermined range is divided into 100 arbitrary units arbitrarily assumed to be equal in both cases, and all values Are prorated in these equally arbitrary units (both within and outside each range).

It is important to note that according to the invention, suitable reversal program rules can be used to reverse the sequence, particularly in the case of safety concerns. For example, if the pre-adhesion temperature or the temporary temperature difference or any temporary fine temperature difference starts to rise at a faster rate than the preset value, regardless of the priority as described above, the corresponding determinant is taken and At least one variable should be appropriately changed at a rate high enough to stop the rise in time before it occurs.

In addition, observing carbon monoxide and carbon dioxide in the off-gas also requires careful attention, since more than unexpected or normal amounts of carbon monoxide and / or carbon dioxide indicate poor or no control. Similar reversal rules applied by the regulators described below help to prevent poor yields, poor conversion rates and even explosions.

The adjustment of parameters or determinants can include changing the predetermined amount of catalyst in the droplets, changing the spraying temperature of the droplets, changing the reaction pressure in the reaction chamber, changing the spraying distance, changing the average droplet particle size, the first flow rate Change in velocity), change in second flow rate (rate at which gas flows), change in rate of volatilization of volatile components in the first liquid, change in first content (content of first reactant in the first liquid) It can be carried out by a step selected from the group consisting of a change in the second content (content of the oxidant in the gas) and combinations thereof.

Temporary conversion before coalescence can be observed by chromatography.

Preferably, the major part of the oxidation product is an organic compound, the first reactant comprises an organic compound, the oxidant is oxygen, and more preferably, the first reactant is cyclohexane, cyclohexanone, cyclohexylhydroperoxide, Cyclohexanol, o-xylene, m-xylene, p-xylene, a mixture of at least two cyclohexanes, cyclohexanone, cyclohexanol and cyclohexylhydroperoxide, at least two o-xylenes, p-xylene And a mixture selected from the group consisting of m-xylene, the oxidizing agent comprising oxygen, the main part of the intermediate oxidation product being adipic acid, cyclohexanol, cyclohexanone, cyclohexylhydroperoxide, phthalic acid , Isophthalic acid, terephthalic acid, at least two adipic acids, cyclohexanone, cyclohexanol and cyclohexylhydroper Comprises a compound selected from the group consisting of a mixture of the side, a mixture of phthalic acid, isophthalic acid and terephthalic acid of at least two species.

If the intermediate oxidation product is a solid, the method may comprise separating the intermediate oxidation product from the second liquid by filtration.

The spraying method is a preferred method for spraying the first liquid onto the surface of the second liquid at a spraying distance from one point, preferably by airless techniques.

The method of the present invention may further comprise the step of internally condensing the condensable material, preferably substantially under reaction pressure. In addition, the non-degradation oxidation process can be carried out in a reaction zone surrounded by a thick film or curtain of liquid.

Preferred temporal conversion ranges from pre-adhesion to 0.05% to 80%, pre-deposition temperature ranges from 50 to 250 ° C, and temporal temperature differences range from 0.1 to 100 ° C.

The invention also includes a reaction chamber having a top end, a bottom end, a partition, and a reaction zone in which the first liquid contacts the gas to react under the reaction pressure,

(a) an atomizer disposed in a reaction chamber, adapted to spray a first liquid into a gas at a spray temperature to form a plurality of droplets in such a manner as to cause droplets to coalesce onto a second liquid mass containing the reaction product (the The droplets have a temperature before coalescence before coalescence, the second liquid mass has a second liquid surface, and the atomizer is sprayed away from the second liquid surface),

(b) a first temperature monitor for measuring spray temperature, a second temperature monitor for measuring pre- coalescence temperature and / or a temporary temperature difference and / or any temporary fine temperature difference, before the droplets coalesce on the second liquid mass; A monitor selected from the group consisting of: a conversion rate detector for monitoring the temporary conversion rate before coalescence, in which the first reactant in the droplet is converted to the reaction product, and combinations thereof, and

(c) connected to at least one of the first temperature monitor, the second temperature monitor, and the conversion rate detector to obtain respective information and obtain the respective information, the temperature of the droplet prior to coalescence, the temporary temperature difference of the droplet, the temporary temperature difference of the droplet, the temporary conversion rate before coalescence, and Reaction from a gas comprising a first liquid and a second reactant containing a first reactant, characterized in that it comprises a regulator for adjusting a parameter or determinant selected from the group consisting of a combination within each predetermined range A device for producing the product.

The apparatus may further comprise a separator in communication with the reaction chamber for separating the reaction product from the second liquid, and / or a recycling branch for recycling at least a portion of the second liquid into the first liquid.

The conversion detector preferably comprises a chromatography device.

The atomizer is preferably disposed towards the upper end and located towards the bottom end at the spray distance. It is preferably airless.

As mentioned above, the present invention relates to a process for the preparation of intermediate oxidation products in which a first reactant introduced into a sprayed liquid is reacted with a gas containing an oxidant under controlled conditions. According to the present invention, spraying conditions require complex and critical adjustments and requirements as described and claimed below.

The present invention enables economical oxidation reactions with improved yields, reduced compression costs and capital, uses a proven catalyst system, reduces the release of off-gas waste streams to the atmosphere, and provides for off-gas cleaning. Capital and cost are reduced, there is no problem of solid clogging or solid formation, high practicality, high conversion rate, and reduced oxygen concentration in the reaction chamber.

The ability to operate at lower oxygen concentrations with acceptable conversion in the reactor, which can be achieved by the present invention, improves yield by reducing peroxidation reactions and explosive oxygen / fuel bladder by operating in non-explosive oxygen / fuel bladder Eliminate safety (explosion) problems associated with operation inside

As will be evident in the course of this discussion, unlike conventional techniques of spraying oxidizing gas onto a mechanically stirred liquid containing the reactants to be oxidized, there are no reaction chamber stirrers and stirrer seals. The simplification of this process is made possible by the unique reaction environment provided by the present invention, which is highly desirable because it costs less and less capital and improves the efficiency of the plant compared to conventional techniques.

Since the oxidation is carried out in the droplets present in the liquid phase according to the invention, this method has the advantage of using an efficient liquid-soluble catalyst system, which achieves efficient reaction conditions almost identical to the reaction conditions in a uniform gas phase. Has the added advantage. Reactions in the gas phase require expensive, uncertain gas phase catalysts or solid catalyst systems.

In addition, the present invention can reduce the proportion of off-gas waste stream as needed, thereby reducing the proportion of off-gas waste stream discharged to the surrounding environment, and reduce off-gas cleaning capital and cost. Low off-gas wastestream ratios can be achieved, for example, using near stoichiometric gaseous oxygen feeds with high conversion rates and / or chemical yields.

In conventional techniques, the reaction chamber non-condensable off-gas is released to the atmosphere without being partially recycled to the reaction chamber. This leads to an increase in oxygen consumption and associated costs, but this is done to avoid expensive and uneconomical recompression costs and capital costs. In the conventional art, the recompression cost and capital are high because the load of the non-condensable material is high and a high recirculation pressure is required.

According to the method and apparatus of the present invention, when performing condensation in a step prior to pressure reduction (internal condensation), for example, as shown in the embodiment of FIG. 11 (prior to valve 864), oxygen associated with conventional techniques is known. Increasing consumption and related costs and uneconomical recompression costs and capital increases can be avoided. According to this embodiment, the oxygen-containing off-gas can be recycled back to the reaction chamber with relatively little or no recompression requirements and costs. Recirculation may be omitted without causing significant economic adverse effects. When condensation is carried out in this step, the proportion of non-condensable off-gas is low (particularly when using a nearly stoichiometric oxygen feed), thereby minimizing the recompression requirements compared to conventional techniques. The low proportion of non-condensable off-gas is due to combining one or more of the high oxygen conversion rates, high chemical yields and internal condensation provided by the present invention with near stoichiometric oxygen feeds.

As illustrated below, it should be emphasized that internal condensation can occur outside or inside the reaction chamber. Internal condensation is condensation that occurs inside the system before the pressure is reduced. External condensation is condensation that occurs outside the system after the pressure has been reduced. Inner or inner inner condensation is condensation that occurs inside the reaction chamber. Outer condensation or inner outer condensation is condensation that occurs inside the system and outside the reaction chamber before the pressure is reduced.

According to the present invention, where an almost stoichiometric oxygen feed is desired, this can be achieved by a high conversion rate of the oxygen feed fed to the reaction chamber per number of passes of the unit, thus requiring little recycling requirements. High chemical yields significantly reduce the off-gas discharge load generated in the reaction chamber because of less formation of non-condensable by-products. The reduced off-gas discharge load in turn reduces the amount of oxygen released from the reaction chamber. Reduced oxygen release from the reaction chamber minimizes oxygen recycle requirements. Since internal condensation outside the reactor reduces the condensable vapor recirculation requirements, performing internal condensation further reduces recompression requirements, while performing internal condensation inside the reactor further reduces oxygen recirculation requirements. Thus, internal condensation, especially internal condensation inside the reactor, significantly reduces the oxygen physical yield loss. To some extent, internal condensation, complete oxygen conversion per unit pass, ie stoichiometric oxygen feed, and non-condensation of non-condensable by-products cause little physical yield loss of oxygen and require little recycling requirements. . Since the non-condensable off-gas ratio can be lowered when performing internal condensation, the costs for recycling are much less than with conventional techniques.

In the present invention, solids are not formed in the reaction chamber because the partition walls of the reaction chamber are preferably washed with a coolant, a liquid solvent containing no catalyst or a liquid reactant containing no catalyst or a mixture thereof. All surfaces of the reaction chamber or certain parts of such surfaces which are liable to form solids can be cleaned in this manner. The wash liquor can be sprayed onto the surface thus washed or produced in situ as a result of internal condensation therein. Solids in contact with the surface are subsequently washed out of the reaction chamber, thereby preventing solid formation. In addition, the reaction in the wash liquid is minimized by lowering the temperature further, using no catalyst, shortening the residence time or combining them. All solids produced in the reaction chamber are removed from the reaction chamber using a wash solution.

According to the present invention, the diffusion rate can be greatly improved by using an extremely high ratio of the gas / liquid interface to the liquid reaction volume, which is obtained by converting the bulk stirred liquid phase into a controlled, controlled droplet size in a continuous gas phase. Can be.

Significantly reducing the oxygen concentration in the gas phase while maintaining the desired high reaction rate by the present invention increases yield by reducing peroxidation reaction, increases safety by operating further away from oxygen / fuel explosive air sacs, and reaction chambers. It is highly desirable because it serves to minimize the amount of oxygen removed from the.

Methods of controlling the average droplet diameter during spraying are well known in the art, and examples include, but are not limited to, nozzle design, various nozzle characteristics, pressure of sprayed material, gas when using a gas in the spraying process. Pressure and the like.

According to the present invention, the temperature before coalescence and / or the temporary temperature difference and / or the temporal conversion before coalescence can be adjusted, for example, by adjusting the oxygen concentration in the reaction chamber. This can be done by using oxygen as a limiting reagent. In this case, it is possible to increase or decrease the rate of oxygen supply to the reaction chamber as necessary in order to control the temperature before the coalescence and / or the temporary temperature difference and / or the temporal conversion before the coalescence. By increasing the oxygen supply rate to increase the oxygen concentration in the reaction chamber-while maintaining all other variables-increasing the pre-adhesion temperature and / or the temporal temperature difference and / or the temporal conversion before pre-adhesion. By reducing the oxygen supply rate to reduce the oxygen concentration in the reaction chamber—while all other variables remain constant—to reduce pre-adhesion temperature and / or temporal temperature difference and / or transient conversion before pre-adhesion.

In addition, by increasing the concentration of catalyst in the liquid feed supplied to the reaction chamber-while maintaining all other variables-increasing the temperature before the coalescence and / or the temporal temperature difference and / or the temporal conversion before coalescence. By reducing the concentration of the catalyst in the liquid feed fed to the reaction chamber—while all other variables remain constant—reduce the temperature before the coalescence and / or the temporal temperature difference and / or the temporary conversion before coalescence.

In addition, by increasing the residence time of the liquid feed in the reaction chamber-while maintaining all other variables-increasing the pre-adhesion temperature and / or the temporal temperature difference and / or the temporal conversion prior to coalescence. By reducing the residence time of the liquid feed in the reaction chamber—while all other variables remain constant—the temperature before and after the coalescence and / or the temporal conversion before the coalescence are reduced. The residence time of the liquid feed in the reaction chamber is controlled by changing the height of the gas phase through the drop down. Increasing the height increases the residence time and decreasing the height reduces the residence time. The height can be adjusted in several ways. For example,

Increase or decrease the height of the droplet ejection nozzles or nozzles;

Can be adjusted by increasing or decreasing the height of the liquid sump at the liquid height at the end of the vertical reaction chamber. The height of the liquid pond can be measured and adjusted by various methods well known in the art.

In addition, by reducing the size of the droplets in the reaction chamber-while maintaining all other variables-increasing the temperature before the coalescence and / or the temporary temperature difference and / or the temporal conversion before coalescence. By increasing the size of the droplets in the reaction chamber—while all other variables remain constant—reduce the temperature before the coalescence and / or the temporal temperature difference and / or the temporal conversion before coalescence. Droplet size adversely affects pre- coalescence temperature and / or temporal temperature difference and / or temporal conversion before coalescence by controlling the migration of oxygen masses to the liquid reaction medium. Since the ratio of surface area to volume in spherical droplets is inversely proportional to the diameter of the droplet, and the oxygen movement from the gas phase is directly proportional to the surface area of the droplet, the ratio of oxygen mass movement to the volume of liquid contained within the droplet is equal to the diameter of the droplet. Reverses. Thus, the relative oxygen mass shift for larger droplets is smaller than the relative oxygen mass shift for smaller droplets, and the pre-adhesion temperature and / or temporal temperature difference and / or the temporal conversion rate prior to coalescence when all other variables remain constant. Decreases correspondingly.

Since the reaction rate is faster at higher temperatures, in the present invention, by increasing the pre-adhesion temperature and / or the temporal temperature difference of the droplets-while keeping all other variables constant-they increase the temporal conversion prior to coalescence. By reducing the pre-adhesion temperature and / or the temporal temperature difference of the droplets in the reaction chamber—while all other variables remain constant—the conversion is reduced.

According to the present invention, the heat of reaction can be removed from the liquid reaction mass as evaporated liquid reactant and evaporated liquid solvent. These evaporated materials can be condensed outside or inside the reaction chamber as discussed below. Removing heat inside the reaction chamber can be done, for example, by using a condensation spray or condensation surface or a combination thereof.

According to the present invention, the regulator makes the pre-adhesion temperature of the droplets, the temporary temperature difference of the droplets, the temporary fine temperature difference of the droplets, the temporary conversion rate before the coalescence, and combinations thereof within a predetermined range. This means that a regulator is applied to change one or more variables, such as the preferred ones listed here by way of example, such that the pre-adhesion temperature, the temporal temperature difference, the temporal conversion before pre-adhesion, or a combination thereof, are each within a predetermined range.

The temperature prior to coalescence and the tempera- ture temperature difference depend on the particular oxidation reaction. As an example, in the case of the oxidation reaction of cyclohexane to adipic acid, the preferred range of the temperature before coalescence is 50 to 150 ° C, more preferably 80 to 130 ° C, most preferably 90 to 120 ° C. Preferred temporary temperature differences range from 0.1 to 100 ° C, more preferably 5 to 100 ° C, particularly preferably 10 to 50 ° C, most preferably 15 to 35 ° C. In preparing phthalic acid, isophthalic acid and terephthalic acid from o-xylene, m-xylene and m-xylene, respectively, the preferred pre-adhesion temperature ranges from 50 to 250 ° C. Suitable ranges of pre-sorption temperature, temporal temperature difference, and preliminary pre-sorption temporal conversion can be determined without undergoing other oxidation reactions or inadequate experimentation with various conditions of the same oxidation reaction.

Preferred temporal conversion prior to predetermined coalescence is between 0.05% and 80%.

Depending on the reaction characteristics, several variables can be somewhat effective and efficient in changing the pre-adhesion temperature or the temporal temperature difference or the temporary conversion before pre-adhesion or a combination thereof. In some cases, changing one variable may not bring the pre-adhesion temperature or tempera- ture temperature difference, or the temporary conversion rate before pre-adhesion, or a combination thereof to fall within a predetermined range. In such cases, it is desirable to apply or program the regulator to select and change one or more additional variables to achieve the desired result.

In the description of the preferred embodiment of the present invention, for the sake of clarity, it is assumed that the particular variable under consideration can be, alone, such that the temperature before the coalescence or the temporal temperature difference or the temporary conversion before the coalescence or a combination thereof is within a predetermined range. This is generally true as long as the controller (s) are selected to select the most efficient variable (s) for the particular reactions performed by the apparatus and methods of the present invention. However, it should be understood that selecting one or more additional variables is also within the scope of the present invention.

The temperature can be observed by any temperature measuring device such as, for example, thermocouples, IR thermometers and the like.

According to the invention, it is important to note that suitable reversal program rules can be used to revers the normal program of the regulator, especially in the case of safety concerns. For example, the temperature in the reaction chamber is preferably observed, and if the temperature begins to rise at a faster rate than a preset value, the regulator may be at a rate high enough to stop the rise in time before catastrophic events occur. You should change one or more variables as appropriate.

In addition, observing carbon monoxide and carbon dioxide in the off-gas also requires careful attention, since more than unexpected or normal amounts of carbon monoxide and / or carbon dioxide indicate poor or no control. Similar reversal rules applied by the regulator help to prevent poor yields, poor conversions and even explosions.

In the following description, the droplets have an average droplet diameter and they are produced at a predetermined first flow rate, the gas flows at a first flow rate, the droplets may contain volatile components that volatilize at a volatilization rate, and the first liquid Contains a first reactant in a first content and the gas contains an oxidant in a second content. The ratio of oxidant to inert gas or other gas determines the amount of oxidant in the gas.

In addition, in the following description, the temporary conversion before coalescence is the conversion when the first reactant is converted to an intermediate oxidation product as droplets of the first liquid move from the atomizer to the sample collector. It should be understood that information regarding the amount of the first reactant and the oxidation product, if present, is observed in the first liquid and that they are fed to the computerized regulator through a conversion monitor with information on the mole percent of intermediate oxidation product in the sample collector. . All this information is collectively referred to as temporary conversion rate information prior to coalescence. Analysis and / or computer manipulations from different lines were performed by techniques well known in the art and these were excluded from the figures for clarity. More specifically, the temporal conversion before coalescence is defined by the ratio [(O ² -O ¹ ) x 100] / [R ¹ xn]. here,

O ¹ is the mole percent of intermediate oxidation product in the first liquid,

O ² is the mole percent of intermediate oxidation product provided to the conversion monitor by the sample collector,

R ¹ is mole% of the first reactant in the first liquid,

n is the number of moles of intermediate oxidation product produced when one mole of the first reactant is completely converted to the intermediate oxidation product.

The inventors recognize that in the case of spray reactors, not only the overall temperature or conversion of the overall process, which has been used in the art so far, but also the coalescing temperature, temporal temperature difference, and the temporal conversion before coalescence are essential for controlling the oxidation reaction. Was done. Adjusting the pre-adhesion temperature or the tempera- ture temperature difference, or both, with or without the temporary conversion rate before coalescence not only helps to improve yield, but also to avoid reactions that cause complete oxidation, combustion, or even explosions. .

In one embodiment of the present invention shown in FIG. 1, an apparatus 10 for producing an intermediate oxidation product from a gas containing a first liquid and a second reactant containing a first reactant is shown. Apparatus 10 includes a reaction chamber 12 having an upper end 14, a bottom end 16, and a reaction zone 18. The reaction chamber 12 also has a partition having an inner surface 21. The chamber 12 preferably has a cylindrical shape which is conical near the bottom end 16 and finally to the liquid outlet 22 connected to the outlet line 24. The outlet line 24 separates the intermediate oxidation product from the reactants along the line and recycles the unreacted reactant through line 11, usually containing various amounts of intermediate oxidation product, solvents, catalysts and other adducts. 19 to the separator 15 for conveying. The separator may be a simple device such as a filter or a complex device such as a set of tanks, washers, extruders, distillation columns and the like, to suit each particular case. A side line line 50, which is connected to the system via side tube valve 52, is used to bypass separator 15 as needed.

Near the upper end 14 of the reaction chamber 12 is provided a gas outlet 23 leading to the gas outlet line 25.

In addition, a liquid dispersion ring 44 is provided on the partition wall 20 of the reaction chamber 12. The liquid dispersion ring 44 is preferably connected to a line 11 'providing a liquid to be recovered. The ring 44 is adapted to distribute the liquid substantially evenly on the inner surface 21 of the partition wall 20 in the form of a thick film or curtain 45.

The reaction chamber 12 is preferably adapted to withstand the reaction conditions within the reaction chamber 12 and to withstand temperatures and pressures suitable for the reactants and reaction products. Such materials and structural properties are well known in the art. For example, depending on the particular reaction, carbon steel, stainless steel, or Hast alloy may be required. In addition, the inner surface 21 may be protected by coating or lining of glass or other material.

In the reaction chamber 12, preferably near the upper end 14, an atomizer 26 is preferably arranged comprising a plurality of nozzles 27. The atomizer 26 is preferably airless (no spraying gas is required in operation). Airless atomizers are well known in the art. The nebulizer 26 may be fixed at a specific location in the reaction chamber 12 or may preferably be moved up and down. The drive device 28 supporting the atomizer 26 is preferably connected to the reaction chamber 12 at the upper end 14. The drive device 28 may be a hydraulic or pneumatic cylinder, or may have mechanical properties such as, for example, in the form of a screw. It is important that the drive device 28 is applied to move the atomizer 26 up and down in a preferably adjustable manner without making holes in the reaction chamber 12.

A gas outlet 34, preferably located near the bottom end 16 of the reaction chamber 12, is connected to a gas feed inlet line 36 that provides a gas containing a second reactant.

Near the bottom end 16 of the reaction chamber 12 collect droplets and transfer them through the sample line 33, preferably as a fine stream of liquid (the term detector according to the invention includes the meaning of the monitor). And a sample collector 30 for conveying the same. The conversion detector 32 can also observe the amount of the first reactant and the intermediate oxidation product in the recycle tank 19 via the sample line 17. This information can, for example, accurately measure the amount of first reactant and intermediate oxidation product delivered to atomizer 26, along with information about the nature and quality of the material supplied in line 41.

Heat exchanger 38 is applied to provide the recycled reaction mixture from recycle tank 19 to refill reservoir 40 via inlet line 39. Replenishment reservoir 40 is also provided via inlet line 41 with freshly prepared reactants, catalysts, solvents and other additives required for the reaction in each particular case. Replenishment reservoir 40 provides a temperature regulator (not shown) and a high pressure, which provide the mixture prepared in reservoir 40 to nozzle 27 of atomizer 26 via line 42 at the desired spray temperature. It may be a container including a pump (not shown). Line 42 can be bent and preferably has a coiled portion 43 to follow any movement of atomizer 26.

The device 10 also preferably comprises a computerized regulator 35 which supplies information about the transient conversion rate of the reactants prior to coalescence of the reactants to the intermediate oxidation product via the input line 31 from the conversion rate detector 32. This controls the heat exchanger 38 via the output line 27, the drive device 28 via the output line 29, and the replenishment reservoir 40 via the output line 37.

Monitor or detector 32 may be any device that can be used to detect intermediate oxidation products or products. This may include, for example, chromatography devices, UV spectrometers, IR spectrometers, visible light spectrometers, mass spectrometers, NMR devices, conductivity monitors, ionization detectors, flame detectors, any other suitable device, or combinations thereof. .

If the intermediate oxidation product is a nonvolatile acid, the monitor or detector 32 preferably comprises HPLC (high pressure / performance liquid chromatography apparatus) with a UV monitor. In addition, the HPLC apparatus has one or more columns, and when the separation time in the column is longer than the predetermined time, a predetermined range of intervals for introducing a series of samples into different columns and performing a plurality of separations to observe the series of samples is determined. Is preferred. If the non-polar organic portion is to be analyzed, it is preferable to include a gas chromatography monitor or detector combined with a suitable monitor such as, for example, an ionization monitor.

The method and apparatus of the present invention are particularly suitable for the oxidation reaction of organic compounds in which the main part of the oxidation product is CO, CO ₂ or a mixture thereof and other oxidation intermediates. One of the reasons is that the complex and critical requirements of the present invention significantly improve the reaction rate, reaction uniformity, yield and other important properties, while the absence of such critical requirements will result in complete oxidation to CO / CO ₂ . Because it is. Indeed, the same spraying conditions that do not have this critical requirement have recently been used to substantially oxidize organic compounds, such as gasoline, to a mixture of CO / CO ₂ in combustion engines and other devices of automobiles.

On the other hand, according to the invention, for example, when the first reactant is cyclohexane, most of the oxidation products are substantially cyclohexanol, cyclohexanone, cyclohexylhydroperoxide, caprolactone, adipic acid and the like and these It may be a mixture of. Organic acids are preferred oxidation products.

Operation of the above embodiments and other embodiments of the present invention will be discussed with respect to any non-degradable oxidation reactions covered by the claims, which include cyclohexane as the first reactant, oxygen as the oxidant in the gas, intermediate oxidation It will be exemplified using adipic acid as the product. As mentioned above, the term intermediate oxidation product means stopping the oxidation reaction before the first reactant is substantially oxidized to carbon monoxide, carbon dioxide or mixtures thereof.

In operation of this embodiment, the first liquid containing the first reactant (eg, cyclohexane) is sprayed by atomizer 26 and nozzle 27 to form a plurality of droplets 48 in a line ( 42 is introduced into the reaction chamber 12. The first liquid enters the nebulizer at a predetermined spray temperature (preferably in the range of 50-150 ° C., more preferably 80-130 ° C., most preferably 90-120 ° C. for cyclohexane). The spray temperature of the first liquid is the temperature just before the liquid is atomized. The temperature of the freshly formed droplets may be the same or different than the spraying temperature. In the case of cyclohexane, the first liquid is preferably a solvent (e.g. acetic acid), a catalyst (e.g. cobalt compound) dissolved in the first liquid, an initiator (e.g. cyclohexanone, methylethylketone, acetaldehyde, etc.) and Mixtures thereof). In the case of oxidizing cyclohexane to adipic acid, the pressure should preferably be high enough to keep the cyclohexane, solvent, initiator and the like substantially in the liquid state. Even pressures in excess of 1,000 psia may be used, but the pressure is preferably in the range of 100 to 400 psia, more preferably 150 to 300 psia.

The atomizer 26 is driven by the drive device 28 to the bottom end 16 of the reaction chamber 12 through the liquid outlet 22 at a low position initially near the bottom end 16 of the reaction chamber 12. It is preferably located spaced apart from the second liquid mass 54 having the second surface 56 which is collected and discharged. The second liquid is a mixture of coalesced droplets 48 and a liquid that forms a thick film or curtain 45. The distance between the nozzle of the atomizer closest to the surface 56 of the lump 54 and the surface 56 of the second liquid lump 54 is defined as the spray distance. When the second liquid 54 has been completely removed from the reaction chamber 12, the distance between this point and the nozzle of the atomizer closest to where the liquid outlet 22 meets the reaction chamber is defined as the spray distance. The spray distance at the start of the operation is preferably about 1/3 to 1/4 of the maximum spray distance. The maximum spray distance is the spray distance when the atomizer is as far from the surface 56 of the second liquid mass 54 as the design of the apparatus 10 and atomizer 26 allows. The atomizer in FIG. 1 has a maximum spray distance.

At the same time that the first liquid is sprayed, a gas containing an oxidant (preferably oxygen in the case of cyclohexane) is passed through the gas inlet supply line 36 near the bottom end 16 of the chamber 12. Flows into). The gas may contain, in addition to the oxidant, a somewhat inert gas such as, for example, nitrogen and / or carbon dioxide. Off gas mixed with vapors of reactants, solvents, mists, etc., is withdrawn from the reaction chamber via gas outlet line 25 and treated as illustrated below.

As the droplets drop downward from atomizer 26 they begin to react with oxidants (eg oxygen). The second liquid 54 is preferably continuously removed through the liquid outlet 22 and pumped to the separator 15 through the liquid outlet line 24 (pump not shown) and the intermediate oxidation product ( Example: adipic acid) is separated from the liquid by techniques well known in the art. In some cases, other oxidation by-products may also be removed from the separator as needed. Reactants, solvents, catalysts and the like are returned to recycle tank 19 via line 11.

After the product and / or byproduct removal treatment, a portion of the second liquid can be conveyed through the line 11 'to the liquid dispersion ring 44 as needed, where it is in the form of a thick film or liquid curtain 45 Is dispersed to cover the inner surface 21 of the partition wall 20 of the reaction chamber 12. When dispersed from the dispersing ring 44, the temperature of this film is adjusted to be lower than the spray temperature. In the case of the conversion of cyclohexane to adipic acid, for example, this is preferably in the range from 20 ° C. to 80 ° C., more preferably from 20 ° C. to 40 ° C. At such low temperatures, no appreciable reaction occurs at all, and droplets adhering to the membrane do not significantly affect the process. Any solid product that does not dissolve in the droplets is washed down by the liquid curtain 45, which, as already mentioned, forms a second liquid 54 together with the coalesced droplets 48. Therefore, no solid adheres to the inner surface 21 of the partition wall 20. The non-recirculated liquid, which may be a solvent, with or without a catalyst or other adduct, or other liquid or combination thereof, replaces or supplements the recycled liquid coming from line 11 '. It should be noted that it can be done. If desired, the second liquid delivered to line 24 may bypass separator 15 partially or wholly through side pipe valve 52 and side pipe line 50. This option can be used when the temporary conversion rate before coalescence is smaller than the desired temporary conversion rate before coalescence, especially at the start of operation.

The height or surface 56 of the second liquid 54 does not move above the point where the sample collector 30 is located to prevent the sample collector 30 from overflowing with the second liquid 54 and failing to sample. Adjust Observation of liquid height is well known in the art and can be performed using any suitable type of liquid height monitor available on the market. The liquid level monitor is a liquid entering the reaction chamber 12 as a curtain 45 through the line 11 ', a liquid entering the droplets through the atomizer 26, or a liquid outlet line in the reaction chamber 12 ( By adjusting the supply amount of the liquid discharged as the second liquid 54 through the 24 or any combination thereof, the height or surface 56 of the second liquid mass 54 is below the desired range below the sample collector 30. Disposed to keep it in. This arrangement is very simple and is not shown in FIG. 1 for clarity. A high supply of liquid through line 11 'and a nebulizer will make the height of surface 56 high, while a low supply will have the opposite effect. Likewise, a faster discharge rate through line 24 will lower the height of surface 56, while a slower discharge rate will have the opposite effect.

A portion of the droplet 48 drops into the sample collector 30 directly above the surface 56 of the second liquid mass 54, from which they can turn the conversion rate detector or monitor 32 to be analyzed for temporary conversion prior to coalescence. Is carried toward. If solids are present in the droplets, care must be taken not to block the liquid delivery line by using a suitable diluent or the like. As mentioned above, in the case of adipic acid or other acid formation, the monitor 32 preferably comprises a chromatography device, more preferably a high performance (or high pressure) liquid chromatography device (HPLC). The apparatus also preferably has a suitable number of columns, as mentioned above, to allow multiple redundant measurements of intermediate oxidation products present in the droplets just before the droplets coalesce in the second liquid mass 54. 1 The transient conversion of the reactants prior to coalescence into the intermediate reaction product should be checked as often as desired in each particular case. For example, if the column separates the intermediate oxide product within 8 minutes, and in certain cases the desired measurement interval is 2 minutes, four columns are required.

It may be desirable to collect the liquid in the recirculation tank 19 or at one point just before the liquid is atomized, which is via line 17 or another line (not shown) to the same detector 32. Or another detector (not shown).

The information obtained from the conversion rate detector or monitor 32 is supplied to the computerized regulator 35 via input line 31, where this information is processed by methods well known in the art. The regulator 35 is, via its output line 46, a temperature in the replenishment reservoir 40 with the temperature of the liquid provided via line 41, which temperature is substantially the same as the spray temperature for all practical purposes. Adjust heat exchanger 38 to determine. The regulator 35 regulates the feed rate of the first liquid through line 42 through its output line 37. The regulator 35 also regulates the drive device 28 through its output line 29.

When the temporary conversion rate before coalescence exceeds the range called the temporal conversion rate range before coalescence according to the present invention because the droplet indicates the temporary conversion rate just before coalescence to the second liquid 54, the drive device 28 It is instructed by the regulator 35 to lower the height of the atomizer in such a way as to reduce the spray distance as defined above. The change in spray distance is preferably at a specific time, preferably in spray distance increments in the range of 10 to 50%, more preferably in the range of 10 to 30%. However, other ranges may be more suitable, depending on the particular conditions, materials, previous measurements, and the like. For example, if a decrease of 10% in spray distance is found to have no appreciable result, the following increment may be for example 30%. On the other hand, if a 10% reduction in spraying distance causes an excessive change in the temporary conversion rate before coalescence, the next increment may be, for example, 5% until the conversion rate is within the desired range, preferably the most desirable range. Can be. However, it should be noted that again the preferred range may vary depending on materials, conditions and the like. The distance between the sample collector 30 and the height 56 or surface 56 of the second liquid mass 54 is preferably a maximum spray distance in the range of 5-10%.

After the transient conversion before coalescence is found to be within the most preferred range, in most cases it is continuously observed to be located near the median of the most preferred range. Continuous observation and control are highly desirable because the conditions in the reaction chamber can change to change the temporal conversion before coalescence.

Preferred temporal conversion prior to predetermined coalescence is between 0.05% and 80%.

If the reaction is very slow or desired for some reason, partial or total recirculation (not shown) directly through line 42 to line 24, with or without additional feed from line 42 from the replenishment reservoir. Not used).

The transient conversion before coalescence may be calculated or measured from a sample of the second liquid after taking into account any factors that change the concentration of the reaction product in the droplet.

Another embodiment of the present invention, shown in FIG. 1A, is further provided with a thermocouple 60a for observing the pre-adhesion temperature of the droplets.

In this case, the regulator 35 is informed about the pre-adhesion temperature via the input line 60a ', and is temporarily via the input line 31 before the coalescence of the reactant to the intermediate oxidation product of the conversion detector 32. Get information about conversion rates. Again, the regulator 35 regulates the heat exchanger 38 via the output line 46 as in the previous case, regulates the drive device 28 via the output line 29, and output line 37. To adjust the replenishment reservoir 40 and to adjust the feed rate in line 42.

In operation of this embodiment, a portion of the droplet 48 drops over the thermocouple 60a, which in turn supplies pre- coalescence temperature information to the regulator 35 via output line 60a '. At the same time, a portion of the droplets also falls into the same collector 30 directly above the surface 56 of the second liquid mass 54, from which they are sent to the conversion rate detector or monitor 32 to be analyzed in relation to the temporary conversion rate prior to coalescence. Is moved. The information obtained from the conversion rate detector or monitor 32 is fed to the computerized regulator 35 via input line 31, where this information is about the pre-adhesion temperature of the droplets obtained via line 60a '. Together with techniques well known in the art.

When the pre-adhesion temperature reaches first relative to the temporary conversion before pre-adhesion, the regulator 35 first determines based on the pre-adhesion temperature. If the pre-adhesion temperature exceeds the pre-adhesion temperature range, the drive device 28 is instructed by the regulator 35 to lower the height of the atomizer in a manner that reduces the spray distance as defined above. The change in spray distance is preferably at a specific time, preferably in spray distance increments in the range of 10 to 50%, more preferably in the range of 10 to 30%. However, other ranges may be more suitable, depending on the particular conditions, materials, previous measurements, and the like. For example, if a decrease of 10% in spray distance is found to have no appreciable result, the following increment may be for example 30%. On the other hand, if a 10% reduction in spraying distance leads to an excessive change in pre-adhesion temperature, then the next increment is, for example, 5% until the pre-adhesion temperature is within the desired range, preferably the most desirable range. can do.

However, it should be noted that again the preferred range may vary depending on materials, conditions and the like. The distance between the thermocouple 60a and the height or surface 56 of the second liquid mass 54 is preferably a maximum spray distance in the range of 5 to 10%.

For example, in the case of oxidation of cyclohexane to adipic acid, the preferred pre-adhesion temperature range is 50 to 150 ° C, more preferably 80 to 130 ° C, most preferably 90 to 120 ° C.

The temperature before coalescence is found to be within the most preferred range (eg, 90-120 ° C. when converting cyclohexane to adipic acid under certain conditions), and in most cases near the median of the most preferred range (eg For example, continuously observed to be located somewhere in the most preferred value (about 105 ℃). Of course, continuous observation and control is highly desirable because the conditions in the reaction chamber can change to change the temperature before coalescence.

The operation is performed until the temporary conversion rate before coalescence is closer to its most preferable set value than the temperature before coalescence. In some respects, if it is found that the temporal conversion prior to coalescing is farther from its respective most desirable value than the temperature before coalescence, or outside of its respective predetermined range, the temporal conversion before coalescence is given priority. The operation as described in the embodiment is performed.

In another embodiment of the present invention shown in FIG. 2, the reaction chamber 112 is provided with a nebulizer 126 near its upper end 114 and a sample collector 130 located near its bottom end 116. do. Also provided is a temperature measuring device such as a supplemental heat exchanger 158 and thermocouple 160, for example. The liquid dispersion ring 144 is shown at the beginning of the cone portion of the reactor, but may be at any location on the reactor septum, or may be omitted together. This is the same for all embodiments of the present invention. The sample collector 130 monitors the conversion rate via line 133 to provide a sample of the droplets 148 collected in the collector just before they adhere to the second liquid mass 154 (of course in the collector). Or connected to detector 132. The thermocouple 160 and the conversion rate monitor or detector 132 are preferably electrically connected to the regulator 135 via input lines 160 ′ and 131, respectively, and again the regulator 135 is a supplemental heat exchanger ( It is preferably electrically connected to the supplemental heat exchanger 158 via an output line 158 ′ to regulate 158. For the sake of clarity, basically only the members of the device 110 illustrating this embodiment and its operation are shown.

In operation of this embodiment, the first liquid containing the first reactant (eg, cyclohexane) is reacted through line 142 in a manner that is atomized by atomizer 126 to form a plurality of droplets 148. Flows into the chamber 112.

At the same time that the first liquid is sprayed, a gas containing an oxidant (preferably oxygen in the case of cyclohexane) is passed through the gas inlet supply line 136 near the bottom end 116 of the chamber 112. Flows into. The gas may contain, in addition to the oxidant, a somewhat inert gas such as, for example, nitrogen and / or carbon dioxide. Off gas mixed with vapors of reactants, solvents, mists, etc., is withdrawn from the reaction chamber via gas outlet line 125 and treated as illustrated below.

As mentioned above, the droplets begin to react with oxidants (eg oxygen). A portion of the droplet 148 falls into the sample collector 130, from which they are conveyed towards the conversion rate detector or monitor 132 to be analyzed for a temporary conversion rate prior to coalescence.

Information obtained at the conversion rate detector or monitor 132 is supplied to the computerized regulator 135 via input line 131, where they are processed by techniques well known in the art. In addition, spray temperature from thermocouple 160 is also supplied to computerized regulator 135. The regulator 135 regulates the heat exchanger 158 through its output line 158 ′.

If the temporary conversion rate before coalescence exceeds the temporary conversion rate range as defined above, the heat exchanger is instructed by the regulator 135 to lower the spray temperature observed by thermocouple 160. Likewise, when the temporary conversion rate before coalescence is less than the temporary conversion range before coalescence according to the present invention, the heat exchanger is instructed by the regulator 35 to increase the spray temperature. The upper and lower limits of the spraying temperature vary depending on the reactants, reaction conditions and the like. For example, in the case of oxidation of cyclohexane to adipic acid, the upper limit is preferably maintained at 170 ° C or lower, more preferably 150 ° C or lower, and the lower limit is preferably 50 ° C or higher, more preferably. Should be maintained above 70 ℃.

The change in spray temperature is preferably at a specific time, preferably in a spray temperature increment of 5 to 10%.

After the transient conversion before coalescence is found to be within the most preferred range, in most cases it is continuously observed to be located near the median of the most preferred range. Continuous observation and control are highly desirable because the conditions in the reaction chamber can change to change the temporal conversion before coalescence.

In another embodiment of the present invention shown in FIG. 2A, thermocouple 160a is disposed at bottom end 116 of reaction chamber 112 to observe the temperature before coalescence. The shield 190 located below the thermocouple 160a is for protecting the thermocouple 160a from temperature changes due to the ventilation of the rising gas. Another thermocouple 160 is placed in atomizer 126 to measure spray temperature. Thermocouples 160 and 160a are both connected to regulator 135 via input lines 160 'and 160a', respectively. Again, the regulator 135 is preferably electrically connected to the supplemental heat exchanger 158 via an output line 158 ′ to regulate the supplemental heat exchanger 158. For the sake of clarity, basically only the members of the device 110 illustrating this embodiment and its operation are shown.

In operation of this embodiment, the first liquid containing the first reactant (eg, cyclohexane) is reacted through line 142 in a manner that is atomized by atomizer 126 to form a plurality of droplets 148. Flows into the chamber 112.

A portion of the droplet 148 is dropped over the thermocouple 160a, which in turn supplies pre-adhesion temperature information to the computerized regulator 135 via the input line 160a ', where this information is known to those skilled in the art. Is processed by Spray temperature from thermocouple 160 is also supplied to computerized regulator 135 via input line 160 ′. The regulator 135 regulates the heat exchanger 158 through its output line 158 ′.

If the pre-sorption temperature is prioritized and exceeds the pre-sorption temperature range as defined above, the heat exchanger is instructed by the regulator 135 to lower the spraying temperature observed by the thermocouple 160. Likewise, if the pre- coalescence temperature is below the pre- coalescence temperature range according to the invention, the heat exchanger is instructed by the regulator 35 to increase the spray temperature. The upper and lower limits of the spraying temperature vary depending on the reactants, reaction conditions and the like. For example, in the case of oxidation of cyclohexane to adipic acid, the upper limit is preferably maintained at 170 ° C or lower, more preferably 150 ° C or lower, and the lower limit is preferably 50 ° C or higher, more preferably. Should be maintained above 70 ℃.

The change in spray temperature is preferably at a specific time, preferably in a spray temperature increment of 5 to 10%.

The temperature before coalescence is found to be within the most preferred range (eg, 90-120 ° C. when converting cyclohexane to adipic acid under certain conditions), and in most cases near the median of the most preferred range (eg For example, it is continuously observed to be located somewhere (about 115 ℃). As in the previous embodiment, continuous observation and control is highly desirable because the conditions in the reaction chamber can change to change the transient conversion rate.

The change in spray temperature necessarily causes a change in the tempera- ture difference, so the tempera- ture temperature difference is a moving target. However, this has nothing to do with recent computerized regulators well known in the art.

If the temporary temperature difference is further away from its most desirable value than the temperature before coalescence, the temporary temperature difference takes precedence. If the temperature difference before coalescence is greater than its most desirable set point, the heat exchanger is instructed by the regulator 135 to lower the spray temperature observed by the thermocouple 160. Likewise, if the temperature difference before coalescence is smaller than its desired set point according to the invention, the heat exchanger is instructed by the regulator 35 to increase the spray temperature. The upper and lower limits of the spraying temperature vary depending on the reactants, reaction conditions and the like. For example, in the case of oxidation of cyclohexane to adipic acid, the upper limit is preferably maintained at 170 ° C or lower, more preferably 150 ° C or lower, and the lower limit is preferably 50 ° C or higher, more preferably. Should be maintained above 70 ℃.

The change in spray temperature is preferably at a specific time, preferably in a spray temperature increment of 5 to 10%.

After the temporary temperature difference is found to be within the most preferred range, in most cases it is continuously observed to be located near the median of the most preferred range. As in the previous embodiment, continuous observation and adjustment is highly desirable because the conditions in the reaction chamber can change to change the temporary temperature difference value before coalescence.

In another embodiment of the present invention shown in FIG. 3, the reaction chamber 212 is provided with a atomizer 226 near its upper end 214 and a sample collector 230 located near its bottom end 216. do. In addition, a gas mixing valve 268 connected on one side to the compression pump 263, the flow meter 266 in line 236, and the oxidant supply line 247, which are in contact with the reaction chamber 212 via line 236. And other gas lines 249 and pressure gauge devices such as, for example, pressure gauges 262 for observing the pressure inside the reaction chamber 212. The liquid dispersion ring 244 is shown approximately in the middle of the partition of the reaction chamber 212, but may be at any location on the partition or may be omitted together. The sample collector 230 monitors the conversion rate via line 233 to provide samples of the droplets 248 collected in the collector just before they adhere to the second liquid mass 254 (of course in the collector). Or connected to detector 232. Pressure gauge 262, flow gauge 266, and conversion rate monitor or detector 232 are preferably electrically connected to regulator 235 via input lines 262 ', 266', and 231, respectively. Connected. Again, regulator 235 is connected to compression pump 263 via output line 263 ', to gas mixing valve 268 via output line 268', and valve 264 through output line 264 '. Is preferably electrically connected. The regulator 235 is applied to regulate the compression pump 263, the gas mixing valve 268 and the valve 264. For the sake of clarity, basically only the members of the device 210 which illustrate this embodiment and its operation are shown.

In operation of this embodiment, the valve 264 is initially closed or turned to the off position. Gas mixing valve 268 measures a predetermined ratio of oxidant to inert gas, obtained from lines 247 and 249, respectively, which ratio determines the amount of oxidant in the total gas defined as the second content above. It is adjusted to deliver to the compression pump 263. The compression pump is then left open until the desired pressure in the reaction chamber 212 is achieved. Thereafter, with the compression pump open, the valve 264 is left open to the extent that the desired pressure in the reaction chamber is maintained. If the flow rate measured from the flow meter 266 (as defined above, the second flow rate is the flow rate of the gas) is too large, the pump is turned at a lower speed and the valve 264 has a lower second flow. It is turned to a less open position to maintain the desired pressure at speed. This continues until both the pressure and the second flow rate reach the desired values. If the second flow rate measured from the flow gauge 266 is too low, the pump will be turned at a higher speed and / or the valve 264 will be opened more open to maintain the desired pressure at the higher second flow rate. Is returned. This continues until both the pressure and the second flow rate reach the desired values.

After both the pressure and the second flow rate have their initial desired values, the first liquid containing the first reactant (eg cyclohexane) is heated to the spray temperature as described above and then atomizer 226 ) Is introduced into reaction chamber 212 through line 242 in a manner that is sprayed by < RTI ID = 0.0 >

At the same time the first liquid is sprayed, a mixed gas containing an oxidant (preferably oxygen in the case of cyclohexane) is passed through the gas inlet supply line 236 near the bottom end 216 of the reaction chamber 212. Flows to 212. The desired ratio of gases (which defines the second content as discussed above) depends on the reaction and conditions and may have any value suitable for the environment. In most cases, the preferred oxidant is oxygen and other gases are inert gases such as, for example, nitrogen or carbon dioxide. Off gas mixed with vapors of reactants, solvents, mists, etc., is withdrawn from reaction chamber 212 via gas outlet line 225 and treated as illustrated below.

As the droplets fall downward from atomizer 226 they begin to react with oxidants (eg oxygen). The second liquid 254 is preferably removed continuously through the liquid outlet 224 as in the previous embodiment.

After the oxidation product and / or by-products are removed in separator 15 shown in FIG. 1, a portion of the second liquid may be conveyed through line 211 ′ to liquid dispersion ring 244, as desired. This is dispersed in the form of a thick film or liquid curtain 245 as in the previous embodiment.

A portion of the droplet 248 falls into the sample collector 230, from which they are conveyed to a conversion rate detector or monitor 232 to be analyzed for a temporary conversion rate prior to coalescence.

The information obtained in the transient conversion rate detector or monitor 232 before coalescence is supplied to the computerized regulator 235 via input line 231, where this information is processed by techniques well known in the art. In addition, the pressure in the reaction chamber obtained from the gauge 262 and the flow rate (second flow rate) of the gas through the line 236 measured by the flow meter 266 are respectively determined by the input lines 262 ′ and 266. ') Is supplied to the computerized regulator 235. As described above, the regulator 235 receives the compression pump 263 through its output line 263 ', the valve 264 through its output line 264', and through its output line 268 '. Adjust gas mixing valve 268.

Adjusting the compression pump means that the regulator is adapted to change the pressure and flow output of the compression pump based on data obtained from input lines 231, 266 ′ and 262 ′ (the data being Processed according to the intended program). Adjusting the valve 264 means that the regulator opens / closes the valve 264 to a desired degree based on the data obtained from the input lines 231, 266 ′ and 262 ′ ( The data is processed according to the desired program). Regulating gas mixing valve 268 is based on data obtained from input lines 231, 266 ′, and 262 ′ by the oxidant and line 249 provided by line 247. It means that the valve 268 is adjusted such that a mixture with other gases provided (eg inert gas) is supplied to the compression pump 263 at the desired weight ratio (the data is processed according to the desired program). Programming of computerized regulators is well known in the art.

As can be seen in FIG. 3, in this embodiment the two members capable of measuring the pressure inside the reaction chamber 212 and the second flow rate are the compression pump 263 and the valve 264. Other members in line 225, such as, for example, condensers (not shown), gas recirculation assemblies (not shown), may also temporarily affect pressure in most cases, but are excluded from FIG. 3 for clarity. . These will be discussed below. As the compression pump distributes more gas into the reaction chamber 212 and the more the valve 264 is submerged, the pressure inside the reaction chamber becomes higher. As the compression pump distributes less gas into the reaction chamber 212 and more valves 264 are opened, the pressure inside the reaction chamber is lower. Of course, the flow or delivery rate of gas by the compression pump 263 and the degree of opening of the valve 264 must be matched to achieve the desired pressure inside the reaction chamber.

The data contained within computerized controller 235 may be used to adjust the temporal conversion rate prior to coalescence after processing by various methods or combinations thereof and to maintain it within the temporal conversion rate range prior to coalescence.

One method is to change the flow rate (second flow rate) of the gas entering the reaction chamber 212 via line 236. Computerized regulator 235 is measured by flow meter 266 when the temporary conversion rate before pre-adhesion monitor or measured at detector 232 has a value greater than the desired temporary conversion rate range before pre-adhesion. The compression pump is instructed to reduce the second flow rate that is achieved. At the same time, valve 264 is instructed by regulator 235 such that the pressure within reaction chamber 212 measured by pressure gauge 262 is in a slightly more closed or restricted position. This continues until the second flow rate reaches a new desired range and the pressure is within the desired range. If the temporary conversion rate before pre-adhesion measured by the conversion rate monitor or detector 232 has a value smaller than the desired conversion range before pre-adhesion, the computerized regulator 235 is measured by the flow meter 266. Instruct the compression pump to increase the second flow rate. At the same time, the valve 264 is in a slightly more open position and is instructed by the regulator 235 such that the pressure inside the reaction chamber 212 measured by the pressure gauge 262 is within the desired range. This continues until the second flow rate reaches a new desired range and the pressure is within the desired range. The change (increase or decrease) in the second flow rate from either value to the new desired value is preferably such that it is in an increment ranging from 5 to 20%, more preferably from 5 to 10%. In addition, the change is preferably indicated by the computerized controller at a time interval long enough for the conversion rate monitor or detector 232 to accommodate at least one new pre-adhesion transient conversion rate measurement.

If the temporary conversion rate before the coalescing under the newly achieved second flow rate is not within the predetermined temporary conversion rate range before the coalescence, the same process is repeated until the temporary conversion rate before the coalescence finally reaches the desired temporary conversion rate range before the coalescence.

Another method is to change the ratio of oxidant to inert or other gas entering the reaction chamber 212 via line 236. If the temporary conversion rate prior to coalescence measured at the conversion rate monitor or detector 232 has a value greater than the temporary conversion rate range before the desired coalescence, the computerized regulator 235 reduces the gas mixing valve 268 to reduce the ratio. ). If the temporary conversion rate prior to coalescence measured by the conversion rate monitor or detector 232 has a value less than the desired range of temporary conversions before coalescence, the computerized regulator 235 will increase the rate of gas mixing valve. (268). The change (increase or decrease) in the ratio from one value to the new desired value is preferably such that it is in the range of 5 to 20%, more preferably in the range of 5 to 10%. In addition, the change is preferably indicated by the computerized controller at a time interval long enough for the conversion rate monitor or detector 232 to accommodate at least one new pre-adhesion transient conversion rate measurement.

Another method is to change the pressure of the gas in the reaction chamber 212, and in many cases increasing the pressure increases the reactivity to a substantial extent. Computerized regulator 235 instructs the compression pump to decelerate if the temporary conversion rate before pre-adhesion monitor or detector 232 has a value greater than the desired temporary conversion rate range before pre-adhesion. At the same time, valve 264 is in a slightly more open position and is instructed by regulator 235 such that the second flow rate measured by flow gauge 266 is within the desired range. This continues until the pressure reaches the new desired value and the second flow rate is within the desired range. Computerized regulator 235 instructs the compression pump to accelerate when the temporary conversion rate prior to coalescence measured by the conversion rate monitor or detector 232 has a value less than the desired range of temporary conversions before coalescence. At the same time, the valve 264 is in the slightly closed position and is instructed by the regulator 235 such that the second flow rate measured by the flow gauge 266 is within the desired range. This continues until the pressure reaches the new desired value and the second flow rate is within the desired range. The change in pressure (increase or decrease) from either value to the new desired value is preferably such that it is in an increment ranging from 2 to 20%, more preferably from 5 to 10%. In addition, the change is preferably indicated by the computerized controller at a time interval long enough for the conversion rate monitor or detector 232 to accommodate at least one new pre-adhesion transient conversion rate measurement.

If the temporary conversion rate before the coalescence under the newly achieved pressure is not within the predetermined temporary conversion rate range before the coalescence, the same treatment is repeated until the temporary conversion rate before the coalescence finally reaches the desired temporary conversion rate range before the coalescence.

In another embodiment of the present invention shown in FIG. 3A, the reaction chamber 212 includes a nebulizer 226 having a thermocouple 260 near its upper end 214 and a bottom end 216 of the reaction chamber 212. The thermocouple 260a is provided near (). Thermocouple 260a is connected to regulator 235 via input line 260 'to provide the temperature of the droplet before droplet 248 adheres to second liquid mass 254. Pressure gauge 262, flow gauge 266, thermocouple 260, and thermocouple 260a are connected to regulator 235 via input lines 262 ', 266', 260 'and 260a', respectively. Is preferably electrically connected. As in the previous embodiment, the regulator 265 is connected to the compression pump 263 via the output line 263 ', to the gas mixing valve 268 via the output line 268', and to the output line 264 '. It is preferably electrically connected to the valve 264 via. The regulator 235 is applied to regulate the compression pump 263, the gas mixing valve 268, and the valve 264.

The operation of this embodiment is quite similar to that of the previous embodiment, except that the measured value is a temporary temperature difference or a temperature before coalescence or a combination thereof.

A portion of droplet 248 falls above thermocouple 260a, which measures their temperature in the form of an electrical signal, which is supplied to input computer 260a 'through input line 260a', which is well known in the art. Is processed by technology. In addition, the spray temperature in atomizer 226 is measured by thermocouple 260 in the form of another electrical signal, which is supplied via input line 260 'to computerized regulator 235 where regulator 235 ) Is processed along with the rest of the information it accepts.

The data contained in computerized regulator 235 may be used to adjust pre-adhesion temperatures and / or transient temperature differences after processing by various methods or combinations thereof and to maintain them within their respective predetermined ranges.

One method is to change the flow rate (second flow rate) of the gas entering the reaction chamber 212 via line 236. If the predominant determinant is greater than each desired range desired, then the computerized regulator 235 instructs the compression pump to reduce the second flow rate measured by flow gauge 266. At the same time, valve 264 is instructed by regulator 235 such that the pressure within reaction chamber 212 measured by pressure gauge 262 is in a slightly more closed or restricted position. This continues until the second flow rate reaches a new desired range and the pressure is within the desired range. If the predominant determinant has a value less than each predetermined range, the computerized regulator 235 instructs the compression pump to increase the second flow rate measured by the flow gauge 266. At the same time, the valve 264 is in a slightly more open position and is instructed by the regulator 235 such that the pressure inside the reaction chamber 212 measured by the pressure gauge 262 is within the desired range. This continues until the second flow rate reaches a new desired range and the pressure is within the desired range. The change (increase or decrease) in the second flow rate from either value to the new desired value is preferably such that it is in an increment ranging from 5 to 20%, more preferably from 5 to 10%. In addition, the change is preferably indicated by the computerized regulator at a time interval long enough to allow for a suitable equilibrium to prevent exceeding the target.

If the predominant determinant under the newly achieved second flow rate is not within each predetermined range, the same process is repeated until the predominant determinant finally reaches the desired predetermined range.

Another method is to change the ratio of oxidant to inert or other gas entering the reaction chamber 212 via line 236. If the predominant determinant has a value greater than each desired range desired, then the computerized regulator 235 instructs gas mixing valve 268 to reduce the ratio. If the predominant determinant has a value smaller than each desired range desired, then the computerized regulator 235 instructs gas mixing valve 268 to increase the ratio. The change (increase or decrease) in the ratio from one value to the new desired value is preferably such that it is in the range of 5 to 20%, more preferably in the range of 5 to 10%. In addition, the change is preferably indicated by the computerized regulator at a time interval long enough to allow for a suitable equilibrium to prevent exceeding the target.

Another method is to change the pressure of the gas in the reaction chamber 212, and in many cases increasing the pressure increases the reactivity to a substantial extent. If the predominant determinant has a value greater than each desired range desired, the computerized regulator 235 instructs the compression pump to decelerate. At the same time, valve 264 is in a slightly more open position and is instructed by regulator 235 such that the second flow rate measured by flow gauge 266 is within the desired range. This continues until the pressure reaches the new desired value and the second flow rate is within the desired range. When the predominant determinant has a value smaller than each desired range desired, the computerized regulator 235 directs the compression pump to acceleration. At the same time, the valve 264 is in the slightly closed position and is instructed by the regulator 235 such that the second flow rate measured by the flow gauge 266 is within the desired range. This continues until the pressure reaches the new desired value and the second flow rate is within the desired range. The change in pressure (increase or decrease) from either value to the new desired value is preferably such that it is in an increment ranging from 2 to 20%, more preferably from 5 to 10%. In addition, the change is preferably indicated by the computerized regulator at a time interval long enough to allow for a suitable equilibrium to prevent exceeding the target.

If the predominant determinant under newly achieved pressure is not within each of the desired predetermined ranges, the same processing is repeated until the predominant determinant finally reaches the desired range.

The preferred program rules and the reverse program rules described above apply in this or other embodiments.

In another embodiment of the present invention shown in FIG. 4, the reaction chamber 312 is provided with a atomizer 326 near its upper end 314 and a sample collector 330 located near its bottom end 316. do. Also, a semi-agitator for mixing the first reactant provided from line 370 with the other liquid provided from line 371 to produce a first liquid in line 342 having a first reactant of the first content. Mixing valve 369 is also provided. The sample collector 330 monitors the conversion rate through the sample line 333 to provide a sample of the droplets 348 collected in the collector just before they adhere to the second liquid mass 354 (of course, in the collector). Or connected to detector 332. The conversion rate monitor or detector 332 is preferably electrically connected to the regulator 335 via an input line 331 to convey temporary conversion rate information prior to coalescence. Again, regulator 335 is preferably electrically connected to reactant mixing valve 369 via output line 369 'to regulate reactant mixing valve 369. For the sake of clarity, basically only the members of the apparatus 310 illustrating this embodiment and its manipulations are shown.

In operation of this embodiment, the first reactant provided from line 370 and the other liquids provided from line 371 may cause the first liquid in line 342 to contain the liquid such that the first liquid in line 342 has a first reactant of a first content. The mixing is carried out at a controlled rate by the reactant mixing valve 369 to produce. The liquid provided from line 371 may contain a solvent, a catalyst, an accelerator, an initiator, a recycled component, a first reactant, and the like. If the liquid provided from line 371 contains a first reactant, the reactant mixing valve, taking into account the content of the first reactant in these liquids in determining the first content of the first reactant in line 342 It should be noted that 369 should allow the first reactant from line 370 in a smaller amount as appropriate.

As the droplets drop downward from atomizer 326 they begin to react with oxidants (eg oxygen). The second liquid 354 is preferably removed continuously through the liquid outlet line 324 as in the previous embodiment.

A portion of the droplet 348 falls into the sample collector 330, from which they are conveyed towards the conversion rate detector or monitor 332 to be analyzed for a temporary conversion rate prior to coalescence.

The information obtained from the conversion rate detector or monitor 332 is supplied to computerized regulator 335 via input line 331, where this information is processed by techniques well known in the art. Regulator 335 regulates the reactant mixing valve through output line 369 '.

If the transient conversion before coalescence exceeds the temporary conversion range before coalescence as defined above, reactant mixing valve 369 provides a ratio of the first reactant provided from line 370 to the liquid supplied from line 371. Instructed by regulator 335 to increase the first reactant by increasing. Likewise, if the temporary conversion rate before coalescence is less than the temporary conversion rate range before coalescence according to the present invention, reactant mixing valve 369 may provide a ratio of the first reactant provided from line 370 to the liquid supplied from line 371. Instructed by regulator 335 to reduce the first reactant by decreasing.

The change in the first content is preferably at a specific time in the first content increment, preferably in the range of 5 to 10%.

After the temporary conversion rate before coalescence is found to be within the most preferred range, the temporary conversion rate before coalescence is observed in most cases to be located somewhere near the median of the most preferred range. As in the previous embodiment, continuous observation and control is highly desirable because the conditions in the reaction chamber can change to change the temporal conversion before coalescence. Valves that are controlled by computerized regulators and that control the proportion of liquid in accordance with certain programs are well known in the art.

In another embodiment of the present invention shown in FIG. 4A, the reaction chamber 312 is provided with a thermocouple 360a located near the bottom end 316 and shielded by a shield 390. Thermocouple 360a is electrically connected to regulator 335 through input line 360a 'to provide temperature data prior to coalescence.

In operation of this embodiment, the first reactant provided from line 370 and the other liquids provided from line 371 may cause the first liquid in line 342 to contain the liquid such that the first liquid in line 342 has a first reactant of a first content. The mixing is carried out at a controlled rate by the reactant mixing valve 369 to produce.

A portion of the droplets 348 prepared and processed as described in this embodiment falls above the thermocouple 360a and their temperature is measured by the thermocouple and provided to the regulator 335 through the input line 360a '. And are treated by techniques well known in the art. Regulator 335 regulates the reactant mixing valve through output line 369 '.

If the pre-sorption temperature exceeds the pre-sorption temperature range as defined above, the reactant mixing valve 369 reduces the ratio of the first reactant provided from line 370 to the liquid supplied from line 371. By the regulator 335 to reduce the first reactant. Likewise, when the pre-sorption temperature is below the pre-sorption temperature range according to the present invention, the reactant mixing valve 369 may increase the ratio of the first reactant provided from line 370 to the liquid supplied from line 371. Instructed by regulator 335 to increase the first reactant.

After the pre-adhesion temperature is found to be within the most preferred range, the pre-adhesion temperature is observed continuously in most cases to be located somewhere near the median of the most preferred range.

In another embodiment of the present invention shown in FIG. 5, the reaction chamber 412 is provided with a atomizer 426 near its upper end 414 and a sample collector 430 located near its bottom end 416. do. Atomizer 426 may be operated by gas or preferably without requiring gas (generally called airless in the art). Atomizer 426 of this embodiment is adapted to adjust droplet size or diameter at will through regulator 472. Such atomizers are well known in the art. For example, droplet diameter can change the pressure of the liquid being atomized, change the orifice size, change the frequency and / or intensity in the case of ultrasonic or other pulsed atomizers, or gas-operated atomizations. In the case of a firearm, the pressure of the gas may be changed, or in the case of a centrifugal atomizer, the rotation or the speed may be changed. For the purposes of the present invention, regulator 472 represents any device known in the art that is adapted to controllably vary any variable parameter of the atomizer that controls the average diameter of the droplets.

The sample collector 430 provides a conversion rate monitor or detector (not shown) via the sample line 433 to provide the samples of the droplets 448 just before they adhere to the second liquid mass 454 (of course, in the collector). 432). Conversion rate monitor or detector 432 is preferably electrically connected to regulator 435 via input line 431 to convey temporary conversion rate information prior to coalescence. Again, the regulator 435 is preferably electrically connected to the regulator 472 via an output line 472 ′ to adjust the regulator 472. For the sake of clarity, basically only the members of the device 410 illustrating this embodiment and its operation are shown.

In operation of this embodiment, the first liquid containing the first reactant (eg, cyclohexane) is reacted through line 442 in a manner that is atomized by atomizer 426 to form multiple droplets 448. Flows into the chamber 412.

A portion of the droplet 448 falls into the sample collector 430, from which they are conveyed towards the conversion rate detector or monitor 432 to be analyzed for a temporary conversion rate prior to coalescence.

Information obtained from the conversion rate detector or monitor 432 is supplied to the computerized regulator 435 via input line 431, where this information is processed by techniques well known in the art. Regulator 435 regulates regulator 472 via output line 472 '.

If the temporary conversion rate before coalescence exceeds the temporary conversion rate range as defined above, regulator 472 is instructed by regulator 435 to increase the average diameter of the droplets. Likewise, when the temporary conversion rate before coalescence is less than the temporary conversion rate range before coalescence according to the present invention, regulator 472 is directed by regulator 435 to reduce the average diameter of the droplets.

The change in droplet diameter is preferably at a specific time, preferably in an average droplet diameter increment in the range of 10-20%.

After it has been found that the temporal conversion before coalescence is within the most desirable range, the temporal conversion before coalescence is, in most cases, continuously observed to be somewhere near the median of the most preferred range (eg about 40%). As in the previous embodiment, continuous observation and control is highly desirable because the conditions in the reaction chamber can change to change the temporary conversion rate before coalescence.

The device 410 may optionally include any monitor 474, preferably in the form of an optical fiber, connected to the image analyzer 476 via a line 474 ′ (the image analyzer may in turn be a line 476). ') To the computerized regulator 435). In operation of this embodiment, the image analyzer 476 measures the average droplet diameter from the image received from the optical monitor 474 and sends this information to the controller 435, which sends this information to the rest of the processed data. In combination with, for example, the change indicated by the adjuster 472 with the resulting drop size change, allowing for better control of the average drop diameter.

In another embodiment of the present invention shown in FIG. 5A, thermocouple 460a is preferably electrically connected to regulator 435 via input line 460a 'to carry pre-bonding temperature information. Again, the regulator 435 is preferably electrically connected to the regulator 472 via an output line 472 ′ to adjust the regulator 472. For the sake of clarity, basically only the members of the device 410 illustrating this embodiment and its operation are shown.

In operation of this embodiment, the first liquid containing the first reactant (eg, cyclohexane) is reacted through line 442 in a manner that is atomized by atomizer 426 to form multiple droplets 448. Flows into the chamber 412.

A portion of droplet 448 falls over thermocouple 460a and their temperature is measured and provided to computerized regulator 435 via input line 460a 'and processed by techniques well known in the art. Regulator 435 regulates regulator 472 via output line 472 '.

If the pre-adhesion temperature exceeds the pre-adhesion temperature range as defined above, the regulator 472 is directed by the regulator 435 to increase the average diameter of the droplets. Likewise, when the pre-adhesion temperature is below the predetermined pre-adhesion temperature range in accordance with the present invention, the regulator 472 is directed by the regulator 435 to reduce the average diameter of the droplets.

The change in droplet diameter is preferably at a specific time, preferably in an average droplet diameter increment in the range of 10-20%.

After it has been found that the temperature before coalescence is within the most preferred range (e.g. 90 to 120 ° C. when converting cyclohexane to adipic acid under certain conditions), the temperature before coalescence is in most cases the median of the most preferred range. Observed continuously to be located somewhere near (eg about 120 ° C.). As in the previous embodiment, continuous observation and control is highly desirable because the conditions in the reaction chamber can change to change the temperature before coalescence. Valves that are controlled by computerized regulators and that control the proportion of liquid in accordance with certain programs are well known in the art.

In another embodiment of the present invention shown in FIG. 6, the reaction chamber 512 is provided with a atomizer 526 near its upper end 514 and a sample collector 530 located near its bottom end 516. do. Also, a first liquid pump 577 for regulating a first flow of the first liquid in line 542, and a flow meter 578 for measuring the first flow rate of the first liquid in line 542. Is provided. Flow gauge 578 is preferably electrically connected to computerized regulator 535 via work line 578 '. The sample collector 530 uses a conversion rate monitor or detector through a sample line 533 to provide a sample of the droplets 548 just before they adhere to the second liquid mass 554 (of course in the collector). 532). The conversion rate monitor or detector 532 is preferably electrically connected to the regulator 535 via an input line 531 to convey temporary conversion rate information prior to coalescence. Again, the regulator 535 is preferably electrically connected to the first liquid pump 577 via an output line 577 'to regulate the first liquid pump 577. For the sake of clarity, basically only the members of the apparatus 510 illustrating this embodiment and its operation are shown.

In operation of this embodiment, the first liquid pump 577 pumps the first liquid in line 542 at the desired first flow rate. In this way, the first liquid containing the first reactant (eg, cyclohexane) in a first content is reacted through line 542 in a manner that is atomized by atomizer 526 to form a plurality of droplets 548. Flows into the chamber 512.

A portion of the droplet 548 falls into the sample collector 530, from which they are conveyed towards the conversion rate detector or monitor 532 to be analyzed for a temporary conversion rate prior to coalescence.

Information obtained from the conversion rate detector or monitor 532 is supplied to the computerized regulator 535 via input line 531, where this information is processed by techniques well known in the art. In addition, flow velocity measurements obtained from flow gauge 578 are processed with information supplied to regulator 535 and received from line 531. The regulator 535 regulates the first liquid pump 577 through the output line 577 'in a manner that increases or decreases the flow rate of the first liquid in a reprogrammed manner.

When the temporary conversion rate before coalescence exceeds the temporary conversion rate range as defined above, the first liquid pump 577 is provided to the regulator 535 to increase the first flow rate, for example by increasing the pump action. Is indicated by Likewise, when the temporary conversion rate before coalescence is less than the temporary conversion rate range before coalescence as defined above, the first liquid pump 577 adjusts the regulator 535 to reduce the first flow rate, for example by reducing the pump action. Is indicated by.

The change in the first flow rate is preferably at a specific time in a first flow rate increment, preferably in the range of 5 to 10%.

After the temporary conversion rate before coalescence is found to be within the most desirable range, the temporary conversion rate before coalescence is observed continuously in most cases to be located near the median of the most preferred range.

In another embodiment of the present invention shown in FIG. 6A, the reaction chamber 512 includes a nebulizer 526 near its upper end 514, and a thermocouple 560 located within the nebulizer to observe the spray temperature; And a thermocouple 560a located near the bottom end 516 of the reaction chamber 512. Thermocouples 560 and 560a are preferably electrically connected to regulator 535 via input lines 560 'and 560a', respectively, to provide spray temperature and pre- coalescence temperature data to the regulator 535. Connected. Again, the regulator 535 is preferably electrically connected to the first liquid pump 577 via an output line 577 'to regulate the first liquid pump 577. For the sake of clarity, basically only the members of the apparatus 510 illustrating this embodiment and its operation are shown.

In operation of this embodiment, the first liquid pump 577 pumps the first liquid in line 542 at the desired first flow rate. In this way, the first liquid containing the first reactant (eg, cyclohexane) in a first content is reacted through line 542 in a manner that is atomized by atomizer 526 to form a plurality of droplets 548. Flows into the chamber 512.

A portion of droplet 548 falls over thermocouple 560a and their temperature is measured and provided to computerized regulator 535 via input line 560a 'and processed by techniques well known in the art herein. In addition, the spray temperature measured by thermocouple 560 is supplied to controller 535 via input line 560 'and is also processed here. Flow velocity measurements provided from flow gauge 578 are supplied to regulator 535 via line 578 'and processed with information provided from lines 560a' and 560 '. The regulator 535 regulates the first liquid pump 577 through the output line 577 'in a manner that increases or decreases the flow rate of the first liquid in a reprogrammed manner.

If the predominant determinant (in this case, the pre-adhesion temperature or the temporal temperature difference) exceeds the predominant determinant target range as defined above, the first liquid pump 577 may, for example, increase the first action by increasing the pump action. Instructed by regulator 535 to increase the flow rate. Likewise, if the predominant determinant is below the predominant determinant target range as defined above, the first liquid pump 577 may be coupled to the regulator 535 to reduce the first flow rate, for example by reducing the pump action. Is indicated by

The change in the first flow rate is preferably at a specific time in a first flow rate increment, preferably in the range of 5 to 10%.

After the predominant determinants have been found to be within the most preferred range, the predominant determinants are observed continuously, as already described, in most cases located somewhere near the median of their most preferred range.

In another embodiment of the present invention shown in FIG. 7, the reaction chamber 612 includes a nebulizer 626 near its upper end 614, and a sample collector 630 located near its bottom end 616. Is provided. A volatile mixture valve 679 is also provided for mixing volatiles provided from line 680 with other liquids provided from line 681 to produce a first liquid in line 642. The sample collector 630 monitors the conversion rate through the sample line 633 to provide a sample of the droplets 648 collected in the collector just before they coalesce into the second liquid mass 654 (of course in the collector). Or detector 632. The conversion rate monitor or detector 632 is preferably electrically connected to the regulator 635 via an input line 631 to convey temporary conversion rate information prior to coalescence. Again, the regulator 635 is preferably electrically connected to the volatile mixture valve 679 via an output line 679 ′ to regulate the volatile mixture valve 679. For the sake of clarity, basically only the members of the apparatus 610 illustrating this embodiment and its operation are shown.

In operation of this embodiment, the volatiles provided from line 680 and other liquids provided from line 681 may be prepared to produce the liquid such that the first liquid in line 642 has the desired volatile content. Mixing at a controlled rate by valve 679. Volatiles are materials that usually have a lower boiling point than the boiling point of the first reactant, which tends to volatilize when the first liquid is sprayed in the reaction chamber under reaction conditions and has a lower conversion rate. The volatiles are preferably low or no reactivity under reaction conditions. When cyclohexane is oxidized to adipic acid, for example acetic acid and / or acetone are volatiles.

The liquid provided from line 681 contains the first reactant with solvent, catalyst, promoter, initiator, recycled components, and the like. The first liquid containing the first reactant (eg cyclohexane) is introduced into the reaction chamber 612 via line 642 in a manner that is atomized by atomizer 626 to form a plurality of droplets 648. .

A portion of the droplet 648 falls into the sample collector 630, from which they are conveyed towards the conversion rate detector or monitor 632 to be analyzed for a temporary conversion rate prior to coalescence.

Information obtained from the conversion rate detector or monitor 632 is supplied to the computerized regulator 635 via input line 631, where this information is processed by techniques well known in the art. Regulator 635 regulates volatile mixing valve 679 via output line 679 '.

If the temporary conversion rate before coalescence exceeds the temporary conversion rate range as defined above, the volatile mixture valve 679 is directed by the regulator 635 to increase the introduction of volatiles obtained from line 680. . Likewise, when the temporary conversion rate before coalescence is less than the temporary conversion rate range before coalescence according to the present invention, the volatile mixture valve 679 is controlled by the regulator 635 so as not to reduce or introduce the introduction of volatiles obtained from line 680. Is directed.

The increase or decrease in volatiles is preferably in increments ranging from 2 to 5%, based on the total weight of the first liquid at a particular time.

After the temporary conversion rate before coalescence is found to be within the most desirable range, the temporary conversion rate before coalescence is observed continuously in most cases to be located near the median of the most preferred range.

If the liquid in line 681 is arranged to contain no catalyst or only a small amount, the catalyst may be added via line 680 in the desired base amount. The addition of higher amounts of catalyst will increase the temporary conversion before coalescence, and the addition of smaller amounts of catalyst will reduce the temporary conversion before coalescence.

The increase or decrease in the amount of catalyst is preferably in increments ranging from 5 to 10%, based on the total weight of the catalyst contained in the first liquid at a particular time.

In another embodiment of the present invention shown in FIG. 7A, the reaction chamber 612 includes an atomizer 626 near its upper end 614, a thermocouple 660 in the atomizer 626, and a bottom end 616. A thermocouple 660a located near) is provided. Thermocouple 660a is preferably electrically connected to regulator 635 via input line 660a 'to provide pre- coalescence temperature information to the regulator 635.

In operation of this embodiment, the volatiles provided from line 680 and other liquids provided from line 681 may be prepared to produce the liquid such that the first liquid in line 642 has the desired volatile content. Mixing at a controlled rate by valve 679.

The liquid provided from line 681 contains the first reactant with solvent, catalyst, promoter, initiator, recycled components, and the like. The first liquid containing the first reactant (eg cyclohexane) is introduced into the reaction chamber 612 via line 642 in a manner that is atomized by atomizer 626 to form a plurality of droplets 648. .

Spray and pre-bond temperature information obtained by thermocouples 660a and 660 is supplied to computerized regulator 635 via lines 660a 'and 660', respectively, where the information According to techniques well known in the art. Regulator 635 regulates volatile mixing valve 679 via input line 679 ′.

A portion of the droplet 648 falls into the sample collector 630, from which they are conveyed towards the conversion rate detector or monitor 632 to be analyzed for a temporary conversion rate prior to coalescence.

In case the prevailing determinant exceeds the predominant determinant predetermined range as defined above, the volatile mixture valve 679 is directed by the regulator 635 to increase the introduction of volatiles obtained from line 680. Likewise, if the predominant determinant is below the predominant determinant predetermined range in accordance with the present invention, the volatile mixture valve 679 is instructed by the regulator 635 so as not to reduce or introduce the introduction of volatiles obtained from line 680. do.

After the predominant determinants are found to be within the most desirable range, the predominant determinants are continuously observed, as already described, in most cases such that the determinants are all located somewhere near the median of their most preferred range.

Again, if the liquid in line 681 is arranged to contain no catalyst or only a small amount, the catalyst may be added via line 680 in the desired base amount. The addition of a larger amount of catalyst will increase the pre- coalescence temperature, the temporal temperature difference and the temporal conversion before coalescence, while the addition of a smaller amount of catalyst will reduce the pre- coalescence temperature, the temporal temperature difference and the temporal conversion before coalescence.

In another embodiment shown in FIG. 8, the reaction chamber 712 has a nebulizer 726 near its upper end 714, and a boat on liquid 754 at the bottom end 716 of the reaction chamber 712. A sample collector 730 is provided that is adapted to float as shown. Sample collector 730 also supports thermocouple 760a for measuring the temperature before coalescence. Atomizer 726 is provided with a first liquid from line 742 with flow gauge 778. A holding tank 753 is also provided which is connected near the bottom end 716 of the reaction chamber 712 via two pumps 751a and 751b. Retention tank 753 is also connected to a pump 751c which serves to deliver the liquid to the separator (shown as 15 in FIG. 1). In addition, a height adjuster 755 is also provided which adjusts the pump 751c based on the height of the liquid in the holding tank 753 by techniques well known in the art. The height adjuster operates pump 751c through output line 751c 'when liquid exceeds height A and does not operate pump 751c when liquid descends below height B.

The sample collector 730 is capable of bending the coil portion 733 'in order to provide a sample of the droplets 748 collected in the collector just before they adhere to the second liquid mass 754 (of course, in the collector). Is connected to a conversion rate monitor or detector 732 via a sample line 733 with. The sample collector 730 has a boat-like structure provided with a sealed floating portion 730a and a sample portion 730b as shown in FIG. The bendable coil portion 733 ′ of line 733, and the bendable coil portion 760a of line 760a ′ allow the boat-type sample collector 730 to have a surface 756 of the second liquid mass 754. To move freely in the The thermocouple 760a supported by the floating sample collector 730 is connected to the regulator 735 via an input line 760a 'having a coil portion 760a. The thermocouple preferably transfers the temperature data before coalescence to the regulator 735 preferably.

The conversion rate monitor or detector 732 is also preferably electrically connected to the regulator 735 via an input line 731 to convey temporary conversion rate information prior to coalescence. The flow meter 778 is also preferably connected to the regulator 735 via an input line 778 ′ to convey flow rate information about the first liquid entering the reaction chamber 712 via the atomizer 726. Is electrically connected. Again, regulator 735 is preferably electrically connected to pumps 751a and 751b through output lines 751a 'and 751b', respectively, to regulate pumps 751a and 751b. .

For the sake of clarity, basically only the members of the apparatus 710 illustrating this embodiment and its operation are shown.

In operation of this embodiment, the first liquid containing the first reactant (eg, cyclohexane) is reacted through line 742 in a manner that is atomized by atomizer 726 to form multiple droplets 748. Flows into the chamber 712.

A portion of the droplet 748 falls into the sample collector 730 from which they are converted through a rate detector or monitor 732 through line 733 and its bendable portion 733 'to be analyzed for temporary conversion prior to coalescence. Hauled toward). In addition, a portion of the droplet falls on the thermocouple 760a measuring the temperature before coalescence, and the thermocouple then conveys this information to the regulator 735 via line 760a 'and its coil portion 760a.

Information obtained from the conversion rate detector or monitor 732 is supplied to the computerized regulator 735 via input line 731, where this information is processed by techniques well known in the art. The regulator 735 regulates the pumps 751a and 751b as described above.

If the predominant determinant (pre-adhesion temperature or pre-adhesion temporal conversion) as described above exceeds the predetermined prevailing determinant range as defined above, the pump 751a is directed to the regulator 735 to stop its pump operation. Is instructed to operate the pump 751b. This raises the surface 756 of the second liquid mass 754, resulting in a smaller spray distance as defined above. Again, the smaller the spray distance, the lower the predominant determinant. Likewise, if the prevailing determinant is below the predetermined prevailing determinant range as defined above, the pump 751a is instructed by the regulator 735 to start or continue its pump operation and the pump 751b stops operating. This lowers the surface 756 of the second liquid mass 754, resulting in a larger spray distance. Again, the greater the spray distance, the greater the predominant determinant.

The height 756 of the second liquid mass 754 is determined by the regulator 735 (as measured by the flow meter 778 and obtained by the regulator 735 via line 778 ′, the atomizer and the pump. Indirectly measured by correlating the inflow of the first liquid through the 7575b and the outflow of the second liquid through the pump 751a, or directly by using a height measuring device (not shown for clarity) in the reaction chamber. Can be measured. Height measuring devices are well known in the art.

The height of the liquid in the holding tank 753 is controlled by the height adjuster 755. When the liquid level falls below the height B, the pump 751c is stopped by the regulator 755. When the liquid height exceeds the height A, the pump 751c is restarted by the regulator 755. Retention tank 753 should contain sufficient liquid at its lowest height B to prepare for any desired variation in liquid height 756 in reaction chamber 712.

The increase or decrease in the spray distance is preferably at a spray distance increment, preferably in the range of 2 to 5%, for the particular measurement time.

After the predominant determinants are found to be within the most desirable range, the predominant determinants are continuously observed, as already described, in most cases such that the determinants are all located somewhere near the median of their most preferred range. As in the previous embodiment, continuous observation and control is highly desirable because the conditions in the reaction chamber can change to change the determinants. Valves that are controlled by computerized regulators and that control the proportion of liquid in accordance with certain programs are well known in the art.

Returning to FIG. 1, separator 15 can be any simple or complex assembly device capable of separating the intermediate oxidation product from the second liquid as described above. Such devices are well known in the art, for example, as disclosed in many patents relating to the separation of adipic acid from mother liquor (in this case a second liquid).

When the adipic acid oxidation product is a solid with limited solubility in the second liquid at the reaction temperature or any other temperature, such as when cyclohexane is oxidized to produce adipic acid, the separator 15 ) May include two filters 15a and 15b connected in parallel as shown in FIG. 10. Separator 15 may also include valves 15w, 15x, 15y and 15z, and any heat removal device 15i that may take the form of crystallizers.

In the operation of this separator, the valves 15x and 15y are opened first, and the valves 15w and 15z are closed. While the valves 15w and 15z are closed, any solid oxidation product that has first accumulated in the filter 15a, such as, for example, adipic acid, can be manually or automatically (e.g., a bag well known in the art). -Flushing, scraping, etc./not shown) is separated from the filter 15a. The second liquid provided from line 24, optionally passing through heat removal device 15i, to bring the liquid temperature to a temperature more suitable for solid separation, passes through filter 15b, where the solid oxidation product is from the second liquid. The second liquid is removed and conveyed through line 11 to be recycled to recycle tank 19 (FIG. 1) or to be further processed in other apparatus (not shown). When the filter 15a is almost empty and the filter 15b is almost full or ready to be emptied, the valves 15w and 15z are opened and the valves 15x and 15y are closed so that the filtration of the solid oxidation product This is now done in filter 15a while filter 15b is emptied. In this process, the cycle is repeated. Of course, other devices such as, for example, rotary drum filters can also be used.

In another embodiment of the present invention shown in FIG. 11, the apparatus 810 of the present invention adds a condenser 857 connected to the gas outlet 823 via line 825 and to the condensate tank 859. (The condensate tank is used as a reservoir of condensate collected from condenser 857). Condensate tank 859 is connected to line 865 'via valve 865 (which in turn is connected to liquid dispersion ring 844), or to line 865 (which is again condensed) To line 811 for recycling the liquid to recycle tank 819). The valve 865 carries all of the condensed liquid to the line 865 ', all to the line 865, or some to the line 865' and some to the line 865, or is closed It is applied not to allow the movement of the condensation liquid.

Apparatus 810 includes a heat exchanger 838 connected to recirculation tank 819, an exhaust or intake 861 connected to heat exchanger 838, an atomizer connected to exhaust 861 at the inlet and at the other end. It further includes a pump 877 connected to 826. Exhaust 861 includes control valve 807 (when control valve 867 is in the open position) and inspection valve 867a that allows flow from line 867 'to the pump, but not vice versa. Is applied to provide vacuum to line 867 '. Line 867 ′ is connected to line 857 ′ between condenser 857 and valve 864. An additional pump (not shown) can be disposed between the heat exchanger 838 and the exhaust 861 that can regulate the vacuum provided to the line 857 ′ by the exhaust 861 along with the pump 877. . This may also be used to prevent depletion of the first liquid in the pump 877. The heat exchanger 838 can be part of the condenser 857 (not shown as such in FIG. 11) so that the heat received from the condensable material can be used as the heat source of the heat exchanger 838.

Lines 841a, 841b, and 841c are used to supply appropriate amounts of raw materials, catalysts, solvents, initiators, accelerators, and the like to the recycle tank.

In operation of this embodiment, the first liquid supplied from the recycle tank is heated to the desired temperature in heat exchanger 838. The heated first liquid is pumped through the pump 877 to the atomizer 826 where it is broken down into droplets 848 and finally coalesced onto the second liquid 854 as already discussed in the above embodiments. . At the same time, a gas containing an oxidant (preferably oxygen) enters the reaction chamber 812 in the flow direction opposite to the droplet as also discussed above, and the oxidant is contained in the droplet of the first liquid. React with reactants. Any off-gas formed during the reaction, which is usually non-condensable unless treated at very low temperatures, exits the reaction chamber 812 through the gas outlet 823 along with the condensable material. Along line 825 they enter condenser 857 where condensable material condenses into condensate, which accumulates in condensate tank 859.

In the case where it is desirable to form the curtain or thick film 845, the condensate is at least partially conveyed through the valve 865 to the line 865 ′, where it is supplied to the liquid dispersion ring 844, and optionally The curtain 845 is useful to prevent the reaction or other solid product from adhering to the septum of the reactor 812. The condensate has an advantage, for example, relative to the recycled liquid flowing through line 11 ′ of FIG. 1, which in most cases is substantially free of catalyst. This is because in the practice of the present invention in most cases non-volatile catalysts such as, for example, metal salts are used.

If there is no need to supply condensate to the liquid dispersion ring, the valve 865 conveys the condensate to line 865, which supplies the condensate to line 811 so that the condensate is finally To be transported to recycle tank 819. In general, as discussed above, valve 865 carries all of the retained liquid to line 865 ', all to line 865, or some to line 865' and some to line ( 865, or closed to allow movement of the condensed liquid.

Non-condensable gas flows along line 857 ′ and exits the system through valve 864 as needed. The valve 864 may be adjusted to open and close, preferably to any degree desired for operation, as also shown in other embodiments. In cases where it is desirable to remove all non-condensable gases from the system, valve 864 opens to a predetermined degree to maintain the pressure inside the system at a predetermined level, and valve 867 is fully closed. If only partial removal of the non-condensable material is desired, both the valves 864 and 867 are opened to some extent such that a vacuum formed by the exhaust or inhaler 861 is introduced into the reaction chamber 812 by vacuum. Recycle part of the non-condensable material. Complete recycling of the non-condensable material without discharging it from the system means that after a certain point no new flow of gas containing the oxidant occurs, so that the pressure inside the reaction chamber 812 does not exceed the final predetermined limit. Only if you do not. The inspection valve 867a does not impede the flow of non-condensable material but prevents the first liquid from entering the line 867 ′ if the intake 861 accidentally pulls out.

In another embodiment of the present invention shown in FIG. 12, the apparatus 910 of the present invention adds a condenser 957 connected to the gas outlet 923 via line 925 and connected to the condensate tank 959. (The condensate tank is used as a reservoir of condensate collected from condenser 957). Condensate tank 959 is connected to liquid dispersion ring 944. Condenser 957 is also connected to valve 964 via line 957 ′, which valve is adapted to release non-condensable material in the open position.

The apparatus 910 further includes a heat exchanger 938 connected to the recycle tank 919 and connected to the atomizer 926 at the other end. The apparatus further comprises a gas pump 961 connected to line 957 'through line 947' which is adapted to convey non-condensable material from line 957 'to gas inlet supply line 936. Include. Replenishment gas line 936 'is also connected to line 936 for providing fresh gas containing an oxidant (preferably oxygen).

The heat exchanger 938 can be part of the condenser 957 (not shown in this way in FIG. 11) so that the heat received from the condensable material can be used as the heat source of the heat exchanger 938.

Lines 941a, 941b and 941c are used to supply appropriate amounts of raw materials, catalysts, solvents, initiators, accelerators, and the like to the recycle tank.

In operation of this embodiment, the first liquid supplied from the recycle tank is heated to the desired temperature in heat exchanger 938, enters atomizer 926, where it is broken down into droplets 948, and finally As already discussed in the above embodiment, it adheres to the second liquid 954. At the same time, a gas containing an oxidant (preferably oxygen) enters the reaction chamber 912 in the flow direction opposite to the droplet as also discussed above, and the oxidant is contained in the droplet of the first liquid. React with reactants. Any off-gas formed during the reaction, which is usually non-condensable unless treated at very low temperatures, exits the reaction chamber 912 through the gas outlet 923 along with the condensable material. Along line 925 they enter condenser 957 where condensable material condenses into condensate, which accumulates in condensate tank 959.

The condensate is conveyed at least in part to the liquid dispersion ring 944 as discussed in other embodiments, such that curtain 945 is useful for preventing any reaction or other solid product from adhering to the septum of reactor 912. To form. This condensate has an advantage over the recycled liquid which enters through line 11 ′ of FIG. 1, for example, which in most cases is substantially free of catalyst. This is because in the practice of the present invention in most cases non-volatile catalysts such as, for example, metal salts are used.

If there is no need to supply condensate to the liquid dispersion ring 944, the condensate may be conveyed elsewhere via line 959 ′.

Non-condensable gas flows along line 957 ′ and exits the system through valve 964 as needed. The valve 964 may be adjusted to open and close, preferably to any degree required for operation, as also shown in other embodiments. In the case where it is desirable to remove all non-condensable gases from the system, valve 964 is opened to a predetermined degree to maintain the pressure inside the system at a predetermined level, and the shimp 961 stops operating. In cases where it is desirable to only partially remove the non-condensable material, the valve 964 opens to a predetermined degree and the pump 961 also operates to a predetermined degree so that a portion of the non-condensable material is recycled to the reaction chamber 912. do. Complete recycling of the non-condensable material without discharging it from the system does not allow fresh flow of the inert gas diluent after a certain point so that the pressure inside the reaction chamber 912 does not finally exceed the predetermined limit. I can do it.

Second liquid 954 is conveyed to separator 915 via line 924 where the intermediate oxidation product is separated and the remaining liquid is sent to another separator (not shown) for further separation of the components, or recycled To the recirculation tank 919 or treated in a combination of both.

In another embodiment of the present invention shown in FIG. 13, the reaction chamber 1012 is preferably a gas outlet 1023 that coincides with the liquid outlet 1022, near the bottom end 1016 of the reaction chamber 1012. Has Both the gas distributor 1073 supplied by the gas inlet line 1036 and the atomizer 1026 supplied by the line 1042 are preferably disposed at the upper end 1014 of the reaction chamber 1012. Gas distributor 1073 and atomizer 1026 may be combined in one unit, and the gas may be used to assist or be solely responsible for the atomization process.

The liquid / gas outlets 1022/1023 may be conical, preferably with a diameter reduced as compared to the diameter of the reaction chamber 1012, as shown in FIG. 13. The liquid dispersion ring 1044 may be located at the bottom of the reaction chamber, as shown in FIG. 13, or at the top 1023 ′ of the liquid / gas outlet 1022/1023. Preferably, the liquid dispersion ring 1044 is adapted to deliver the liquid in a vortex fashion. Place a cooler (not shown) in line 1011 'to cool the liquid to a predetermined temperature suitable for condensing the condensable material exiting reaction chamber 1012 through liquid / gas outlet 1022/1023. You can.

Also provided is a liquid / gas separator 1075 for receiving condensed and non-condensable material from the reaction chamber 1012 via line 1025 and for separating the second liquid 1054 from the non-condensable material. The liquid / gas separator 1075 is in turn connected to a separator 1015 that is applied to separate intermediate oxidation products from reactants and other materials introduced into the system in the process.

In operation of this embodiment, the first liquid is introduced to atomizer 1026 via line 1042, where it is broken up into droplets 1048 and finally preferably in liquid / gas outlet 1022/1023. Adhesion near bottom end 1016 on curtain or thick membrane 1045. At the same time, a gas containing an oxidant (preferably oxygen) enters the reaction chamber 1012 in the same direction as the movement of the droplets, and both the droplet and the gas are at the upper end 1014 of the reaction chamber 1012. As it moves from the bottom end 1016 direction, it reacts with the first reactant contained in the droplets of the first liquid. The condensable material condenses on the swirling cold liquid entering the system via line 1011 ′. Liquid entering the reaction chamber via line 1011 ′ may be obtained from within the system or from outside the system. Any off-gas formed during the reaction, which is usually non-condensable unless treated at very low temperatures, exits the reaction chamber 1012 through the liquid / gas outlet 1022/1023 along with the condensable material. Along line 1025 they enter the liquid / gas separator 1075, where the second liquid 1054 is separated from the non-condensable material, and the non-condensable material is removed through line 1057 ′ and valve 1064. (The valve may be operated as already discussed in the previous embodiment).

Second liquid 1054 is conveyed to separator 1015 where it is treated as already discussed in the previous embodiment.

As mentioned earlier, condensation of the condensable material may be used to remove non-condensable materials, such as various off-gases, which may include, for example, one or more oxygen, nitrogen, carbon monoxide, carbon dioxide, etc., in FIGS. 11 and 12. It may take place in each condenser 857 and 957 before each valve 864 and 964 inside a compression device such as each device 810 and 910 used. According to the invention this particular form of condensation is defined as internal condensation even if carried out outside the reaction chamber, which takes place at a pressure substantially equal to the reaction pressure.

According to the invention, internal condensation inside the reactor can also occur, and in most cases internal condensation outside is preferred. Internal condensation (before the actual pressure drop) is much more desirable than external condensation (after the actual or overall pressure drop). Internal internal condensation is particularly suitable when an oxidant is used which is close to a stoichiometric amount in the oxidation process.

One embodiment of the invention utilizing internal inner condensation is shown in FIG. 14, where only a limited number of members are shown for clarity. A cooling film 1183 is provided that surrounds all or part of the height of the reaction chamber 1112. In addition, the reaction chamber 1112 includes the same member as in the previous embodiment.

Operation of this embodiment is similar to that of the previous embodiment except that coolant enters membrane 1183 via line 1182 and exits through line 1182 ′. The temperature of the coolant is the temperature at which the partition 1120 is cooled such that the vapor of condensable material in the reaction chamber is condensed to form a thick film or curtain 1145. Since catalysts (eg metal salts such as cobalt acetate) are not volatile in most cases, they do not transfer to the curtain. In addition, the temperature of the thick film is lower than the temperature of the droplets. Thus, substantially no reaction takes place in the curtain, and in addition to other advantages, the thick film or curtain 1145 prevents solids from adhering to the septum of the condenser.

Another embodiment of the present invention utilizing internal internal condensation is shown in FIG. 15, where only a limited number of members are shown for clarity. A cooling coil 1283 inside the reaction chamber 1212 is provided, having a coolant inlet line 1282 and a coolant outlet line 1282 ′. This coil may extend over the entire height of the reactor or only over a portion thereof. The coil 1283 may be positioned vertically, horizontally, or any other position suitable for the direction of the surrounding environment, as shown in FIG. 15. In addition, the reaction chamber 1212 includes the same members as in the previous embodiment.

Operation of this embodiment is similar to that of the previous embodiment except that coolant enters the coil 1283 through line 1282 and exits through line 1282 '. The temperature of the coolant is the temperature at which the coil 1283 is cooled such that steam of condensable material in the reaction chamber is suitable for condensation on the coil 1283. Since the catalyst (eg a metal salt such as cobalt acetate) is not volatile in most cases, it does not migrate to the condensate on the coil. In addition, the temperature of the condensate on the coil 1283 is lower than the temperature of the droplets. Thus, the reactants and catalyst contained in the droplets condensed on the coil are significantly diluted and substantially no reaction occurs in thick membranes (not shown) formed on the coil from the concentrate and coalesced liquid. The thick film also prevents solids from adhering to the coil.

Another embodiment of the invention utilizing internal inner condensation is shown in FIG. 16, where only a limited number of members are shown for clarity. At the upper end 1314 of the reaction chamber 1312, which has a cooling liquid inlet line 1384, is preferably provided a cooling liquid injector 1385 disposed above the top of the atomizer 1326. In addition, the reaction chamber 1312 includes the same member as the previous embodiment.

Operation of this embodiment is similar to that of the previous embodiment, except that cooling liquid enters the cooling liquid injector 1385 via line 1384. This liquid is then sprayed by injector 1385. The cooling liquid preferably comprises the same solvent contained in the first liquid or the same first reactant contained in the first liquid. For example, when preparing adipic acid from cyclohexane, the cooling liquid preferably comprises acetic acid (solvent), or cyclohexane (first reactant), or mixtures thereof. Preferably, the catalyst is not contained in the cooling liquid. The temperature at which the cooling liquid is sprayed is the temperature at which the condensable material condenses on the droplets of the sprayed cooling liquid to cause internal internal condensation. As mentioned above, the droplets of the first liquid are not mixed with the cooling liquid droplets for all practical purposes, both of which are suspended in a gas so that the oxidation reaction is not disturbed in the droplets of the first liquid. Finally, two kinds of droplets are coalesced together at the bottom end 1316 of the reaction chamber 1312 to form a second liquid 1335, which is then used for further processing as described in the previous embodiment. Removed via line 1324. In measuring the temporary conversion rate before coalescence, the flow rate of the cooling liquid and the flow rate of the first liquid should be taken into account by techniques well known in the art in a regulator (e.g., shown as (35) in FIG. 1).

Another embodiment of the invention utilizing internal inner condensation is shown in FIG. 17, where only a limited number of members are shown for clarity. There is provided a cooling liquid injector 1485 having a cooling liquid inlet line 1484, preferably disposed at the upper end 1414 of the reaction chamber 1412. Injector 1485 preferably has a plurality of spray nozzles 1486 around its periphery. The spray nozzle 1486 is directed towards the partition wall 1420 of the reaction chamber 1412. In addition, the reaction chamber 1412 includes the same members as the previous embodiment.

Operation of this embodiment is similar to that of the previous embodiment except that cooling liquid enters the cooling liquid injector 1485 via line 1484. This liquid is then sprayed by the injector 1485 and falls over the partition 1420 of the reaction chamber 1412, where it forms a thick film or curtain 1445. The cooling liquid preferably comprises the same solvent contained in the first liquid or the same first reactant contained in the first liquid. For example, when preparing adipic acid from cyclohexane, the cooling liquid preferably comprises acetic acid (solvent), or cyclohexane (first reactant), or mixtures thereof. Preferably, the catalyst is not contained in the cooling liquid. The temperature at which the cooling liquid is sprayed is the temperature at which the condensable material condenses on the droplets of the sprayed cooling liquid and on the curtain 1445 to cause internal internal condensation. Since the catalyst (eg a metal salt such as cobalt acetate) is not volatile in most cases, it is not transferred to the curtain 1445. In addition, the temperature of the thick film is lower than the temperature of the first liquid droplets. Thus, substantially no reaction occurs in the curtain 1445, and in addition to other advantages, the thick film or curtain 1445 prevents solids from adhering to the partition walls of the condenser. The liquid and droplets are finally mixed together at the bottom end 1416 of the reaction chamber 1412 to form a second liquid 1454, which is line 1424 for further processing as described in the previous embodiment. Is removed.

In another embodiment of the present invention shown in FIG. 18, one or more thermocouples 1560b and / or sample collector 1530 ′ arranged within the reaction zone 1534 are provided, which are preferably computerized regulators ( Not shown). Thermocouple 1560b and / or sample collector 1530 ′ react to observe the temperature and / or conversion rate of the droplets deposited at different distances between the top end 1532 and bottom end 1542 of reaction chamber 1522. May be placed in any suitable location of the band 1534.

In operation of this embodiment, thermocouple 1560b takes the temperature of the droplets and supplies this information to a regulator (not shown) as described in the above embodiments. Similarly, the sample collector supplies the liquid adhered from the droplets to the conversion rate monitor (not shown), which in turn supplies the conversion rate information to a regulator (not shown) as described in the above embodiments. Based on this information, the regulator adjusts the reaction as needed and gives appropriate instructions to the other members of the device so that the temperature does not deviate from the intended range in order to prevent catastrophic events occurring when too much reaction heat is released. This provides additional safety.

One thermocouple (preferably, a thermocouple close to the bottom end 1542) may be used to observe the temperature, but one or more thermocouples in the reaction zone 1534 may be used to measure the rate of temperature rise or the temperature profile within the droplet path. It is more preferable to use 1560b. The temperature difference between these two thermocouples is called the temporary fine temperature difference. The larger the temperature change (temporary fine temperature difference) from thermocouple to thermocouple, the greater the changer indicates.

In another embodiment of the present invention shown in FIG. 19, an apparatus 1610 is shown for producing an intermediate oxidation product from a gas containing a first liquid and a second reactant containing a first reactant. The device 1610 includes a reaction chamber 1612 having a top end 1614 and a bottom end 1616. Chamber 1612 preferably has a cylindrical shape that is conical near bottom end 1616 and finally leads to liquid outlet 1622 connected to outlet line 1624. The outlet line 1624 leads to a pump 1618 that connects to the first valve 1615 via line 1624a. The first valve 1619 is applied to connect line 1624a to line 1624b or line 1624c, or to connect some to line 1624b and some to line 1624c. Line 1624b again leads to reaction chamber 1612 at atomizer 1626 (via line 1641), preferably located at upper end 1614 of reaction chamber 1612. Atomizer 1626 preferably has a plurality of nozzles 1627, which are more preferably in airless form as is well known in the art. The atomizer 1626 may be fixed at a specific location in the reaction chamber 1612, or may preferably move in an up-down manner as described above, for example.

Line 1624c is a second valve 1615a that is applied to connect line 1624c to line 1624d or line 1624f, or partly to line 1624d and partly to line 1624f. Leads to. Line 1624d separates the intermediate oxidation product from the reactants and recycles unreacted reactants through line 1611 (not shown), usually containing varying amounts of intermediate oxidation products, solvents, catalysts and other adducts. It leads to the separator 1615 to convey. The separator may also be a simple device such as a filter or a complex device such as a set of tanks, washers, extruders, distillation columns and the like, to suit each particular case as described above. Line 1624f leads to device 1612a which may be another reaction chamber or a set of reaction chambers or other apparatus including, but not limited to, tanks, washers, extruders, distillation columns, and the like. Device 1612a is connected to separator 1615 via line 1611a, particularly when device 1612a is a simple reaction chamber or a set of reaction chambers.

Near the upper end 1614 of the reaction chamber 1612 is provided a gas outlet 1623 which leads to a gas outlet line 1625.

A gas inlet 1634, preferably located near the bottom end 1616 of the reaction chamber 1612, provides a gas inlet supply for providing a gas containing a second reactant (preferably an oxidant such as, for example, oxygen). Is connected to line 1636.

Thermocouple 60 or other temperature measuring means is preferably arranged in the atomizer to measure the spray temperature, which is the temperature of the first liquid immediately before spraying. One or more thermocouples 60a are disposed in reaction chamber 1612, while thermocouple 60b is disposed in second liquid 1654 at the bottom of reaction chamber 1612 to measure the temperature of second liquid 1654. do.

Within the reaction chamber 1612, as also described above, a droplet rate detector, which collects the droplets, preferably via a sample line 1633 as a fine stream of liquid (the detector according to the invention also includes the meaning of a monitor). There is further provided a (one or more) sample collector 1630 for conveying 1616. Conversion detector 1632 may measure the amount of first reactant and the amount of intermediate oxidation product as the first liquid enters the nebulizer through suitable sample line (s) (not shown for clarity). This information can, for example, accurately measure the amount of first reactant and intermediate oxidation product delivered to atomizer 1626, along with information about the nature and quality of the material supplied in line 1641. The conversion rate in the second liquid 1654 can also be detected or observed through the sample line 1633 'connecting the line 1624a and the conversion rate detector 1632.

The device 1610 further comprises a computerized regulator 1635, preferably provided with information about the temperature via input lines 60 ′, 60 a ′ and 60 b ′. The regulator 1635 is also provided with information regarding the conversion rate of the reactant to the intermediate oxidation product from the detector 1632 via an input line 1631. Again, the regulator 1635 adjusts a number of means for adjusting the conversion rate and / or temperature to control the rate of oxidation through one or more output lines 1636 as detailed above. Such means and their operation (examples described above) include, but are not limited to, heat exchangers (e.g., heat exchanger 1645 in line 1644), and spray temperature, reaction pressure, spray distance, Average droplet diameter, first flow rate (speed at which droplets are generated from the first liquid), second flow rate (flow rate of gas), volatilization rate (speed at which volatile components contained in the droplets volatize), first content ( Other means for changing the content of the first reactant in the first liquid), the second content (the content of the second reactant in the gas, preferably the oxidant), the catalyst content (in the first liquid), and combinations thereof Included. For the sake of simplicity and clarity, these means are excluded from FIG. 19.

Monitor or detector 1632 can be any device that can be applied to detect intermediate oxidation products or products. This is for example a chromatographic device (e.g. GC and / or HPLC), UV spectrometer, IR spectrometer, visible light spectrometer, mass spectrometer, NMR device, conductivity monitor, ionization detector, flame detector, any other suitable device, Or combinations thereof.

If the intermediate oxidation product is a nonvolatile acid, the monitor or detector 1632 preferably comprises HPLC (high pressure / performance liquid chromatography apparatus) with a UV monitor. In addition, the HPLC apparatus has one or more columns, and when the separation time in the column is longer than the predetermined time, a predetermined range of intervals for introducing a series of samples into different columns and performing a plurality of separations to observe the series of samples is determined. Is preferred. If the non-polar organic portion is to be analyzed, it is preferable to include a gas chromatography monitor or detector combined with a suitable monitor such as, for example, an ionization monitor.

Combinations of HPLC and GC can be used where polar and nonpolar components are included.

The method and apparatus of the present invention are particularly suitable for the oxidation reaction of organic compounds in which the main part of the oxidation product is CO, CO ₂ or a mixture thereof and other oxidation intermediates. One reason is that the complex determinants of the present invention will significantly improve the reaction rate, reaction uniformity, yield and other important properties, while the absence of such determinants will result in complete oxidation to CO / CO ₂ . Because. Indeed, the same spraying conditions without these determinants have recently been used in automobile combustion engines and other devices to substantially completely oxidize (ie, burn) organic compounds such as gasoline into a mixture of CO / CO ₂ . .

On the other hand, according to the invention, for example, when the first reactant is cyclohexane, most of the oxidation products are substantially cyclohexanol, cyclohexanone, cyclohexylhydroperoxide, caprolactone, adipic acid and the like and these It may be a mixture of. Organic acids are preferred intermediate oxidation products.

Operation of embodiments of the present invention will be discussed for any non-degradable oxidation reaction encompassed by the claims, which includes cyclohexane as the first reactant, oxygen as the oxidant in the gas, and adipic acid as the intermediate oxidation product. Will be illustrated using. The term intermediate oxidation product means stopping the oxidation reaction before the first reactant is substantially oxidized to carbon monoxide, carbon dioxide or a mixture thereof.

Although three sample lines for three thermocouples and conversion rates are shown, these members can be used in fewer or larger numbers. However, at least one thermocouple or one sample line should be used. Also, device 1610 need not have all of the illustrated members, such as device (s) 1612a, for example.

In operation, a first liquid containing a first reactant (eg, cyclohexane) is introduced into the reaction chamber 1612 via line 1644 and in a manner to form a plurality of droplets 1648. ) And nozzle 1627. The first liquid enters the nebulizer at a predetermined spray temperature (preferably in the range of 50-150 ° C., more preferably 80-130 ° C., most preferably 90-120 ° C. for cyclohexane). Of course, other temperatures may be used depending on the particular environment. The spray temperature of the first liquid is the temperature just before the liquid is atomized. The temperature of the freshly formed droplets may be the same or different than the spraying temperature. In the case of cyclohexane, the first liquid is preferably a solvent (e.g. acetic acid), a catalyst (e.g. cobalt compound) dissolved in the first liquid, an initiator (e.g. cyclohexanone, methylethylketone, acetaldehyde, etc.) and Mixtures thereof). In the case of oxidizing cyclohexane to adipic acid, the pressure should preferably be high enough to keep the cyclohexane, solvent, initiator and the like substantially in the liquid state. Even pressures in excess of 1,000 psia may be used, but the pressure is preferably in the range of 100 to 400 psia, more preferably 150 to 300 psia.

At the same time that the first liquid is sprayed, a gas containing an oxidant (preferably oxygen in the case of cyclohexane) is passed through the gas inlet supply line 1636 near the bottom end 1616 of the chamber 1612. Flows into). The gas may contain, in addition to the oxidant, a somewhat inert gas such as, for example, nitrogen and / or carbon dioxide. Off gas mixed with vapors of reactants, solvents, mists, etc., exits the reaction chamber via gas outlet line 1625.

As the droplets drop downward from atomizer 1626 they begin to react with oxidants (eg oxygen). The second liquid 1654 is preferably removed continuously through the liquid outlet 1622 and pumped through the liquid outlet line 1624 by the pump 1618.

If continuous operation is desired, the second liquid is first recycled through lines 1624a, 1624b and 1624 until the conversion reaches a desired value. At this point, the valve 1615 passes a portion of the second liquid having a desired conversion value through the separators 1615 via lines 1624c and 1624d, or for lines 1624c and (for further processing). Open to some extent to pass through device 1612a through 1624f. Valve 1619a may deliver all liquid from line 1624c to separator 1615 or device 1612a, or to a portion of separator 1615 and a portion to device 1612a, depending on the particular environment. Can be. The remaining second liquid that did not enter line 1624c is recycled to atomizer 1626 via lines 1624b and 1624. Replenishment liquid containing the first reactant and the like enters the system via replenishment line 1641. The composition and amount of replenishment liquid entering the system is a value that preferably replenishes the amount of component removed via line 1624c.

In the case of batch operation, when a suitable first liquid is supplied to the device 1610 via the refill line 1641, the total amount of the second liquid is in line 1624b and 1642 until the desired conversion rate is reached. Is recycled to atomizer 1626, at which point the second liquid is reacted to the reaction chamber 1612 via suitably activated valve 1619 (and valve 1619a as needed) and line 1624c. May be discharged from and introduced into separator 1615 or device 1612a for further processing, or a portion may enter separator 1615 and a portion may enter device 1612a. Fresh first liquid enters the system via refill line 1641 and the circulation is repeated.

In separator 1615, the intermediate oxidation product (eg, adipic acid) is separated from the liquid by techniques well known in the art. In some cases, other oxidation by-products may also be removed from the separator as needed. Reactants, solvents, catalysts, etc., are returned via line 1611 to a recycle tank (not shown). If at least a portion of the second liquid 1654 is at least partially conveyed to the device 1612a, it may be conveyed back to the separator 1615 through line 1611a after any treatment in the device 1612a. have.

A portion of droplet 1648 falls over thermocouple 60a, which in turn supplies temperature information to regulator 1635 via output line 60a '. The spray temperature and the temperature of the second liquid are also supplied to the regulator 1635 via input lines 1660 'and 1660b', respectively. At the same time, a portion of the droplets also fall into the same collector 1630, from which they are moved to a conversion rate detector or monitor 1632 to be analyzed for conversion rate. If solids are present in the droplets, care should be taken to avoid clogging of the liquid transfer line by using a suitable diluent or the like. In addition, a small stream of second liquid is conveyed through the line 1633 'to the conversion rate detector 1632 to be analyzed for conversion. As mentioned above, in the case of adipic acid or other acid formation, the monitor 1632 preferably comprises a chromatography device, more preferably a high performance (or high pressure) liquid chromatography device (HPLC), and more Preferably in combination with a GC (gas chromatography) apparatus. This system also preferably has a suitable number of columns, as mentioned above, allowing the droplet to measure multiple times the intermediate oxidation product present in the second liquid mass 1654, thereby providing intermediate reaction products of the first reactant. Each conversion rate to the furnace should be checked as often as desired in each particular case. For example, if the column separates the intermediate oxide product within 8 minutes, and in certain cases the desired measurement interval is 2 minutes, four columns are required.

It may also be desirable to collect the liquid at other locations, which may be performed using the same detector 1632 or different detectors (not shown).

Information obtained from the conversion rate detector or monitor 1632 is supplied to the computerized regulator 1635 via an input line 1631, where this information is associated with lines 1660 ', 1660a' with respect to respective temperatures. The information received through 1660b 'is processed by methods well known in the art.

The regulator 1635 adjusts the aforementioned heat exchanger 1645 (not shown) or any of a variety of means that may be used to adjust any determinant as detailed in the applicant's co-pending application. do. For the purpose of simplicity, simplicity and clarity, a heat exchanger 1645 will be discussed here that illustrates one means of adjusting the determinants to control the rate of oxidation, and the same principles apply to any other means. You have to understand.

In the control of the reaction rate, the temperature of the thermocouple 1660 for measuring the temperature inside the reactor is given priority, followed by the spray temperature of the thermocouple 1660, and then the second liquid 1654 measured by the thermocouple 1660b. It is preferable to give priority to temperature. The conversion of the first reactant to the intermediate oxidation product in the same collector 1630 is preferentially followed by the conversion of the first reactant to the oxidation product provided in the paths of lines 1624a and 1633 '. do. It may be desirable to adjust one or more determinants to control the rate of oxidation, especially for fast reactions or very long reaction chambers, but only one determinant may be used, especially for relatively slow reactions. There are other cases that allow. Indeed, in the case of very fast or very long reaction chambers, it is desirable to measure the temperature and conversion over the entire length of the reaction chamber using multiple thermocouples 1660a and sample collector 1630.

The regulator 1635 is preferably applied by techniques well known in the art to determine what action should be taken to adjust the determinant not only by the absolute value of the measured value, but also by the difference in absolute value and the rate at which the determinant changes. For example, in the case where the temperature difference between thermocouples 60 and 60a increases at a faster rate than the desired rate, the regulator may be particularly hot even if the temperature of thermocouple 1660a is higher than the temperature of thermocouple 1660. More thorough measurements will need to be instructed than if they do not rise at a rapid rate. This also applies to thermocouples 1660a when there are multiple thermocouples 1660a, and also to conversions and conversion rates from samples provided by different sample collectors 1630 when multiple sample collectors 1630 are used. .

Assuming at least one thermocouple 1660a is present, regulator 1635 first determines based on the temperature provided by thermocouple 60a. If the temperature exceeds the desired temperature range, heat exchanger 1645 is directed by regulator 1635 to reduce the temperature of the first liquid conveyed from line 1644 to atomizer 1626. This change is 10 to 50%, more preferably 10 to 30% increments of the temperature of the liquid as it enters the heat exchanger, measured by thermocouple (not shown for clarity) and provided to the regulator 1635. It is preferable. However, other ranges may be more suitable, depending on the particular conditions, materials, previous measurements, and the like. For example, if a decrease of 10% in temperature is found to have no appreciable result, the following increment may be made, for example, 30%. On the other hand, if a 10% reduction in spray distance causes an excessive change in temperature, until the temperature reaches a value in the desired range, preferably the most preferred range, more preferably near its most preferred set point The following increment may be 5%, for example.

For example, in the case of oxidizing cyclohexane to adipic acid, the preferred temperature range is 50 to 150 ° C, more preferably 80 to 130 ° C, most preferably 90 to 120 ° C. However, depending on the particular circumstances, other temperatures that are much higher or much lower than the temperature may be more suitable when the cyclohexane is oxidized to adipic acid.

After the temperature is found to be within the most preferred range, in most cases it is continuously observed to be located near the median of the most preferred range. Of course, continuous observation and control is highly desirable because the conditions in the reaction chamber can change to change the temperature before coalescence.

Preferred ranges may be constant or may vary with time, conversion and other desired parameters.

After the first determinant has been found to be within its preferred range, other determinants may be adjusted within their preferred range one by one in the order described above so long as they do not interfere with the first determinant. In the absence of a first determinant, the second determinant is given priority and the same technique is performed as described above for the first determinant until the second determinant is within its predetermined range.

Usually, the predetermined range for thermocouple 1660 should be lower than the range for thermocouple 1660a. The temperature change exhibited by the thermocouple 1660b is essentially slower than the temperature change exhibited by the thermocouple 1660a due to the second liquid mass 1654. If the determinant is the temperature of the thermocouple 1660b, the volume of the second liquid 1654 at the bottom end 1616 of the reaction chamber 1612 is as fast as possible for the temperature change of the droplets in the reaction chamber 1612. It is important to be as small as possible in order to respond.

It is highly desirable to use one temperature determinant and one conversion determinant simultaneously to control the rate of oxidation.

The rapid oxidation and / or long reaction chamber may require one or more sample collectors 1630, as already mentioned, and the slow oxidation and / or short reaction chamber may be via the second liquid 1654 via line 1633 '. Can only depend on the conversion rate measured in

Conversion of the initial position between the atomizer and the point where lines 1641 and 1642 meet, and any subsequent point before any recycle or after any number of recycles, can be determined by any It can be carried out in consideration of external influences, from which the oxidation rate can be calculated. The regulator 1635 directs the heat exchanger 1645 from the conversion rate data in a manner similar to that made from the temperature data. The conversion per measurement time interval (in a single pass or any desired number of recycles) may preferably be maintained between 0.05% and 80%, although other values may be suitable in certain cases. This is also true for adipic acid formation, which in some cases may have very low conversion values and in others it may be very large. However, the range of 0.05% to 80% is the preferred range.

Many catalysts used for oxidation are transition metals having one or more valence states. Their main catalysis occurs when they have a higher valence state than the lowest valence state when they are present as ions. One good example is cobalt when oxidizing cyclohexane to adipic acid. The initial time before initiation of the oxidation reaction is often devoted to the investigation of the addition of cobalt ions having a valence state of II. Cobalt catalysts are added in valence II, for example, because divalent cobalt acetate is the easiest to purchase and cheaper than trivalent cobalt acetate. Thus, if so far no Cobalt II is used or if Cobalt II has not been pre-oxidized, it takes time to oxidize the bivalent cobalt ions to trivalent cobalt ions and to initiate the action as a catalyst according to the methods of the art. In addition, it takes time to oxidize cobalt II ions to cobalt III ions due to the small interface provided by the bubbling of gas through the solution.

In the case of the present invention, this oxidation time is significantly reduced due to the provision of high surface areas.

In addition, divalent cobalt ions can be oxidized in advance to trivalent cobalt ions.

As mentioned above, the oxidation reaction according to the invention is a non-degradable oxidation reaction in which the oxidation product is not carbon monoxide, carbon dioxide, and mixtures thereof. Of course, small amounts of these compounds may be formed with oxidation products, which may be one product or a mixed product.

Examples include, but are not limited to, the following.

Preparation of C ₅ -C ₈ aliphatic dibasic acids from the corresponding saturated alicyclic hydrocarbons, for example the production of adipic acid from cyclohexane.

Preparation of C ₅ -C ₈ aliphatic dibasic acids from hydroperoxides of corresponding ketones, alcohols, and saturated cycloaliphatic hydrocarbons (e.g. Adip from cyclohexanone, cyclohexanol, and cyclohexylhydroperoxide) Production of acids).

Preparation of C ₅ -C ₈ cyclic ketones, alcohols and hydroperoxides from the corresponding saturated cycloaliphatic hydrocarbons, for example the preparation of cyclohexanone, cyclohexanol and cyclohexylhydroperoxide from cyclohexane.

Preparation of aromatic polyacids from the corresponding polyalkyl aromatic compounds (eg preparation of phthalic acid, isophthalic acid and terephthalic acid from o-xylene, m-xylene and p-xylene, respectively).

Regarding adipic acid, its preparation is particularly suitable for the methods and apparatus of the present invention, and general information is found in many US patents, among other documents. This includes, but is not limited to:

-US Pat. Nos. 2,223,493, 2,589,648, 2,285,914, 3,231,608, 3,234,271, 3,361,806, 3,390,174, 3,530,185, 3,649,685, 3,657,334, 3,953,876,100 4,032,569, 4,105,856, 4,158,739 (glutaric acid), 4,263,453, 4,331,608, 4,605,863, 4,902,827, 5,221,800, 5,321,157 and 5,463,119.

The examples illustrating the operation of the present invention are described for illustrative purposes only and do not limit the scope of the present invention in any way. It should also be emphasized that the preferred embodiments discussed in detail above, and any other embodiments within the scope of the present invention, may be implemented individually or in any combination, in accordance with common sense and / or expert opinion. In accordance with the present invention, individual portions of an embodiment may be practiced individually or in combination with other individual portions of their overall embodiment. Such combinations are also within the scope of the present invention. In addition, any description attempted in the above discussion is merely theoretical and does not limit the scope of the invention.

In Figures 1 to 18, the symbols that differ by 100 represent members that are substantially the same or perform the same function. Thus, in one embodiment, once one member is defined, in other embodiments no redefinition of members exemplified by the same reference numerals or 100 different signs in these figures is necessary and is often omitted from the above description for clarity. It was. In FIG. 19, this rule is not followed for all codes.

The terms inlet line and outlet line are used to mean a line for conveying a material for performing a process, for example volatiles, intermediate oxidation products, off-gases and the like. The terms input line and output line are used to mean a line for transmitting a signal, which is in most cases an electrical signal, but may be, for example, a hydraulic, atmospheric, optical, acoustic signal, or the like. .

The diagonal arrow through the member means that the member is preferably electrically controlled through the line connected to the arrow.

Internal condensation according to the invention is the condensation of condensable material which takes place before the pressure is reduced to approximately atmospheric pressure in the compressed system. Internal internal condensation is condensation in the reaction chamber.

Condensable materials are those having a boiling point above 15 ° C., and non-condensable materials are those having a boiling point below 15 ° C. Since a small amount of one kind will almost always be mixed with the other, it should be understood that condensable material means material that is almost condensable and noncondensable material means material that is almost non-condensable.

If dilution or concentration occurs when the droplets move from the atomizer to the sample collector, such dilution may be used to monitor the dilution or concentration source using techniques well known in the art to determine the temporal conversion prior to coalescence in a properly programmed controller. Should be taken into account when calculating.

The response time between the change of one variable or parameter and the result thereof should also be taken into account and the regulator should be appropriately calibrated or programmed by techniques well known in the art.

Claims (22)

A process for preparing an intermediate oxidation product from a first liquid containing a first reactant and a gas containing an oxidant, (A) spraying a first liquid at a spray temperature and a spray distance from the second liquid mass to form a plurality of gaseous droplets, (B) causing a substantially non-degradable oxidation reaction between the first reactant and the oxidant at an oxidation pressure to form an intermediate oxidation product, (b) (C) adhering the droplets to the second liquid mass and Spray temperature, droplet temperature, temperature of the second liquid, temperature before the coalescence of the droplet, temporary temperature difference of the droplet, temporary fine temperature difference of the droplet, conversion of the first reactant to the intermediate product in the droplet, in the first liquid To within each predetermined range a parameter or determinant selected from the group consisting of the conversion of the first reactant to the intermediate product, the conversion of the first reactant to the intermediate product in the second liquid, the transient conversion before coalescence, and combinations thereof. Adjusting (d) the substantially non-degradable oxidation reaction by adjusting. The method of claim 1 further comprising separating the intermediate oxidation product from the second liquid. The method of claim 1, wherein the droplets contain the catalyst in a predetermined amount, and wherein adjustment of the parameter or determinant is performed by varying the predetermined amount of catalyst. The method of claim 1, wherein the droplets have an average droplet diameter and are produced at a desired first flow rate, the gas flows at a second flow rate, contains volatile components that volatilize at a volatilization rate, and the first liquid is The first reactant is contained in the first content, the gas contains the oxidant in the second content, and the adjustment of the parameters or determinants is such as a change in spray temperature, a change in reaction pressure, a change in spray distance, a change in average droplet diameter, The method is carried out by a step selected from the group consisting of a first flow rate change, a second flow rate change, a volatilization rate change, a first content change, a second content change, and combinations thereof. The method of claim 1, wherein the transient conversion before coalescence is monitored by chromatography. The method of claim 1, wherein the major portion of the oxidation product is an organic compound, the first reactant comprises an organic compound, and the oxidant is oxygen. The method of claim 6, wherein the first reactant is cyclohexane, cyclohexanone, cyclohexylhydroperoxide, cyclohexanol, o-xylene, m-xylene, p-xylene, two or more types of cyclohexane, cyclohexanone, cyclo A compound selected from the group consisting of a mixture of hexanol and cyclohexylhydroperoxide, and a mixture of two or more o-xylenes, p-xylenes and m-xylenes, the oxidant comprising oxygen and the mains of the intermediate oxidation product Adipic acid, cyclohexanol, cyclohexanone, cyclohexyl hydroperoxide, phthalic acid, isophthalic acid, terephthalic acid, a mixture of two or more adipic acids, cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide, And a mixture selected from the group consisting of two or more kinds of phthalic acid, isophthalic acid and terephthalic acid. Methods involving incorporation. The method of claim 1, wherein the intermediate oxidation product is a solid, and separating the intermediate oxidation product from the second liquid comprises filtering the intermediate oxidation product from the second liquid. The method of claim 1 wherein the spraying step is performed by spraying the first liquid by an airless technique. The method of claim 1, further comprising internally condensing the condensable material under substantially reaction pressure. The process of claim 1, wherein the non-degradation oxidation reaction is carried out in a reaction zone surrounded by a film or curtain of liquid. The process of claim 1, wherein the conversion of the first reactant into the intermediate product in the droplets, the conversion of the first reactant into the intermediate product in the first liquid, the intermediate product of the first reactant in the second liquid Wherein the predetermined range of the one or more determinants selected from the group consisting of conversion and temporal conversion before coalescence is between 0.05% and 80%. The predetermined range of the at least one determinant of claim 1, wherein the predetermined range of one or more determinants selected from the group consisting of spray temperature, droplet temperature, temperature of the second liquid, pre-adhesion temperature of the droplet, temporal temperature difference of the droplets, and temporal fine temperature difference of the droplets is 50 To 250 ° C. The method of claim 1 wherein the temporary temperature difference is between 0.1 and 100 ° C. 3. From a gas containing a first liquid and a second reactant, including a reaction chamber having a top end, a bottom end, a partition and a reaction zone in which the first liquid is in contact with the gas to react under reaction pressure. In the apparatus for producing a reaction product, (a) a nebulizer disposed in a reaction chamber suitable for pulverizing the first liquid into a plurality of gaseous liquid droplets at a spraying temperature in such a manner that the droplets adhere to the second liquid mass containing the reaction product (before the droplets are coalesced); Has a temperature before coalescence, the second liquid mass has a second liquid surface, and the atomizer is spaced from the second liquid surface by a spraying distance), (b) a first temperature monitor for measuring spray temperature, a temperature before coalescence and / or a temporary temperature difference and / or a temporary fine temperature difference and / or a second temperature for measuring the temperature of a droplet and / or a second liquid Monitor, conversion of the first reactant to the intermediate product in the droplets and / or conversion of the first reactant to the intermediate product in the first liquid and / or to the intermediate product in the second liquid One or more monitors selected from the group consisting of conversion rate monitors and combinations thereof to monitor conversion rates and / or transient conversion rates prior to coalescence; and (c) connected to at least one of the first temperature monitor, the second temperature monitor, and the conversion rate detector to obtain respective information, the spray temperature, the droplet temperature, the temperature of the second liquid, the temperature before the coalescence of the droplets, and the temporary temperature of the droplets; Difference, temporal fine temperature difference of the droplets, conversion of the first reactant to the intermediate product in the droplet, conversion of the first reactant to the intermediate product in the first liquid, intermediate of the first reactant in the second liquid And a regulator for adjusting within each predetermined range a parameter or determinant selected from the group consisting of conversion to product, transient conversion before coalescence, and combinations thereof. The apparatus of claim 15, further comprising a separator connected to the reaction chamber to separate the reaction product from the second liquid. The liquid according to claim 15, wherein the droplets have an average droplet diameter and are produced at a desired first flow rate, the gas flows at a second flow rate, contains volatile components that volatilize at a volatilization rate, and the first liquid is Containing the first reactant in the first content, the gas containing the second reactant in the second content, and the regulator changing the spray temperature, changing the reaction pressure, changing the spray distance, changing the average droplet diameter, first flow 12. An apparatus for adjusting a determinant to a predetermined range by varying a variable selected from the group consisting of a change in velocity, a change in second flow rate, a change in volatilization rate, a change in first content, a change in second content, and a combination thereof. The apparatus of claim 15, wherein the conversion detector comprises a chromatography device. 16. The apparatus of claim 15, wherein the atomizer is disposed toward the top end and positioned toward the bottom end at a spray distance. 20. The apparatus of claim 19, wherein the atomizer is airless. The apparatus of claim 15, further comprising a recirculation branch for recycling at least a portion of the second liquid into the first liquid. The apparatus of claim 15 further comprising means for condensing volatiles in the reaction chamber.