KR101581577B1 - Apparatus for manufacturing diene compound and manufacturing method of diene compound - Google Patents

Abstract

The present invention relates to a process for producing a diene compound by an oxidative dehydrogenation reaction, which comprises, in addition to elimination of water by a demister, an occlusion of pipelines such as acidic substances, basic substances and sublimable substances in by- And a process for producing a diene compound. The apparatus for producing a diene compound according to the present invention comprises: a reactor in which a dehydrogenation reaction is performed; And a dehydration / deionizer fluidly connected to the reactor, for removing water and ionic substances from the reaction product flowing out of the reactor together.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for producing a diene compound and a method for producing the same,

The present invention relates to an apparatus for producing a diene compound and a method for producing a diene compound, and more particularly, to a method for producing a diene compound by an oxidative dehydrogenation reaction, To a process for producing a diene compound and a process for producing the diene compound, which are capable of removing by-products which may cause pipe clogging, corrosion of the device, and malfunction of the device such as acidic substances, basic substances and sublimable substances in the by-products.

Methods for producing diene compounds as intermediates in many petrochemical products include naphtha cracking, direct dehydrogenation of alkene, and oxidative dehydrogenation of alkene. Among them, the naphtha cracking process has a high energy consumption due to the high reaction temperature. In order to satisfy the demand of the diene compound which is increased through the naphtha cracking process, a new naphtha cracker should be newly installed and / or expanded. It is not preferable that the investment and operation of the naphtha cracker can not be optimally adjusted to the production demand of the diene compound and another basic oil is produced in excess in addition to the diene compound.

Therefore, there is a need for a process for producing a diene compound alone. An alternative to this is a method for producing diene compounds through dehydrogenation reaction from alkene.

The direct dehydrogenation reaction of the double alkene is an endothermic reaction in which the reaction heat is very high. In order to produce the diene compound with a high yield, the conditions of high temperature and low pressure And is thermodynamically disadvantageous, and thus is not suitable as a commercialization process for producing a diene compound.

On the other hand, the oxidative dehydrogenation reaction of alkene is a reaction in which oxygen and oxygen react with each other to produce a diene compound and water, which is thermodynamically very advantageous because it produces stable water as a product. In addition, unlike the direct dehydrogenation reaction of alkene, it is an exothermic reaction, so that a diene compound having a high yield can be obtained even at a low reaction temperature as compared with the direct dehydrogenation reaction.

Thus, although the oxidative dehydrogenation reaction of an alkene, preferably n-butene (for example, 1-butene, trans-2-butene, cis-2-butene) is an effective method for producing a diene compound alone In this reaction, since oxygen is used as a reactant, many side reactions such as a complete oxidation reaction are expected, and it is inevitable that various side products are included in the reaction products due to such side reactions.

Particularly, among the by-products contained in the reaction product, a large amount of acidic substances, basic substances and sublimable substances may be contained. Of these by-products, particularly acidic substances and / or basic substances, Can cause corrosion of the apparatus and / or malfunction of the apparatus in the manufacturing apparatus for manufacturing, and the sublimation materials cause obstruction of the pipe in particular.

In the case of a conventional apparatus for producing a diene compound, as shown in Fig. 1, in order to remove a large amount of water necessarily occurring in an oxidative dehydrogenation reaction, the reactor (1) in which the oxidative dehydrogenation reaction takes place, And a demister (2) is used for removing water by being fluidly connected to the reactor (1).

However, the employment of the above-described demister (2) alone can not sufficiently remove acidic substances and / or basic substances and / or sublimable substances as by-products contained in the reaction product, It is necessary to stop the operation of the manufacturing apparatus and disassemble and clean the manufacturing apparatus. Thus, it takes a lot of time and effort to maintain the product, and the productivity of the diene compound is lowered It causes.

It is an object of the present invention to provide a process for producing a diene compound by an oxidative dehydrogenation reaction, which comprises, in addition to elimination of moisture by a demister, an obstruction of pipelines such as acidic substances, basic substances and sublimable substances, And to provide a method for manufacturing a diene compound and a method for producing a diene compound, which can remove by-products that may cause corrosion of the device and malfunction of the device.

An apparatus for producing a diene compound by an oxidative dehydrogenation reaction of an alkene according to the present invention comprises: a reactor in which a dehydrogenation reaction is performed; And a dehydration / deionizer fluidly connected to the reactor, for removing water and ionic substances together from the reaction product flowing out of the reactor.

The dehydration / deionizer may further comprise a cooling trap, for example, which effectively removes the sublimable material from the reaction product.

The cooling trap is not particularly limited in the case of a cooling trap capable of removing a sublimable material.

Further, a method for producing a diene compound by an oxidative dehydrogenation reaction of an alkene according to the present invention comprises the steps of: (1) bringing a hydrocarbon mixture including an alkene, air, and steam into contact with a catalyst in a reactor to perform an oxidative dehydrogenation reaction A reaction step; And (2) a dehydration / deionization step of removing moisture and ionic substances from the reaction product flowing out of the reactor after the reaction step.

According to the present invention, in the production of a diene compound by an oxidative dehydrogenation reaction, the elimination of water by a demister and, in particular, the clogging of pipelines such as acidic substances, basic substances and sublimable substances in by- By-products that may cause corrosion of the device and malfunction of the device, thereby making it possible to stably operate the diene manufacturing apparatus, thereby improving the productivity and enabling the production of a high quality diene compound .

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing the structure of a conventional diene producing apparatus. Fig.
2 is a schematic diagram showing the configuration of a diene producing apparatus according to one embodiment of the present invention.

As shown in FIG. 2, an apparatus for producing a diene compound by an oxidative dehydrogenation reaction of an alkene according to the present invention comprises a reactor 1 in which a dehydrogenation reaction is carried out; And a dehydration / deionizer (11) fluidly connected to the reactor (1) for removing water and ionic substances from the reaction product flowing out of the reactor (1) .

That is, in the present invention, in an apparatus for producing a diene compound by an oxidative dehydrogenation reaction, the dehydrogenation reaction for dehydration from a reaction product flowing from the reactor (1) is connected to a reactor (1) By connecting the dehydration / deionizer (11) comprising means (13) and deionization means (12) for the removal of ionic substances to the rear end of the reactor (1) Thereby removing moisture and byproducts which may lead to the occlusion of pipelines, corrosion of the apparatus and malfunction of the apparatus, such as acidic substances, basic substances and sublimable substances in the by-products contained in the reaction products, It is possible to stably operate the production apparatus, thereby improving the productivity and enabling the production of high quality diene compounds.

The reactor 1 and the dehydration / deionizer 11 may be fluidly connected to each other, for example, by a first conduit 3. Here, the expression "fluid connection" means that fluid, i.e., liquid or gas, is interconnected so that a flowable material can flow.

The dehydration / deionizer 11 may preferably comprise a dehydrating means 13 and a deionization means 12 in a single housing. It is possible to make both the dehydration function and the deionization function both performed without changing the configuration and arrangement of the manufacturing apparatus of the entire diene by including the dehydration unit 13 and the deionization unit 12 together in one housing It is effective.

The dehydrating means 13 constituting the dehydration / deionizer 11 may be a dehydrator filled with a fibrous object. The fibrous body is an object in which fibers, preferably long fibers and / or short fibers are aggregated into a net structure or a randomly entangled structure, and when the reaction product containing moisture passes through the fibrous body, And functions to separate from the reaction product to function as dehydration. The fibers may preferably be metal fibers, more preferably corrosion resistant metal fibers, and most preferably stainless steel fibers. This is preferable because it includes corrosive substances such as an acidic substance and / or a basic substance contained in the reaction product, so that it is not corroded by these corrosive substances and performs a dewatering function for a long time.

The deionization means 12 constituting the dehydration / deionizer 11 may be an ion exchange resin. Such an ion exchange resin means an insoluble synthetic resin having an ion capable of ion exchange, and includes a cation exchange resin and an anion exchange resin, as well as an amphiphilic resin, an electron exchange resin, and a chelate resin.

The cation exchange resin is again divided into a strong acid type and a weak acid type. The strong acid type is a group having a sulfonic acid group (-SO ₃ H) as a group for ion exchange, cation exchange is possible over a wide pH range, Hard water), and pure water, and is most widely used. The weak acid type has a large capacity and can be regenerated because it has a carboxy group (-COOH).

The anion exchange resin is also classified into a strong base type and a weak base type. The strong base type is a quaternary ammonium salt group, which is R ₄ NOH type. It has a strong basicity and is capable of anion exchange over a wide pH range, The type has first, second and third amino groups, weak basicity but strong ability and stability.

The ion exchange resin shows the following neutralization, neutral salination and metathesis (R is the matrix of the resin), respectively.

(1) R-H + NaOH ↔ R-Na + H ₂ O

(2) R-H + NaCl ↔ R-Na + HCl

(3) R-Na + KCl ↔ R-K + NaCl

(4) R-OH + HCl ↔ R-Cl + H ₂ O

(5) R-OH + NaCl ↔ R-Cl + NaOH

(6) R-Cl + NaBr ↔ R-Br + NaCl

There are also amphoteric ion exchange resins, which can exchange both cations and anions at the same time. These ion exchange resins are all well known to be commercially available and commercially available from leading domestic and foreign manufacturers.

The dehydration / deionizer (11) comprises a housing; A deionization means (12) located on the upper side of the interior of the housing with respect to a direction in which the reaction product flows; And dehydrating means (13) located below the deionization means (12). That is, acidic substances and / or basic substances are highly likely to be present as ions when they are present together with moisture, and when they are present as ions, they are advantageous in that they are removed by ion exchange by ion exchange resins, The invention is not limited thereto, but otherwise the dehydration / deionizer 11 comprises a housing; A dehydrating means (13) located on the upper side of the interior of the housing with respect to a direction in which the reaction product flows; And deionization means (12) positioned below the dehydrating means (13). With this configuration, the amount of the substance in contact with the deionization means 12 is reduced by the amount of water removed by the dehydration means 13, and the deionization means 12 and the ionic substance, that is, the acidic substance and / The amount of contact with the substance may be increased.

The dewatering / deionizing device 11 is configured to mount the dewatering means 13 and deionization means 12 together in one housing so that they can be removed from the housing by means of these dewatering means 13 and / The dehydrating means 12 can be removed and the new dewatering means 13 and / or deionization means 12 can be replaced to be mounted, thereby enabling the dewatering efficiency and deionization efficiency to be maintained at a high level at all times .

Although not shown in the drawings for the sake of simplicity, other configurations of the known diene compound production apparatus may be connected subsequent to the dehydration / deionizer, for example, separation and purification of a diene compound and an alkane compound from a reaction product A flow control valve for controlling the flow rate or a pressure control valve for controlling the pressure may be connected. In FIG. 2, the second channel 4 is shown for simplification of the drawing. It will be understood by those skilled in the art that the components of other devices can be connected through this second conduit 4.

In the above, it can be understood that the first conduit 3 and the second conduit 4 all consist of conduit connections through which the fluid can flow.

The water pipe 5 connected to the dehydrator 2 and the dehydrating / deionizing device 11 is connected to the drain 2 and the dehydrating / deionizing device 11 via the drain pipe 5, As shown in Fig.

As a byproduct which can be contained in the reaction product flowing out of the reactor 1 in which the oxidative dehydrogenation reaction is carried out during operation of the apparatus for producing a diene through the oxidative dehydrogenation reaction through the above- Corrosive material, i. E. Acidic and / or basic materials, can be simultaneously dehydrated and deionized through the dehydration / deionizer according to the invention, It is possible to prevent malfunctions, thereby increasing the operation time of the manufacturing apparatus to increase the productivity, and to reduce the time and effort required for maintenance.

The dehydration / deionizer may be an apparatus filled with an ion exchange resin as a de-ionization means, for example. In this case, water, ionic substances and heavy substances having a large molecular weight can be economically removed .

Further, a method for producing a diene compound by an oxidative dehydrogenation reaction of an alkene according to the present invention comprises the steps of: (1) bringing a hydrocarbon mixture including an alkene, air, and steam into contact with a catalyst in a reactor to perform an oxidative dehydrogenation reaction A reaction step; And (2) a dehydration / deionization step of removing moisture and ionic substances from the reaction product flowing out of the reactor after the reaction step.

The reaction step (1) is carried out by bringing a hydrocarbon mixture containing alkene, air and steam into contact with a catalyst in a reactor to carry out an oxidative dehydrogenation reaction. Such a reaction step can be carried out in a manner well known to those skilled in the art .

The dehydration / deionization step (2) may be carried out by passing the reaction product flowing out of the reactor through a dehydration / deionizer according to the present invention after the reaction step, Dehydration and deionization are carried out by means of the apparatus.

Here, the dehydrating means is not particularly limited as long as it is dehydrating means capable of removing steam in the mixed gas generated after the oxidative dehydrogenation reaction, and may be a demister, for example. The deionization means may be, for example, an ion exchange resin.

The dehydration process can also be performed by passing the reaction product through the dehydration means, and the deionization process can also be performed by contacting the reaction product with the deionization means, i.e., the ion exchange resin.

The dehydration / deionization step can remove not only water vapor but also a heavy molecular substance which is a cause of pipe obstruction, thereby removing a larger amount of by-products from the reaction product.

According to an embodiment of the present invention, the dehydration / deionization step may further include a purification step of separating and purifying the diene compound and the alkane compound from the dehydrated / deionized reaction product.

By separating the desired diene compound through such a purification step, it is possible to obtain the diene compound intended by the present invention.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

Example 1

A basic anion exchange resin was charged as a demistering means and the apparatus was installed at the rear end of a butadiene reactor, and the condensate obtained by passing through a product mixture gas from the rear end of the reactor was analyzed.

Comparative Example 1

For comparison with Example 1 above, an ion exchange resin was used as a demistering means The same procedure was carried out except that no filling was carried out.

[Test Example]

Samples were taken from the condensed water obtained in Example 1 and Comparative Example 1 and analyzed by gas chromatography (GC). For comparison, a quantitative sample of the condensate was analyzed by GC and the GC area values of the components contained in the condensate were respectively listed in Table 1 below. At this time, the removal rate (%) of each component was measured at a decreasing rate from the GC area value of Example 1 based on the GC area value of Comparative Example 1.

Comparative Example 1 Example 1 Removal rate Butenone 20.0 13.2 34.1% Maleic anhydride 27.8 11.4 58.9% Unknown1 6.1 - 100.0% Cyclohexene-dicarboxy 10.2 5.4 46.7% Coumarin 4.4 2.7 39.2% Unknown2 3.0 3.0 0.1% 9-fluorenone 74.7 12.4 83.3% Unknown3 6.7 - 100.0% Unknown4 11.4 - 100.0% Unknown5 32.9 5.1 84.5% Anthraquinone 105.5 19.9 81.1%

As shown in Table 1, in the case of the condensed water obtained by passing through the dehydration / deionizer according to the present invention (Example 1), the substances capable of causing the pipe clogging compared to the condensed water obtained by passing only the dehydrator (Comparative Example 1) And 60 ~ 70% were removed.

1: Reactor 2: Dimer
3: first conduit 4: second conduit
5: drain pipe 11: dehydration / deionizer
12 dehydration means 13 deionization means

Claims (9)

A reactor in which the dehydrogenation reaction is carried out; And
A dehydration / deionizer fluidly connected to the reactor, the dehydration / deionizer for removing moisture and ionic material from the reaction product leaving the reactor;
Wherein the oxidizing dehydrogenation reaction of the diene compound is carried out by an oxidative dehydrogenation reaction of an alkene. The method according to claim 1,
Wherein the dehydration / deionizer comprises dehydrating means and deionization means in one housing together with an oxidizing dehydrogenation reaction of the alkene. 3. The method of claim 2,
Wherein the dehydrating means constituting the dehydrating / deionizing device is a dehydrator filled with a fibrous object. The method of claim 3,
Wherein the fibrous material is an object in which the fibers are aggregated into a net structure or a random tangled structure. 5. The method of claim 4,
Wherein the fiber is a metal fiber of corrosion resistance, wherein the diene compound is produced by an oxidative dehydrogenation reaction of an alkene. 3. The method of claim 2,
Wherein the deionization means constituting the dehydration / deionizer is an ion exchange resin. ≪ RTI ID = 0.0 > 8. < / RTI > 3. The method of claim 2,
Said dehydration / deionizer comprising: a housing;
A deionization means located on the upper side of the inside of the housing with respect to a direction in which the reaction product flows; And
Dehydrating means located below the deionization means;
Wherein the diene compound is prepared by an oxidative dehydrogenation reaction of an alkene. (1) a reaction step in which an oxidative dehydrogenation reaction is carried out by contacting a hydrocarbon mixture containing alkene, air and steam with a catalyst in a reactor; And
(2) a dehydration / deionization step of removing water and ionic substances from the reaction product flowing out of the reactor after the reaction step;
Wherein the oxidizing dehydrogenation reaction of the diene compound is carried out in an oxidative dehydrogenation reaction of an alkene. 9. The method of claim 8,
The method of claim 1, further comprising, after the dehydration / deionization step, a purification step of separating and purifying the diene compound and the alkane compound from the dehydrated / deionized reaction product, Gt;

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