CN101842339A - Process for preparing chlorohydrin by reaction of polyol with hydrochloric acid - Google Patents
Process for preparing chlorohydrin by reaction of polyol with hydrochloric acid Download PDFInfo
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Abstract
The present invention relates to a method for preparing chlorohydrin by chlorination of polyol such as glycerin with hydrogen chloride. The method of the present invention is composed of the following processes: reaction mixture feed comprising polyol, hydrogen chloride and organic acid (catalyst for chlorination) is loaded into the first reactor, in which chlorohydrin is generated by chlorination; the first product mixture feed containing the chlorohydrin and non- reacted reaction mixture discharged from the first reactor and the additional polyol feed are supplied to the second reactor, in which chlorohydrin is generated by additional chlorination; the second product mixture feed containing the chlorohydrin discharged from the second reactor is loaded in distillation column and then distillation product containing chlorohydrin is separated through the top of the distillation column; and some re-circulated feed of distillation residual solution containing chlorohydrin, is re-circulated into the first reactor.
Description
Technical field
The present invention relates to by utilizing hydrogenchloride to be used to make the method for the chloro-hydrin(e) of Epicholorohydrin (raw material of Resins, epoxy) carry out chlorination preparation such as polyvalent alcohols such as glycerol.
Background technology
One of modal method of making Epicholorohydrin (ECH) is made of the following step: the chlorination by propylene under the high temperature (450 ℃～550 ℃) prepares chlorallylene (ALC); Make the chlorallylene that makes and hypochlorous acid solution reaction to obtain dichlorohydrins (dichlorohydrine) solution; Make dichlorohydrins dehydrochlorination Epicholorohydrin by using as alkali lye such as milk of lime or sodium hydroxide solutions.
But, the disadvantage of aforesaid method is raw material efficient aspect, says exactly, needs 2 moles chlorine and 2 normal alkali to make 1 mole Epicholorohydrin, showing only has 25% chlorine to can be used for the synthetic of Epicholorohydrin in theory, and remaining chlorine changes into hydrogenchloride or waste salt by neutralization.Aspect reaction efficiency, aforesaid method is also followed different side reactions, generates dichloropropylene, trichloropropane, propenyl chloride, propylene dichloride and isopropyl chloride in the process of preparation chlorallylene, causes the productive rate of target chlorallylene to reduce and the production cost rising.Aforesaid method generates 2, and the 3-dichlorohydrins is 1 as intermediate, the twice of the amount of 3-dichlorohydrins.1, the 3-dichlorohydrins changes into the conversion rate of Epicholorohydrin faster than 2, and the conversion rate of 3-dichlorohydrins shows that this method is subjected to the restriction of reaction efficiency.In addition, making hypochlorous acid needs a large amount of process waters, has caused generating the dichlorohydrins solution that is about 1%～10% lower concentration, final, has generated a large amount of brine wastes because of making Epicholorohydrin.
Another kind of commercial methods is made of following steps: the oxidation/acetoxylation by propylene and acetate prepares allyl acetate under the situation of palladium catalyst existing; The allyl acetate that hydrolysis makes is with the preparation vinyl carbinol; Addition reaction by vinyl carbinol and chlorine under the situation that has liquid hydrogenchloride (spirit of salt) catalyzer prepares 2, the 3-dichlorohydrins; With by using alkali lye to make dichlorohydrins dehydrochlorination Epicholorohydrin.
In theory, according to aforesaid method, the chlorine that needs 1 mole to be making 1 mole Epicholorohydrin, and can omit the process of preparation chlorallylene, therefore can not generate byproduct hydrogen chloride.In addition, consume 1 normal alkali in theory and make 1 mole Epicholorohydrin, and do not have hypochlorous acid solution, and reduced the amount of waste water.
The not business-like as yet method for preparing Epicholorohydrin that also has other.For example, reported comprise at high temperature make acrylonitrile-chlorinated with preparation chlorallylene and existing under the situation of titanium-silicon molecular sieve catalyst by utilizing hydrogen peroxide to make the direct epoxidation of chlorallylene prepare the method for the step of Epicholorohydrin, comprise that the oxidation by propylene prepares propenal, by chlorine addition reaction preparation 2,3-dichloro propionic aldehyde and by 2, the hydrogenation preparation 2 of 3-dichloro propionic aldehyde, the preparation 2 of the step of 3-dichlorohydrins, the method of 3-dichlorohydrins, and comprise that the oxidation by propylene prepares acetone, prepare Dichloro acetone and the preparation of the hydrogenization by Dichloro acetone 1 by the chlorine addition reaction, the preparation 1 of the step of 3-dichlorohydrins, the method for 3-dichlorohydrins.
Aforesaid method all uses propylene and chlorine as raw material.Yet the cost of propylene etc. worldwide constantly increase, and cause production cost to increase.
Based on the global concern that the surrogate of limited petroleum resources is developed in environmental problem and effort, the fast development of biofuel industry is to replace traditional transport fuel.Biofuel is from as extracting the plants such as rape, thereby it not only helps environment but also has huge purposes as renewable energy source.In the methanol decomposition process of preparation biofuel, generated glycerol.As the novel C that can replace propylene-3 source, glycerol has also caused people's attention.
Glycerol not only can be used as the by product of making biofuel and generates, and can be used as and use animal/vegetables oil or lipid (as oil or fat) hydrolysis to generate with the by product of making the soap class to make lipid acid or saponification.
Because the increase of the supply of the glycerol due to the manufacturing of active biofuel, the price of glycerol has been reduced to and has been enough to replace propylene and originates as C-3 along with recently.Therefore, opposite with the traditional method of the synthetic glycerol of preparation, it is more favourable economically with regard to the aspects such as operability of production cost and glycerol (by glycerol) preparation Epicholorohydrin.It is favourable preparing Epicholorohydrin by glycerol because reaction herein use the anhydrous hydrogen chloride that generates as by product at a large amount of industrial circles or spirit of salt as raw material to replace chlorine.
The German Patent communique has been described the method that is converted into chloro-hydrin(e) by catalytic hydrochlorination with glycerol 197308 (1908) numbers, it is characterized in that the balanced reaction that is made of following reaction: glycerol and anhydrous chlorides of rase H-H reaction are to obtain a chloro-hydrin(e) (glycerine monochlorohydrin in the presence of the carboxylic acid catalyst, MCH) and dichlorohydrins (dichlorohydrine, and generate water byproduct DCH).
Aforesaid method is existing report before 100 years, but because commercialization not yet due to the price of glycerol.Just after 21 century in recent years, along with the reduction of the increase of glycerol supply and the glycerol price that causes thus, attempted making this method commercialization.
Different with the method for prepared in reaction chloro-hydrin(e) by propylene and chlorine, use this preparation method of glycerol and hydrogenchloride significantly to reduce the organic chloride that side reaction generated, reason is that this method does not need chlorallylene reaction, thereby and does not use hypochlorous acid solution to reduce wastewater flow rate by direct manufacturing dichlorohydrins.According to traditional commercial methods, the dichlorohydrins that this method generates can be converted into Epicholorohydrin by using as alkali lye dehydrochlorinations such as milk of lime or sodium hydroxide solutions.
The German Patent communique has been described the batch-type balanced reaction of carrying out at about 100 ℃ (95 ℃～120 ℃) for 197308 (1908) numbers.This reaction is a kind of liquid phase reaction that causes in the anhydrous hydrogen chloride dissolving back that provides.But in this reaction, can't remove reaction water continuously so that balance moves towards the direction that generates chloro-hydrin(e).The pressure that above-mentioned patent has been described reaction can be normal atmosphere, also can pressurize so that the solubleness of anhydrous hydrogen chloride increases to promote reaction.Acetate, propionic acid, formic acid, styracin, nonane diacid, succsinic acid or toluylic acid can be used as the carboxylic acid catalyst.The preferred amounts that above-mentioned patent also proposes catalyzer because the increase of catalyst content may cause side reaction, causes productive rate to descend for the about 1 weight %～2 weight % of the glycerol that provides.
In No. 197309 (1908), German Patent communique, (for example use spirit of salt, the hydrochloric acid solution of 37 weight %) replace anhydrous hydrogen chloride, the 2 weight %～30 weight % of the weight of the glycerol that provides are provided the amount of acetic acid catalyst, the amount when this measures greater than anhydrous hydrogen chloride.
The German Patent communique has been described by the reaction of anhydrous hydrogen chloride and glycerol for 238341 (1911) numbers and has been made a chloro-hydrin(e) and dichlorohydrins.
Above-mentioned patent all relates at normal atmosphere or adds the batch-type reaction of depressing initiation.Therefore, owing to due to the accumulation of formation equilibrated reaction water, transform fully and need expend long time (24 hours～48 hours).10 hours～20 hours reaction can not provide high conversion, only can obtain the productive rate of extremely low dichlorohydrins (useful, necessary material).Therefore, attempted reacting and increasing productive rate by using semi-batch, this reaction provides excessive anhydrous hydrogen chloride continuously so that balance moves to the direction of generation dichlorohydrins.
Conant etc. are at its paper Organic Syntheses, Coll.Vol.1, p.292 (1941) and Organic Syntheses, Coll.Vol.2, p.29 report in (1942) uses 90% glycerol and anhydrous hydrogen chloride and acetic acid catalyst to cause the semi-batch reaction.At this moment, the amount of acetic acid catalyst is 2 weight % of 90% glycerol, and reaction preferably under atmospheric pressure causes in the time of 100 ℃～110 ℃.According to the method for Conant, anhydrous hydrogen chloride without interruption to be dissolved in commitment very fast, and along with the reaction times passage, speed reduces.In addition, the gross weight of reactor in early days the stage change always, but when a certain weight, settle out, show reaction terminating.More accurate, according to the method for Conant, by collecting undissolved anhydrous hydrogen chloride with gas phase whole anhydrous hydrogen chlorides without interruption.For making the loss minimum of anhydrous hydrogen chloride, adjust the supply of anhydrous hydrogen chloride according to the variation of total reactor weight.In theory, the amount of dissolved anhydrous hydrogen chloride when reaction terminating (eliminating loss amount) is 125%, and showing has 25% to be oversupply for reaction.When reaction is finished, cooled reaction solution.The unreacted hydrogen chloride (or spirit of salt) and the acetate that are dissolved in the reaction soln are handled to neutralize with SODA ASH LIGHT 99.2.At this moment, for salting out of promoting neutralization and prevent to generate, additionally add water again.The method of Conant is also described, and isolates the liquid phase layer by fractionation by the neutral reaction soln, and to obtain the final objective compound, remaining organic layer (unpurified dichlorohydrins solution) carries out vacuum distilling to reduce the concentration of water at 14mmHg.Therefore, when temperature reaches 68 ℃, obtain a large amount of water, thereby the water that obtains distills once more to remove the dichlorohydrins solution of the acquisition high density of anhydrating.This solution mixed prior to the retort solution of 68 ℃～75 ℃ of preparations with morning, with the dichlorohydrins solution (concentration is 70% in theory) that obtains high density.Be to increase concentration, at 14mmHg vacuum distilling dichlorohydrins solution once more.At last, make 55%～57% dichlorohydrins solution in 70 ℃～73 ℃ in theory.
The disadvantage of the method for Conant etc. is in the accumulation, neutralization (with unreacted hydrogen chloride (spirit of salt) and acetate) process of massive losses, the reaction water of anhydrous hydrogen chloride and divides the loss of the dichlorohydrins in the process of dried up and dichlorohydrins, even and also be difficult to reclaim dichlorohydrins after all complex separation process.
Disclose for a long time based on these class methods of semi-batch distillatory, thus its approximately at least 120 ℃ carry out along with reaction and remove reaction water continuously and balance is moved to generate dichlorohydrins increasing productive rate by distillation.According to these methods, under the temperature that increases, cause dehydrochlorination reaction, therefore generated can not recirculation chloro-hydrin(e), glyceryl ester, resinous polymer and other high boiling side reaction resistatess.Distillation is equally also carried out under the temperature that increases.Therefore, the retort solution of removing from reactant is the liquid acidic mixture of a kind of corrodibility, and this mixture comprises a large amount of dichlorohydrins (have very high boiling point, but together remove with water owing to form azeotrope with water), spirit of salt and acetate.Extremely difficulty reclaims dichlorohydrins thus.United States Patent (USP) 2,198 has been described the method for preparing anhydrous dichlorohydrins 600 (1940) numbers, wherein when reaction is finished the reaction residual solution is carried out vacuum distilling removing a large amount of water, thereby obtains dichlorohydrins; And suitable organic solvent added in the solution of fractionation by distillation to extract dichlorohydrins by it; Extract carries out fractionation to obtain extra anhydrous dichlorohydrins.
United States Patent (USP) 2,144, describe for 612 (1939) numbers, be accompanied by use be selected from by anhydrous hydrogen chloride, spirit of salt, acetate and as the catalyzer of the group formed of aliphatic carboxylic acids such as formic acid in normal atmosphere or decompression or add the semi-batch of depressing and distill, thereby suppress the generation of high boiling point side reaction resistates that can not recirculation in the low temperature initiation reaction, and select for use appropriate organic solvent to dewater only to steam by the component distillation that suppresses the dichloro-alcohol and water.At this moment, organic solvent can not have reactivity, and must be able to dissolve dichlorohydrins and do not mix with water.Temperature of reaction depends on organic solvent.Usually, the vapor distillation temperature (reach about 100 ℃, this is a temperature of leaving the gas phase mixture of reaction zone) that is reflected at reaction mixture (comprising solvent) causes.The acidic solution of removing from the reactant distillation is made of water, spirit of salt, a spot of acetate, solvent and dichlorohydrins.This retort solution abandons when reactive distillation is finished, perhaps use other glycerol to carry out the spirit of salt DeR to increase the usability of spirit of salt at 80 ℃～95 ℃, it can also be further used for next reaction batch, perhaps where necessary solvent and the extra glycerol that is used for the spirit of salt DeR are together added, anhydrate thereby remove.Simultaneously, finish reaction needed with aforesaid method and expend at least 35 hours, wherein finishing of reaction is meant not regeneration distilled acidic solution.Reaction is when finishing, with remaining reaction mixture cooling, and dried up by rectifying then, dichlorohydrins, organic solvent and a chloro-hydrin(e) and other resistatess that has high boiling point and constitute by unreacted glycerol to divide respectively.Discard isolating water.The organic solvent recirculation of reclaiming.Have high boiling resistates and be used for next reaction batch once more.
United States Patent (USP) 2,144 has been described the successive reaction distillating method 612 (1939) numbers, and wherein anhydrous hydrogen chloride, glycerol and acetic acid catalyst are continuously supplied in the reactor; Reacted to take out and dewatered to be used for rectifying to a part of reaction mixture to a certain degree; Only there is the dichlorohydrins product separated; Recovered solvent and unreacted glycerol, a chloro-hydrin(e) and acetic acid catalyst are recycled in the reactor; The organic solvent layer from the distilled acidic solution through distilling with gas phase separation is back to reactor; Discard the liquid phase layer; Amount glycerol without interruption with the dichlorohydrins of corresponding manufacturing; Acetic acid catalyst without interruption, its amount is many as losing with the liquid phase layer that discards.
The following simply expression of the method in described 20th century: batch-type reaction, semi-batch are reacted (HCl is without interruption), (HCl is without interruption for the semi-batch reaction distillation, with the gas phase continuous dewatering esterase) and continuous reaction distillation (HCl, glycerol, acid catalyst are without interruption, with gas phase (reaction distillation) and liquid phase continuous dewatering esterase).All these methods are all used carboxylic acid, and particularly acetate is as catalyzer.The technical characterictic of the method before described in the prior is as follows.
-glycerol is not limited to pure glycerol, and HCl can be anhydrous hydrogen chloride or spirit of salt.
-when anhydrous hydrogen chloride when the catalyzer, the amount of catalyzer is the 1 weight %～5 weight % of glycerol, when spirit of salt during as catalyzer, its amount is 2 weight % of glycerol～30 weight %, because this catalyzer comprises a large amount of water, makes sluggish.
If-reaction is batch-type reaction or semi-batch reaction, then in the temperature initiation reaction that reaches 120 ℃, if semi-batch reaction distillation or continuous reaction distillation, then reaction distillation carries out at least 120 ℃ temperature.By using appropriate solvent or can reducing the temperature that is used for reaction distillation by reducing pressure.
If-reaction is batch-type reaction or semi-batch reaction, then be reflected at normal atmosphere or pressurization (when anhydrous hydrogen chloride when the catalyzer to increase solubleness) cause down, if reaction is semi-batch reaction distillation or continuous reaction distillation, then reaction distillation carries out under normal atmosphere or pressurization or decompression.
-in each described method, finish reaction to need 24 hours～48 hours.From reaction residue, remove and anhydrate, with reactant rectifying under reduced pressure only to separate dichlorohydrins.
Above described method can not business-like reason be the high price of glycerol, the reaction times of growing and difficulty of sepn process or the like.Yet since 21 century, the price of glycerol reduces, and the price of propylene and chlorine goes up always, and the demand of Resins, epoxy is increasing in addition.Therefore, the dichlorohydrins as the intermediate that generates in the process of making Epicholorohydrin has caused our concern.Submitted relate to used glycerol patent application as the method for feedstock production Epicholorohydrin and dichlorohydrins thereafter.
WO05/021476 by the Spolek application has described the continuous production technology in the recent period, it is characterized in that anhydrous hydrogen chloride without interruption, glycerol and acetic acid catalyst.The method of Spolek is in normal atmosphere work, or adding the work of depressing to increase the solubleness of anhydrous hydrogen chloride, is similar to traditional batch-type/semi-batch reaction process that 20 beginnings of the century proposed, and the preferred temperature of reaction is 100 ℃～110 ℃.Continuous processing in the above method is similar to United States Patent (USP) 2,144, the continuous reaction distillation of describing in 612 (1939) numbers, but make an amendment slightly, for example, dewater and only carry out with liquid phase.The details of this method is described below.
-in the first embodiment, reaction soln cycles through reactor and distillation tower continuously.Particularly, the reaction soln autoreactor is discharged continuously, enters vacuum tower then to obtain reaction product (reaction water and dichlorohydrins).After collecting dichlorohydrins and reaction water, the distilled resistates returns to reactor to be used for further circulation.At this moment, a part distillates resistates and enters the secondary vacuum distillation tower but not reactor.A dichlorohydrins and a chloro-hydrin(e) be by recovered overhead, and then return to reactor, handled as waste with high boiling point by the resistates that distillates that obtains at the bottom of the tower.
-in second embodiment, 1～3 reactors in series is to be used for the substep circulation.Anhydrous hydrogen chloride, glycerol and acetic acid catalyst are packed in first reactor continuously, and the anhydrous hydrogen chloride of consumption and the fill-in of catalyzer are packed in the second and the 3rd reactor continuously.Reaction soln is discharged continuously from first reactor, enters the single flash tower then to obtain dichlorohydrins and the reaction water as reaction product.The distilled resistates enters second reactor.Reaction soln is also discharged continuously from second reactor, enters after-fractionating tower then to obtain dichlorohydrins and reaction water, and the distilled resistates is delivered to the 3rd reactor.After a series of these processes, collect dichlorohydrins and reaction water, enter vacuum tower by its distilled resistates and collect by the distillation tower of last reactor.A dichlorohydrins and a chloro-hydrin(e) are returned to first reactor then by recovered overhead, will be handled as waste with high boiling point by the resistates that distillates that obtains at the bottom of the tower.
The WO06/020234 of Dow Co. application has also described and the above similar continuous processing of Spolek method.This patent of Dow Co. application is emphasized " not removing a large amount of water ", and this method with Spolek is different.Yet, not being removed if make the reaction water that generates in the series reaction of dichlorohydrins, water will be accumulated in reactive system continuously, so that it will cause reactor excessive.Be difficult to finish successive processes thus.Thereby " not removing a large amount of water " can realize in the reaction of batch-type or semi-batch, and can not realize in described continuous processing.Therefore, described patent has only illustrated the semi-batch reaction in all embodiments.According to the patent of Dow, specifically noted that in the dividing potential drop that adds the anhydrous hydrogen chloride of depressing supply the pressure condition of the previous method report of announcing with twentieth century is similar, this condition also is that pressurized conditions is to increase the solubleness of anhydrous hydrogen chloride.Thereby, this method with depress the traditional semi-batch reaction of carrying out and there is no significant difference adding, and only attempt depressing initiation reaction in height to acceptable adding.
The WO05/054167 of Solvay Co. application has described the method for preparing chloro-hydrin(e) by liquid hydrogen chloric acid without interruption and glycerol.The continuous processing of Solvay and the U.S. 2,144, the continuous reaction of describing in 612 (1939) numbers distillation is similar, wherein uses extra distillation tower to prevent the loss by the dichlorohydrins in the reactive distillation gas phase removal process.But extra distillation tower usually promptly is regarded as being used to prevent the loss of dichlorohydrins in traditional method, therefore described method fundamentally with United States Patent (USP) 2,144,612 (1939) numbers institute's reported method and indistinctions.The details of this method is described below.
-this system is constructed as follows: the reactor that can work under the reactive distillation condition, distillation tower that is connected with the gas phase of reactor and the distillation tower that is connected with the liquid phase of reactor.Water is by the top removal of the tower that is connected with gas phase, and dichlorohydrins is collected by the top of the tower that is connected with liquid phase, and liquid phase recirculation enters in the reactor at the bottom of the tower of two towers.
-only there is the distillation tower that is connected with gas phase under the situation of not having the distillation tower that is connected with the liquid phase of reactor, arbitrarily to operate.At this moment, be separated in the solution that distillates that the top of distillation tower compiles, and reclaim dichlorohydrins by its organic layer.
Nearest preparation method seems that those methods that propose than 20th century are more simple, and this only is because omitted the complex steps that is used to separate pure dichlorohydrins.Raw-material dichlorohydrins as the preparation Epicholorohydrin needs not to be pure anhydrous dichlorohydrins.Even reaction mixture contains water, preparation process is also no problem, shows dichlorohydrins to be separated fully with water.Therefore, the traditional method by glycerol manufacturing chloro-hydrin(e) that proposes in the constitutive characteristic of method and 20th century in the recent period there is no significant difference.
Summary of the invention
Technical problem
The inventor is by confirming that can make chloro-hydrin(e) in the following manner cost-effectively finishes the present invention: adjusting to pack into first and second reactors polyvalent alcohol, be circulated to the recirculation feed in first reactor flow velocity, remain in the concentration of the unreacted hydrogen chloride in the feed that is supplied to second reactor and the amount of the extra polyvalent alcohol feed of second reactor of packing into.An object of the present invention is to provide by using hydrogenchloride to carry out chlorination by the method for preparing chloro-hydrin(e) as polyvalent alcohols such as glycerol with big technical scale.
Technical scheme
For achieving the above object, the invention provides the method for preparing chloro-hydrin(e) that comprises following process: the reaction mixture feed that will comprise polyvalent alcohol, hydrogenchloride and organic acid (chlorination catalyzer) first reactor of packing into wherein generates chloro-hydrin(e) by chlorination; To be supplied to second reactor by the first product mixtures feed that comprises chloro-hydrin(e) and non-reacted reaction mixture of first reactor discharge and extra polyvalent alcohol feed, wherein generate chloro-hydrin(e) by other chlorination; Will be by the second product mixtures feed that comprises chloro-hydrin(e) that second reactor is discharged distillation tower of packing into, the top portion by distillation tower is from the product of distillation that comprises chloro-hydrin(e) then; A part of recirculation feed that will comprise the distillation residual solution of chloro-hydrin(e) is recycled in first reactor.
In the method for the invention, the non-reacted reaction mixture of the first product mixtures feed of being discharged by first reactor comprises polyvalent alcohol, hydrogenchloride, organic acid catalyst and water.The recirculation feed that re-circulates in first reactor comprises chloro-hydrin(e) and unreacted polyvalent alcohol.Comprise chloro-hydrin(e), organic acid catalyst and water by the isolating product of distillation in the top of distillation tower.When considering the efficient of process, the content of chloro-hydrin(e) is preferably 50 weight %～90 weight % in the product of distillation.Product of distillation preferably separates by vacuum distilling.
The temperature of reaction of first reactor is preferably 70 ℃～140 ℃.The described temperature of reaction of first reactor can be kept as thermal source by the heat of use recirculation feed and the solution heat of anhydrous hydrogen chloride.
The feature of method of the present invention also be to pack into the ratio of flow velocity and the flow velocity of recirculation feed of polyvalent alcohol of first and second reactors satisfies following formula (1).
In the formula (1), V
1Be the effective volume (l) of first reactor, G is the overall flow rate (kg/hr) that is supplied to the polyvalent alcohol of first and second reactors, and R is the flow velocity (kg/hr) that is circulated to the recirculation feed of first reactor by distillation tower, k
1Be that flow velocity is optimized constant, be preferably 0.3kg/ (l-hr)～5kg/ (l-hr), more preferably 0.5kg/ (l-hr)～1.5kg/ (l-hr).
The concentration that the feature for preparing the method for chloro-hydrin(e) of the present invention also is to be supplied to the unreacted hydrogen chloride (spirit of salt) in the feed of second reactor satisfies following formula (2).
In the formula (2), C
1Be the concentration (weight %) of the unreacted hydrogen chloride (spirit of salt) in the first product mixtures feed, V
1Be the effective volume (l) of first reactor, R is the flow velocity (kg/hr) that is circulated to the recirculation feed of first reactor by distillation tower, k
2Be that flow velocity is optimized constant, be preferably 3～5.
Flow velocity, the flow velocity of recirculation feed and the concentration of the unreacted hydrogen chloride (spirit of salt) in first product mixtures that the feature of method of the present invention also is to be supplied to the extra polyvalent alcohol feed of second reactor satisfy following formula (3):
In the formula (3), G
2Be the flow velocity (kg/hr) that is supplied to the polyvalent alcohol of second reactor, G
1It is the flow velocity (kg/hr) of the polyvalent alcohol that comprised in the reaction mixture feed in first reactor, G is the overall flow rate (kg/hr) that is supplied to the polyvalent alcohol of first and second reactors, R is the flow velocity (kg/hr) that is circulated to the recirculation feed of first reactor by distillation tower, C
1Be the concentration (weight %) of the unreacted hydrogen chloride (spirit of salt) in the first product mixtures feed, k
3Be that flow velocity is optimized constant, it is preferably 0.7～2.5.
Describe the method for preparing chloro-hydrin(e) of the present invention below in detail.
The polyvalent alcohol that is used as raw material among the present invention can be any two pure and mild triols.Particularly, described polyvalent alcohol can be selected from by 1,2-ethane diol (ethylene glycol) and ester, 1 thereof, 2-propylene glycol and ester thereof, 1, ammediol and ester thereof, 3-chloro-1,2-propylene glycol (3-one chloro-hydrin(e)) and ester thereof, glycerin (2-one chloro-hydrin(e)) and ester, 1 thereof, 2, the group that the mixture of 3-glycerol (glycerol, glycerine) and ester and aforementioned substances is formed.Preferably, described polyvalent alcohol is selected from by 3-chloro-1,2-propylene glycol (3-one chloro-hydrin(e)) and ester thereof, glycerin (2-one chloro-hydrin(e)) and ester, 1 thereof, 2, the group that the mixture of 3-glycerol (glycerol, glycerine) and ester and aforementioned substances is formed.
Polyvalent alcohol of the present invention most preferably 1,2,3-glycerol (glycerol, glycerine).In the method for the invention, 3-chloro-1,2-propylene glycol (3-one chloro-hydrin(e)) and ester thereof, 2-chloro-1, ammediol (2-one chloro-hydrin(e)) and ester and 1,2,3-glycerol (glycerol, glycerine) and ester thereof are by generating with the reaction of hydrogenchloride in the presence of the carboxylic acid catalyst, thereby different reaction mixtures is formed in preparation.These reaction mixtures are as the intermediary material of manufacturing objective product.
Be used for glycerol that glycerol of the present invention comprises that the process of making biofuel by vegetable material generates as by product or by the glycerol that generates as by product in the process of making lipid acid or soap class such as raw materials such as animal/vegetables oil, lipid or fat.The glycerol that described glycerol preferably generates in the process of making biofuel or lipid acid.The purity that is used for glycerol of the present invention is preferably at least 50%, and more preferably 70%～100%, most preferably be 80%～100%.Those skilled in the art know these conditions already.
The source of hydrogenchloride is anhydrous hydrogen chloride or spirit of salt among the present invention, is more preferably those hydrogenchloride as the by product generation of the various process of making vinylchlorid (VCM), isocyanic ester (MDI, TDI) or chlorallylene.The hydrogenchloride that generates as the by product of said process is the form of anhydrous hydrogen chloride preferably, and preferred without interruption to depress initiation reaction adding.
Catalyzer of the present invention can be the carboxylic-acid catalyzer.Particularly, when using lower boiling carboxylic acid catalyst, need consume a large amount of catalyzer when generating dichlorohydrins.Must consider the consuming cost of catalyzer when therefore, calculating the cost of production.Described catalyzer is acetate preferably.Acetate is the most cheap compound in the various carboxylic acids.It is suitable economically for the present invention, considers the consuming cost of catalyzer, and preferred acetic acid content is the 1 weight %～5 weight % of glycerol.For selecting appropriate catalyst for use, must take all factors into consideration such as various factorss such as efficient, productive rate, boiling point, solubleness, mixedness and viscosity.If select high boiling carboxylic acid for use, because of the loss of removing the catalyzer that heavy by product caused must together be considered with the recovery of catalyzer.
By method of the present invention use glycerol as the chloro-hydrin(e) compound of starting material manufacturing be 3-one chloro-hydrin(e) (3-chloro-1, the 2-propylene glycol, 3-MCH), 2-one chloro-hydrin(e) (2-chloro-1, ammediol, 2-MCH), 1, the 3-dichlorohydrins (1, the 3-dichlorohydrine, 1,3-DCH) with 2, and the 3-dichlorohydrins (2, the 3-dichlorohydrine, 2,3-DCH).Particularly, different with traditional method, method of the present invention has optionally obtained than 2, and 3-DCH is more 1,3-DCH, and this helps making Epicholorohydrin (ECH).Among the present invention 1,3-DCH is with respect to 2, and the selectivity of 3-DCH is 90%～99%.The concentration of the dichlorohydrins mixture that is made by above sepn process is higher than the concentration that is obtained by traditional method, and it is approximately 50 weight %～90 weight %, more preferably 60 weight %～80 weight %.The high density dichlorohydrins mixing solutions that obtains uses according to traditional commercial methods and is converted into Epicholorohydrin (ECH) as alkali lye such as milk of lime or sodium hydroxide solutions by dehydrochlorination.
Method of the present invention is in that fundamentally the traditional method with the preparation chloro-hydrin(e) that proposed in 20th century is identical.Its principal reaction approach is made of another substitution reaction that glycerol and hydrogenchloride generate the substitution reaction of a chloro alcohol and water and a chloro-hydrin(e) that obtains and hydrogenchloride generation dichloro-alcohol and water.More precisely, this method comprises the carboxylic acid catalyzed reaction.For example, when acetate was used as catalyzer, the esterification of glycerol and acetate was initiated and obtains glycerol acetate and water.Then, the substitution reaction by this glycerol acetate and hydrogenchloride generates a chloro-hydrin(e), and corresponding recovery acetate.Equally, generate a chloro-hydrin(e) acetic ester and a water, by the substitution reaction manufacturing dichlorohydrins of a chloro-hydrin(e) acetic ester, reclaim acetate afterwards then with hydrogenchloride by the esterification of a chloro-hydrin(e) and acetate.Direct substitution reaction by glycerol and hydrogenchloride when not having catalyzer can generate a chloro-hydrin(e) fast.But for making dichlorohydrins, direct substitution reaction does not become extremely slow when having catalyzer.Therefore, for making reaction effectively, must use catalyzer.
The method for preparing chloro-hydrin(e) of the present invention satisfies desired speed of response of commercialization and required yield level, also can be by helping that the minimized effecting reaction of waste and the sepn process of raw material, catalyzer and product are constituted.For example, when raw material was anhydrous hydrogen chloride or acetic acid catalyst, estimating had a large amount of losses or waste in reaction and sepn process, because the boiling point of these compounds is lower than the boiling point of glycerol or chloro-hydrin(e) compound.Particularly in reactive distillation processes, the amount of these lower boiling raw materials of being wasted during the course is quite big.Therefore, must design a kind of method makes reaction and still-process divide open shop.
The method according to this invention, reaction is separately carried out at different sections with distillation, and this answers still-process different with the classical inverse that reaction and distillation are carried out in a reactor together.The preferred pressure reactor that is to use sealing reacts thereby material is participated in to prevent the loss of lower boiling raw material.Say that exactly the pressure reactor of sealing is used for preventing that material from evaporating in temperature of reaction, perhaps be used for unlikelyly exceedingly supplying raw material, because oversupply may cause dissolving and causing thus the waste of material to reaction mixture.That is to say, for guaranteeing that enough pressure is so that solubilizing reaction mixture and raising reaction participate in the pressure reacting container of use sealing again.The also preferred pressure reacting container of being furnished with stirrer or outer circulation device that uses is with mixed reactant effectively and make uniformity of temperature profile.
In the method for the invention, separate and do not need to comprise any complex process of adding organic solvent, also do not need accurate equipment.Only need the most basic material, i.e. distillation tower.Therefore, method of the present invention helps effectively separating dichlorohydrins solution from reaction mixture.Reaction mixture herein is made of unreacted glycerol and ester, a chloro-hydrin(e) and ester, dichlorohydrins, catalyzer, water and unreacted hydrogen chloride (spirit of salt).For separating dichlorohydrins, reaction mixture carries out vacuum distilling.When dichlorohydrins separated by air distillation, that causes at the bottom of tower under the high temperature generated unwanted high boiling residue as side reactions such as thermolysis and polymerizations.Thereby, suppress side reaction by reducing column bottom temperature with reduction pressure, obtain dichlorohydrins thus.
The dichlorohydrins that can be used for making Epicholorohydrin carries out dehydrochlorination and neutralization by using as alkali lye such as milk of lime or sodium hydroxide solutions, shows whether the dichlorohydrins mixture comprises water or hydrogenchloride (spirit of salt) or wait other acidic components unimportant as the carboxylic acid catalyst.Described dichlorohydrins solution can be directly used in the manufacturing Epicholorohydrin, and need not any extra sepn process to increase purity.Therefore, as mentioned above, do not need process complicated or difficulty to be used for separating separately pure dichlorohydrins with equipment.Only need to be designed for the process of the minimization of loss that makes hydrogenchloride (spirit of salt) and carboxylic acid catalyst.
Method of the present invention preferably is made of following process: glycerol, acetate and anhydrous hydrogen chloride are continuously supplied in the airtight pressure reactor to depress initiation reaction adding.A certain amount of reaction mixture is continuously supplied to the vacuum tower that is used to prepare the dichlorohydrins mixing solutions of connection.The distilled residual solution is circulated in the reactor continuously.The distilled residual solution comprises a chloro-hydrin(e), dichlorohydrins, unreacted glycerol and acetic ester or the like.According to the method for the present invention of operate continuously, the composition that continuous round-robin distillates the dichlorohydrins of residual solution is clocklike kept, and the feed same without interruption by the vacuum distilling column overhead generates dichlorohydrins by other reaction.
As shown in fig. 1, preferred process of the present invention is realized by two airtight pressure reactors and vacuum tower.Say exactly, pipeline (11) supply of glycerol by being connected with first reactor (23), the carboxylic acid catalyst packs into by pipeline (12), and hydrogenchloride provides via pipeline (13).The liquid reaction mixture of first reactor (23) is supplied to second reactor (24) by pipeline (14), then with the glycerol reaction that wherein additionally replenishes via pipeline (15), the liquid reaction mixture of second reactor (24) is transferred to vacuum tower (25) by pipeline (16), and the steam that distillates product that generates in the vacuum tower (25) is by pipeline (17) condenser (26) of packing into.The distilled residual solution enters first reactor (23) by pipeline (22) circulation.In the said process, a part of reaction mixture can pass through pipeline (21) and discharge to regulate the concentration of the full-bodied resistates of high boiling point.Be back to vacuum tower (25) by a part of dichlorohydrins solution that condenser (26) obtains by pipeline (19) by pipeline (18), obtain reaction product dichlorohydrins solution by pipeline (20) then.
In process shown in Figure 1, in first reactor, cause principal reaction, show that dichlorohydrins mainly results from first reactor.For promote the generation of dichlorohydrins by continuous shifting balance, a certain amount of liquid reaction mixture must be shifted out first reactor continuously and enter second reactor.This is in order constantly to shift out the dichloro-alcohol and water from reactor.Move in order to carry out more effective balance, preferred excessive supply anhydrous hydrogen chloride must prevent that simultaneously it from increasing along with solubleness and waste, and Given this must use airtight pressure reactor.
In the present invention, make the second reactor work to handle unreacted hydrogen chloride (spirit of salt), it is caused by excessive supply and at the anhydrous hydrogen chloride of dissolved under pressure in first reactor.The liquid reaction mixture that is supplied to second reactor by first reactor comprises a large amount of hydrogenchloride that has neither part nor lot in the reaction in first reactor (spirit of salt), and it will be wasted in the process of being collected the dichlorohydrins mixing solutions by vacuum tower.Therefore, second reactor design is the minimization of loss that makes hydrogenchloride (spirit of salt), thereby increases the efficient of hydrogenchloride (spirit of salt) reaction.The reaction of the glycerol of Extra Supply is converted into the chloro-hydrin(e) compound thus in this unreacted hydrogen chloride (spirit of salt) and second reactor.
The stress level of regulating first reactor is in the scope of the speed of response of solubleness that helps anhydrous hydrogen chloride and glycerol.Supply pressure by conditioned reaction thing anhydrous hydrogen chloride comes the suitably stagnation pressure of conditioned reaction device.The temperature of reaction of first reactor is 70 ℃～140 ℃, is preferably 90 ℃～120 ℃.The invention is characterized in the temperature of reaction that does not need extra heating to keep first reactor.The heat that is used for keeping the temperature of first reactor gets that free vacuum tower round-robin distillates the temperature of residual solution and the solution heat of the anhydrous hydrogen chloride that provided.
The working temperature of second reactor is determined by the temperature of the liquid reaction mixture that first reactor provides.The operating pressure of second reactor is by the pressure of first reactor and the amount decision of the glycerol that is supplied to second reactor.The pressure of second reactor shows that by unreacted anhydrous chlorides of rase hydrogen evolution residual in first reactor pressure reduces when adding glycerol.
The optimum flow rate of manufacturing process of the present invention all plays a key effect for the pressure and temperature condition of reactor and for speed of response and productive rate.The device that is used for continuous flow procedure in exploitation is when being used for commercialization, if the balance between the input and output is destroyed, then reactant will accumulation continuously in device, and the result causes increasing by the amount of pipeline (21) discharge.Therefore, if there is not effective running of extra recovery system, must cause a large amount of losses of reactant, cause productive rate to descend, this is disadvantageous for commercialization.Imbalance between input and the output mainly is that two reasons cause.First reason is that speed of response crosses slow so that device can not be applied to continuous processing, shows that input is not very successful to the conversion of output.In this case, for increasing primitive reaction, need new catalyst, perhaps reactor needs custom-designed structure, perhaps attempts batch-type technology.Although second reason is speed of response for enough fast operating in the device of this continuous processing, input transforms fully but the size of reactor or hold-time are not enough.If this is the case, the size of input, circulation velocity and reactor must be optimized.
The optimum flow rate of method of the present invention is determined by following three technical factors.
First, enter the glycerol in the standard-sized reactor, each self-flow rate of acetic acid catalyst and anhydrous hydrogen chloride (pipeline (11), (12), (13) and (15)) summation and the balance between the flow velocity (pipeline (20)) of the dichlorohydrins that makes mean in glycerol, the summation of each self-flow rate of acetic acid catalyst and anhydrous hydrogen chloride and between vacuum tower (25) recirculation enters flow velocity first reactor (23), have dependency via pipeline (22), more precisely, between the flow velocity of the glycerol of the flow velocity of the glycerol that adds and recirculation, there is dependency.Exploitation in the present invention be used for business-like continuous manufacturing apparatus, the top condition that is used for dependency is as follows, wherein the effective volume of first reactor is expressed as V
1(l), the overall flow rate of glycerol (summation of pipeline (11) and pipeline (15)) is expressed as G (kg/hr), and the recirculation flow velocity is expressed as R (kg/hr).
In the formula (1), k
1Be to optimize constant of speed of flow, it is preferably 0.3kg/ (l-hr)～5kg/ (l-hr), and 0.5kg/ (l-hr)～1.5kg/ (l-hr) more preferably is to obtain best glycerol transformation efficiency (95%～100%) and the highest dichlorohydrins productive rate (90%～95%).
Second condition of the optimization flow velocity of determining according to the present invention is, in flow velocity R (kg/hr) that enters first reactor via pipeline (22) recirculation and the concentration C that remains in the unreacted hydrogen chloride (spirit of salt) the liquid reaction mixture that is supplied to second reactor (24) via pipeline (14) from first reactor (23)
1There is dependency between (weight %).
In the formula (2), the effective ways of the concentration of reduction unreacted hydrogen chloride (spirit of salt) have been proposed.That is, by increasing the concentration that recirculation flow velocity R (kg/hr) can reduce unreacted hydrogen chloride (spirit of salt).Yet if increase the level that recirculation flow velocity R (kg/hr) reduces unreacted hydrogen chloride (spirit of salt), the flow velocity of the glycerol of the supply of formula (1) will descend.Therefore, productivity that recirculation flow velocity R (kg/hr) must consideration equipment and unreacted hydrogen chloride (spirit of salt) but receiving amount determine.In the formula (2), work as k
2Be 3～5 o'clock, according to technology of the present invention, glycerol transformation efficiency and dichlorohydrins productive rate that can anticipated optimal set.
Simultaneously, also can show that the concentration of water is directly proportional with the solubleness of hydrogenchloride (spirit of salt) via pipeline (14) from the concentration (weight %) that first reactor (23) is supplied to the water W the liquid reaction mixture of second reactor (24) by formula (2) expression.In the present invention, according to formula (2), by regulate recirculation flow velocity R can controlling reactor in the content of hydrogenchloride (spirit of salt) and water, thus by all right reaction speed of mobile response balance.
The 3rd condition that is used for optimizing flow velocity is to remain in the unreacted hydrogen chloride (spirit of salt) that is supplied to the liquid reaction mixture of second reactor (24) from first reactor (23) via pipeline (14) to react with glycerol via pipeline (15) Extra Supply to the second reactor (24).Then, the level of unreacted hydrogen chloride (spirit of salt) descends, and has prevented the loss of hydrogenchloride (spirit of salt) thus in vacuum tower.The required flow rate (pipeline (15)) of the glycerol that add this moment is expressed as the G in the following formula
2(kg/hr).
In the formula (3), work as k
3Be 0.7～2.5 o'clock, according to technology of the present invention, glycerol transformation efficiency and dichlorohydrins productive rate that can anticipated optimal set.
Advantage
The invention provides by using hydrogenchloride to carry out chlorination by the method for preparing the economical and efficient of chloro-hydrin(e) as polyvalent alcohols such as glycerol with big technical scale.
Description of drawings
Above and other purpose of the present invention, feature and advantage will be by the descriptions of the in conjunction with the accompanying drawings following and preferred implementation that provides and are clearer.
Fig. 1 is a schema of describing method of the present invention.
Description of reference numerals
11: the glycerol supply line
12: carboxylic acid catalyst's supply line
13: the hydrogenchloride supply line
14: the liquid reaction mixture feeding pipeline
15: extra glycerol supply line
17: distillate the product vapor pipeline
22: distillation residual solution circulating line
23: the first reactors
24: the second reactors
25: vacuum tower
26: condenser
Embodiment
Shown in following embodiment, reality of the present invention and preferred embodiment be illustrative at present.
But, should be understood that those skilled in the art can make amendment and improve within the spirit and scope of the present invention when considering present disclosure.
Embodiment
Embodiment 1
As shown in Figure 1, supply glycerol, acetate and anhydrous hydrogen chloride continuously in by two reactors and experimental installation that vacuum tower constituted prepare dichlorohydrins by series reaction.The effective reacting volume of two reactors is respectively 1l, and first reactor is at 110 ℃ and 5Kgf/cm
2G work.Glycerol (75.42g/hr) and acetate (3.55g/hr) are continuously supplied to first reactor.(29.83f/hr) is continuously supplied to second reactor with glycerol.The fluid level of two reactors maintains certain level.The flow velocity that is recycled to first reactor by vacuum tower maintains 633.28g/hr.According to continuous operations under the described conditions, obtain remaining in the constant of expression in the concentration of the unreacted hydrogen chloride (spirit of salt) in the reactor and formula (1)～(3), total glycerol transformation efficiency and the productive rate of dichlorohydrins, and be presented in the table 1.
Table 1
| The concentration (weight %) of unreacted hydrogen chloride in first reactor (spirit of salt) | ??4.41 |
| The concentration (weight %) of unreacted hydrogen chloride in second reactor (spirit of salt) | ??1.99 |
| The constant of formula (1) | ??0.74 |
| The concentration (weight %) of unreacted hydrogen chloride in first reactor (spirit of salt) | ??4.41 |
| The constant of formula (2) | ??3.51 |
| The constant of formula (3) | ??0.94 |
| Total glycerol transformation efficiency (mole %) | ??100 |
| 1,3-dichlorohydrins+2, the productive rate of 3-dichlorohydrins (mole %) | ??97.58 |
Embodiment 2
As shown in Figure 1, supply glycerol, acetate and anhydrous hydrogen chloride continuously in by two reactors and experimental installation that vacuum tower constituted prepare dichlorohydrins by series reaction.The effective reacting volume of two reactors is respectively 1l, and first reactor is at 110 ℃ and 5Kgf/cm
2G work.Glycerol (192.35g/hr) and acetate (9.06g/hr) are continuously supplied to first reactor.(19.33g/hr) is continuously supplied to second reactor with glycerol.The fluid level of two reactors maintains certain level.The flow velocity that is recycled to first reactor by vacuum tower maintains 597.83g/hr.According to continuous operations under the described conditions, obtain remaining in the constant of expression in the concentration of the unreacted hydrogen chloride (spirit of salt) in the reactor and formula (1)～(3), total glycerol transformation efficiency and the productive rate of dichlorohydrins, and be presented in the table 2.
Table 2
| The concentration (weight %) of unreacted hydrogen chloride in first reactor (spirit of salt) | ??6.49 |
| The concentration (weight %) of unreacted hydrogen chloride in second reactor (spirit of salt) | ??2.64 |
| The constant of formula (1) | ??0.81 |
| The constant of formula (2) | ??5.02 |
| The constant of formula (3) | ??2.01 |
| Total glycerol transformation efficiency (mole %) | ??100 |
| 1,3-dichlorohydrins+2, the productive rate of 3-dichlorohydrins (mole %) | ??90.78 |
Embodiment 3
As shown in Figure 1, supply glycerol, acetate and anhydrous hydrogen chloride continuously in by two reactors and experimental installation that vacuum tower constituted prepare dichlorohydrins by series reaction.The effective reacting volume of two reactors is respectively 1l, and first reactor is at 110 ℃ and 5Kgf/cm
2G work.Glycerol (180.95g/hr) and acetate (8.53g/hr) are continuously supplied to first reactor.(16.51g/hr) is continuously supplied to second reactor with glycerol.The fluid level of two reactors maintains certain level.The flow velocity that is recycled to first reactor by vacuum tower maintains 990.2g/hr.According to continuous operations under the described conditions, obtain remaining in the constant of expression in the concentration of the unreacted hydrogen chloride (spirit of salt) in the reactor and formula (1)～(3), total glycerol transformation efficiency and the productive rate of dichlorohydrins, and be presented in the table 3.
Table 3
| The concentration (weight %) of unreacted hydrogen chloride in first reactor (spirit of salt) | ??3.6 |
| The concentration (weight %) of unreacted hydrogen chloride in second reactor (spirit of salt) | ??2 |
| The constant of formula (1) | ??1.19 |
| The constant of formula (2) | ??3.58 |
| The constant of formula (3) | ??2.16 |
| Total glycerol transformation efficiency (mole %) | ??100 |
| 1,3-dichlorohydrins+2, the productive rate of 3-dichlorohydrins (mole %) | ??92.88 |
Embodiment 4
As shown in Figure 1, supply glycerol, acetate and anhydrous hydrogen chloride continuously in by two reactors and experimental installation that vacuum tower constituted prepare dichlorohydrins by series reaction.The effective reacting volume of two reactors is respectively 1l, and first reactor is at 120 ℃ and 5Kgf/cm
2G work.Glycerol (181.4g/hr) and acetate (8.55g/hr) are continuously supplied to first reactor.(18.5g/hr) is continuously supplied to second reactor with glycerol.The fluid level of two reactors maintains certain level.The flow velocity that is recycled to first reactor by vacuum tower maintains 961.4g/hr.According to continuous operations under the described conditions, obtain remaining in the constant of expression in the concentration of the unreacted hydrogen chloride (spirit of salt) in the reactor and formula (1)～(3), total glycerol transformation efficiency and the productive rate of dichlorohydrins, and be presented in the table 4.
Table 4
| The concentration (weight %) of unreacted hydrogen chloride in first reactor (spirit of salt) | ??3.82 |
| The concentration (weight %) of unreacted hydrogen chloride in second reactor (spirit of salt) | ??3.08 |
| The constant of formula (1) | ??1.16 |
| The constant of formula (2) | ??3.74 |
| The constant of formula (3) | ??1.98 |
| Total glycerol transformation efficiency (mole %) | ??100 |
| 1,3-dichlorohydrins+2, the productive rate of 3-dichlorohydrins (mole %) | ??97.76 |
Embodiment 5
As shown in Figure 1, supply glycerol, acetate and anhydrous hydrogen chloride continuously in by two reactors and experimental installation that vacuum tower constituted prepare dichlorohydrins by series reaction.The effective reacting volume of two reactors is respectively 1l, and first reactor is at 120 ℃ and 5Kgf/cm
2G work.Glycerol (189.96g/hr) and acetate (3.88g/hr) are continuously supplied to first reactor.(19.5g/hr) is continuously supplied to second reactor with glycerol.The fluid level of two reactors maintains certain level.The flow velocity that is recycled to first reactor by vacuum tower maintains 956.74g/hr.According to continuous operations under the described conditions, obtain remaining in the constant of expression in the concentration of the unreacted hydrogen chloride (spirit of salt) in the reactor and formula (1)～(3), total glycerol transformation efficiency and the productive rate of dichlorohydrins, and be presented in the table 5.
Table 5
| The concentration (weight %) of unreacted hydrogen chloride in first reactor (spirit of salt) | ??3.72 |
| The concentration (weight %) of unreacted hydrogen chloride in second reactor (spirit of salt) | ??3.15 |
| The constant of formula (1) | ??1.17 |
| The constant of formula (2) | ??3.64 |
| The constant of formula (3) | ??1.83 |
| Total glycerol transformation efficiency (mole %) | ??100 |
| 1,3-dichlorohydrins+2, the productive rate of 3-dichlorohydrins (mole %) | ??92.71 |
Comparative example
As shown in Figure 1, supply glycerol, acetate and anhydrous hydrogen chloride continuously in by two reactors and experimental installation that vacuum tower constituted prepare dichlorohydrins by series reaction.The effective reacting volume of two reactors is respectively 1l, and first reactor is at 110 ℃ and 5Kgf/cm
2G work.Glycerol (90g/hr) and acetate (5.25g/hr) are continuously supplied to first reactor.(110.25g/hr) is continuously supplied to second reactor with glycerol.The fluid level of two reactors maintains certain level.The flow velocity that is recycled to first reactor by vacuum tower maintains 946.8g/hr.According to continuous operations under the described conditions, obtain remaining in the constant of expression in the concentration of the unreacted hydrogen chloride (spirit of salt) in the reactor and formula (1)～(3), total glycerol transformation efficiency and the productive rate of dichlorohydrins, and be presented in the table 6.
Table 6
| The concentration (weight %) of unreacted hydrogen chloride in first reactor (spirit of salt) | ??5.99 |
| The concentration (weight %) of unreacted hydrogen chloride in second reactor (spirit of salt) | ??2.40 |
| The constant of formula (1) | ??1.15 |
| The constant of formula (2) | ??5.82 |
| The constant of formula (3) | ??0.51 |
| Total glycerol transformation efficiency (mole %) | ??62.60 |
| 1,3-dichlorohydrins+2, the productive rate of 3-dichlorohydrins (mole %) | ??36.88 |
The result of embodiment 1～5 and comparative example confirms that as follows with the top condition of big technical scale manufacturing chloro-hydrin(e) by using hydrogenchloride that polyvalent alcohol is carried out chlorination: the flow velocity of the decision polyvalent alcohol flow velocity and the ratio of recirculation feed flow velocity is optimized constant k
1Be 0.3kg/ (l-hr)～5kg/ (l-hr); The flow velocity that determines the effective volume (l) of unreacted hydrogen chloride (spirit of salt) content (weight %), first reactor in the first product mixtures feed and/or be circulated to the dependency between the flow velocity (weight %) of the recirculation feed in first reactor is optimized constant k
2Be 3kg/ (l-hr)～5kg/ (l-hr); Decision is supplied to the flow velocity of the concentration of unreacted hydrogen chloride (spirit of salt) in the flow velocity of the polyvalent alcohol feed of second reactor and recirculation feed and first product mixtures and optimizes constant k
3Be 0.7～2.5.
It will be understood by those of skill in the art that disclosed design and embodiment in the above stated specification are easy to making an amendment or designing other the basis of embodiment that is used to realize the identical purpose of the present invention.Those skilled in the art it is also understood that these equivalent embodiments do not deviate from the spirit and scope of the invention as illustrating in the claims.
Claims (20)
1. one kind prepares the method for chloro-hydrin(e) by series reaction, and described method comprises following process:
The reaction mixture feed that will comprise polyvalent alcohol, hydrogenchloride and organic acid (chlorination catalyzer) is packed in first reactor, generates chloro-hydrin(e) by chlorination in described first reactor;
To be supplied to second reactor by the first product mixtures feed that comprises chloro-hydrin(e) and non-reacted reaction mixture of described first reactor discharge and extra polyvalent alcohol, in described second reactor, generate chloro-hydrin(e) by other chlorination;
Will be by the second product mixtures feed that comprises chloro-hydrin(e) that described second reactor is discharged distillation tower of packing into, the top portion by distillation tower is from the product of distillation that comprises chloro-hydrin(e) then; With
A part of recirculation feed that will comprise the distillation residual solution of chloro-hydrin(e) is recycled in described first reactor.
2. as claimed in claim 1ly prepare the method for chloro-hydrin(e) by series reaction, wherein, the ratio of flow velocity and the flow velocity of the feed of recirculation that is supplied to the polyvalent alcohol of described first reactor and second reactor satisfies following formula (1):
[in the formula (1), V
lBe the effective volume (l) of described first reactor, G is the overall flow rate (kg/hr) that is supplied to the polyvalent alcohol of described first reactor and second reactor, and R is the flow velocity (kg/hr) that is circulated to the recirculation feed of described first reactor by distillation tower, k
1Be that flow velocity is optimized constant, be preferably 0.3kg/ (l-hr)～5kg/ (l-hr)].
3. as claimed in claim 2ly prepare the method for chloro-hydrin(e) by series reaction, wherein, k
1Be 0.5kg/ (l-hr)～1.5kg/ (l-hr).
4. as claimed in claim 1ly prepare the method for chloro-hydrin(e) by series reaction, wherein, the concentration that remains in the unreacted hydrogen chloride (spirit of salt) in the described first product mixtures feed that is supplied to described second reactor satisfies following formula (2):
[in the formula (2), C
1Be the concentration (weight %) of the unreacted hydrogen chloride (spirit of salt) in the described first product mixtures feed, V
1Be the effective volume (l) of described first reactor, R is the flow velocity (kg/hr) that is circulated to the recirculation feed of described first reactor by distillation tower, k
2Be that flow velocity is optimized constant, be preferably 3～5].
5. the method for preparing chloro-hydrin(e) by series reaction as claimed in claim 1, wherein, Extra Supply to the flow velocity of the flow velocity of the polyvalent alcohol of described second reactor, recirculation feed and the concentration that remains in the unreacted hydrogen chloride (spirit of salt) in described first product mixtures satisfies following formula (3):
[in the formula (3), G
2Be the flow velocity (kg/hr) that is supplied to the polyvalent alcohol of described second reactor, G
1It is the flow velocity (kg/hr) of the polyvalent alcohol that comprised of the described reaction mixture feed of described first reactor, G is the overall flow rate (kg/hr) that is supplied to the polyvalent alcohol of described first reactor and second reactor, R is the flow velocity (kg/hr) that is circulated to the recirculation feed of described first reactor by distillation tower, C
1Be the concentration (weight %) of the unreacted hydrogen chloride (spirit of salt) in the described first product mixtures feed, k
3Be the constant of speed of flow of optimizing, it is preferably 0.7～2.5].
6. as each described method for preparing chloro-hydrin(e) by series reaction in the claim 1～5, wherein, the non-reacted reaction mixture that remains in described first product mixtures of being discharged by described first reactor comprises polyvalent alcohol, hydrogenchloride, organic acid catalyst and water.
7. as each describedly prepares the method for chloro-hydrin(e) by series reaction in the claim 1～5, wherein, the described recirculation feed that is recycled in described first reactor comprises chloro-hydrin(e) and unreacted polyvalent alcohol.
8. as each described method for preparing chloro-hydrin(e) by series reaction in the claim 1～5, wherein, described polyvalent alcohol is selected from by 1,2-ethylene glycol, 1,2-propylene glycol, 1, ammediol, 3-chloro-1, the group that 2-propylene glycol, glycerin and glycerol and their ester cpds and composition thereof are formed.
9. as claimed in claim 8ly prepare the method for chloro-hydrin(e) by series reaction, wherein, described polyvalent alcohol is a glycerol.
10. as each describedly prepares the method for chloro-hydrin(e) by series reaction in the claim 1～5, wherein, described organic acid is selected from the group of being made up of monocarboxylic acid or dicarboxylic acid, its acid anhydrides, salt and ester cpds.
11. as claimed in claim 10ly prepare the method for chloro-hydrin(e) by series reaction, wherein, described organic acid is an acetate.
12. as each describedly prepares the method for chloro-hydrin(e) by series reaction in the claim 1～5, wherein, described hydrogenchloride is anhydride.
13. as claimed in claim 12ly prepare the method for chloro-hydrin(e) by series reaction, wherein, the temperature of reaction of described first reactor is 70 ℃～140 ℃.
14. as claimed in claim 12ly prepare the method for chloro-hydrin(e) by series reaction, wherein, the temperature of reaction of described first reactor is kept by the temperature of recirculation feed and the solution heat of anhydrous hydrogen chloride.
15. as claimed in claim 14ly prepare the method for chloro-hydrin(e) by series reaction, wherein, described anhydrous hydrogen chloride without interruption is to depress initiation reaction adding.
16., wherein, comprise chloro-hydrin(e), organic acid catalyst and water by the isolating described product of distillation in the top of described distillation tower as each describedly prepares the method for chloro-hydrin(e) by series reaction in the claim 1～5.
17. as claimed in claim 16ly prepare the method for chloro-hydrin(e) by series reaction, wherein, the content of the chloro-hydrin(e) in the described product of distillation is 50 weight %～90 weight %.
18. as claimed in claim 16ly prepare the method for chloro-hydrin(e) by series reaction, wherein, described product of distillation separates by vacuum distilling.
19. a chloro-hydrin(e) that is generated by the described method of claim 9 prepares the method for Epicholorohydrin.
The method of not having any sepn process 20. the product of distillation that comprises chloro-hydrin(e) by the preparation of the described method of claim 16 prepares Epicholorohydrin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2007-0097675 | 2007-09-28 | ||
| KR1020070097675A KR101410019B1 (en) | 2007-09-28 | 2007-09-28 | Process for preparing chlorohydrin by reaction of polyol with hydrochloric acid |
| PCT/KR2008/005474 WO2009041766A1 (en) | 2007-09-28 | 2008-09-17 | Process for preparing chlorohydrin by reaction of polyol with hydrochloric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101842339A true CN101842339A (en) | 2010-09-22 |
| CN101842339B CN101842339B (en) | 2013-08-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801143217A Expired - Fee Related CN101842339B (en) | 2007-09-28 | 2008-09-17 | Process for preparing chlorohydrin by reaction of polyol with hydrochloric acid |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101410019B1 (en) |
| CN (1) | CN101842339B (en) |
| WO (1) | WO2009041766A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922299A (en) * | 2019-11-07 | 2020-03-27 | 无锡市银杏塑业科技有限公司 | Continuous preparation method of high-content 2-chloroethanol |
| CN113234041A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101705210B1 (en) | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | Method of preparing composition of chlorohydrins and method of preparing epichlorohydrin using composition of chlorohydrins prepared by the same |
| KR101705208B1 (en) * | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | Method of preparing composition of chlorohydrins and method of preparing epichlorohydrin using composition of chlorohydrins prepared by the same |
| KR101705209B1 (en) * | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | Method of preparing composition of chlorohydrins and method of preparing epichlorohydrin using composition of chlorohydrins prepared by the same |
| KR101705205B1 (en) * | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | Method of preparing chlorohydrins and method of preparing epichlorohydrin using chlorohydrins prepared by the same |
| KR101705206B1 (en) * | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | Method of preparing chlorohydrins and method of preparing epichlorohydrin using chlorohydrins prepared by the same |
| KR101705207B1 (en) | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | Method of preparing chlorohydrins and method of preparing epichlorohydrin using chlorohydrins prepared by the same |
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|---|---|---|---|---|
| US4634784A (en) * | 1984-06-04 | 1987-01-06 | Showa Denko Kabushiki Kaisha | Process for production of epichlorohydrin |
| US4665240A (en) * | 1986-05-27 | 1987-05-12 | Shell Oil Company | Process for the production of dichlorohydrin |
| WO2006020234A1 (en) * | 2004-07-21 | 2006-02-23 | Dow Global Technologies Inc. | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
| WO2006106154A1 (en) * | 2005-05-20 | 2006-10-12 | Solvay (Société Anonyme) | Continuous method for making chlorhydrines |
-
2007
- 2007-09-28 KR KR1020070097675A patent/KR101410019B1/en active IP Right Grant
-
2008
- 2008-09-17 CN CN2008801143217A patent/CN101842339B/en not_active Expired - Fee Related
- 2008-09-17 WO PCT/KR2008/005474 patent/WO2009041766A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4634784A (en) * | 1984-06-04 | 1987-01-06 | Showa Denko Kabushiki Kaisha | Process for production of epichlorohydrin |
| US4665240A (en) * | 1986-05-27 | 1987-05-12 | Shell Oil Company | Process for the production of dichlorohydrin |
| WO2006020234A1 (en) * | 2004-07-21 | 2006-02-23 | Dow Global Technologies Inc. | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
| WO2006106154A1 (en) * | 2005-05-20 | 2006-10-12 | Solvay (Société Anonyme) | Continuous method for making chlorhydrines |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922299A (en) * | 2019-11-07 | 2020-03-27 | 无锡市银杏塑业科技有限公司 | Continuous preparation method of high-content 2-chloroethanol |
| CN113234041A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
| CN113234041B (en) * | 2021-04-07 | 2023-03-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101410019B1 (en) | 2014-06-26 |
| KR20090032429A (en) | 2009-04-01 |
| WO2009041766A1 (en) | 2009-04-02 |
| CN101842339B (en) | 2013-08-28 |
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