CN106518683A - Method and device for synthesizing triethyl citrate by applying vapor permeation dehydration technique - Google Patents
Method and device for synthesizing triethyl citrate by applying vapor permeation dehydration technique Download PDFInfo
- Publication number
- CN106518683A CN106518683A CN201611023875.9A CN201611023875A CN106518683A CN 106518683 A CN106518683 A CN 106518683A CN 201611023875 A CN201611023875 A CN 201611023875A CN 106518683 A CN106518683 A CN 106518683A
- Authority
- CN
- China
- Prior art keywords
- ethanol
- water
- reactor
- reaction
- citric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method and a device for synthesizing triethyl citrate by applying a vapor permeation dehydration technique, belonging to the technical field of permeation gasification membrane separation application and organism synthesis. The method comprises the following steps: adding citric acid, ethanol and a catalyst into a reaction kettle according to a certain ratio, and heating to certain temperature, wherein triethyl citrate and water are mainly generated from reactants under the catalytic action of the catalyst. In the reaction process, rising vapor and downstream backflow liquid inside the reaction kettle play roles of heat conduction and mass transfer in a rectifying column, generated ethanol and water are distilled out from the tower top of the rectifying column, and the distillate is dehydrated as a vapor permeation dehydration raw material. After the distillate is dehydrated, ethanol vapor with relatively high purity is condensed and fed back to the reaction kettle. As ethanol is adopted as a water carrying agent, water carried by the raw materials and water generated in the reaction process can be continuously removed, the reaction can be promoted to the direction of ester production, and thus the conversion rate of the reaction can be increased. According to the method and the device, the triethyl citrate is high in esterification rate and purity, ethanol amount is low, recycling process is not needed, the process is simple and the operation energy consumption is low.
Description
Technical field
The present invention relates to a kind of Steam soak dehydration technique is used for the method and apparatus of synthesizing citric acid triethyl, belongs to and ooze
Vaporize thoroughly UF membrane application and organic synthesis technical field.
Background technology
Triethyl citrate is a kind of important industrial chemicals, is mainly used as the thermoplastic resin such as cellulose family, vinyl-based
The plasticizer of fat.In food service industry, it is widely used in additive, antioxidant and fumet.In tobacco industry, it is that vinegar is fine
The best substitute of filter stick plasticizer triacetyl glycerine.FDA Food and Drug Administration's approved triethyl citrate conduct
Nontoxic plasticizer, for packaging for foodstuff, medical apparatus, toy for children and personal hygiene article.Therefore, research and develop citric acid
Triethyl has very important significance.
Industrial triethyl citrate is mainly with the concentrated sulfuric acid as catalyst at present, with benzene or toluene as water entrainer, passes through
The esterification of citric acid and ethanol is synthesizing.Make catalyst with the concentrated sulfuric acid and side reaction easily occur, be mixed with causing product a small amount of ether,
Sulfuric ester etc., affects product quality；Secondly, sulfuric acid meeting severe corrosion equipment, equipment will be regularly updated, and cost is improved.With benzene or
Toluene makees water entrainer, and benzene and toluene toxicity are big, and are not suitable for medicine, tobacco, packaging for foodstuff, medical apparatus and toy for children
In.It is developing direction as water entrainer with ethanol, some processes such as Chinese patent, Authorization Notice No. CN102584590 B are disclosed
's《A kind of method of synthesizing citric acid triethyl》, disclosed in Authorization Notice No. CN102079704B《A kind of triethyl citrate
Preparation method》And disclosed in application publication number CN102336667A《A kind of non-toxic efficient plasticizer triethyl citrate
Preparation method》Describe using absolute ethyl alcohol as do not refer in reactant and water entrainer, but patent ethanol reclaim problem,
And ethanol actual amount is much larger than reaction consumption in course of reaction.
The content of the invention
The technical problem to be solved in the present invention be realize triethyl citrate synthetic reaction in carry water with generate water and
When remove, it is to avoid the process during follow-up refined to water, it is proposed that a kind of Steam soak dehydration technique is used for synthesizing citric acid
The method and apparatus of triethyl.The distillate that reactor is distillated is steamed by rectifying column, feed pump, membrane module, condenser
Vapour permeating and dewatering, the water generated in constantly removing the water that carries and course of reaction, it is to avoid it is follow-up it is refined during water is taken off
Remove, improve conversion ratio and product quality, it is ensured that final products water content maintains relatively low level, prevent product product
The reduction of matter, reduce further production cost.
A kind of method that Steam soak dehydration technique is used for synthesizing citric acid triethyl, comprises the steps：
1st step, citric acid, ethanol and catalyst are added in reactor carries out esterification；
2nd step, heating is carried out to reaction kettle of the esterification makes part ethanol and water vapor, steam enter rectifying in rectifying column, and steam exists
Obtain mainly containing the distillate of second alcohol and water after capital condensation；
3rd step, the distillate of capital are dehydrated in being re-fed into infiltrating and vaporizing membrane, and the material ethanol after dehydration is back to reaction
Kettle；
4th step, after reaction terminates, washes to reactant, then activated carbon decolorizing is added in reactant, then carry out decompression steaming
Evaporate, collect distillate and obtain triethyl citrate product.
In the 1st described step, catalyst is cationic catalysts resin, the concentrated sulfuric acid, p-methyl benzenesulfonic acid or phosphoric acid.
In the 1st described step, the reactant ethanol 0.1～10wt.% of water content of input, preferably 0.5～1 wt.%.
In the 2nd described step, rectifying column tower top pressure mode of operation elects normal pressure or pressurization, preferred normal pressure as；Rectifying column tower
The reflux ratio that top adopts is 0.1～5.
In the 3rd described step, the gauge pressure of infiltrating and vaporizing membrane feed side is 0～0.6MPa, and the temperature of feed side is 70～160
℃；The absolute pressure of the per-meate side of infiltrating and vaporizing membrane is 100～10000Pa.
The film that described Pervaporation membrane separator is adopted is preferential water permeable membrane, can be molecular screen membrane, silicon dioxide film
Or PVA film, optimum is molecular screen membrane.
In the 3rd described step, the material ethanol water content control after dehydration is in 0.03～2wt.%.
In the 4th described step, the temperature of reaction kettle of triethyl citrate vacuum distillation is 100～180 DEG C.
In the 4th described step, before washing to reactant, reactant is carried out in alkali cleaning using aqueous sodium carbonate
With.
In the 4th described step, the washings obtained to alkali cleaning and washing reclaim ethanol using rectifying, osmotic, evaporating and dewatering.
A kind of Steam soak dehydration technique is used for the device of synthesizing citric acid triethyl, includes reactor, in reactor
Top is provided with rectifying column, and the capital of rectifying column passes sequentially through overhead condenser, ethanol and receives tank, hydrous ethanol delivery pump, steams
Send out device to be connected with the feed liquid side entrance of infiltration vaporization membrane module；Citric acid three is also equipped with the condensate outlet of overhead condenser
Ethyl ester receives tank；The per-meate side of infiltration vaporization membrane module is connected with penetrating fluid condenser, infiltration flow container successively, in infiltration liquid condensing
Vacuum buffer tank and vavuum pump are disposed with device also；The feed liquid side outlet of infiltration vaporization membrane module passes sequentially through finished product condensation
Device, finished product temporary storage tank, absolute ethyl alcohol delivery pump are connected with reactor.
What is installed in infiltration vaporization membrane module is molecular screen membrane, silicon dioxide film or PVA film, preferred molecular sieve film.
Alkali wash water is also provided with reactor and adds tank, for alkali lye being added in reactor；Can also arrange
Water lotion adds tank, for adding washing water in reactor；Activated carbon can also be set and add mouth, for adding in reactor
Enter activated carbon；Can be carried out for the reactant liquor after operating to activated carbon decolorizing with connecting equipment for separating liquid from solid on reactor
Leach activated carbon operation.
Washings can also be set on reactor and receive tank, washings are received tank and are connected with rectifying column again, for washing
Wash ethanol in water rectifying, reuse after osmotic, evaporating and dewatering again.
Beneficial effect
Compared with conventional art, the water that reaction is generated can be continuously taken off with the water for carrying in esterification reaction process of the present invention
Remove, instead of the dewatering type for adding the water entrainers such as toluene, benzene, promote reaction process, eliminate reaction and terminate at rear ethanol
The technique of reason, reduces recovery cost, improves product quality, reduces production cost.The process is using ethanol as band simultaneously
Aqua, can direct circulation utilize, improve the service efficiency of ethanol；Infiltrating and vaporizing membrane material dehydration efficiency high, shorter anti-
Higher reaction conversion ratio can be ensured in seasonable；Rectifying column tower top pressure mode of operation on the reactor of the present invention is more
During sample, i.e. pressurized operation, overhead is capable of achieving Jing after partial condensation, steam Jing concurrent heatings are directly entered infiltration evaporation UF membrane
System, it is to avoid double evaporation-cooling, reduces energy consumption；During atmospheric operation, after distillate is condensed, partial reflux, partly as steaming
The raw material of vapour permeable membrane separate System, Jing after evaporimeter vaporization, is dehydrated into membrane module, and the process causes reactor and steams
Vapour permeable membrane element is separate in terms of operating condition, easy to operate, and system is easy to stable；In later stage subtractive process, kettle liquid
Water content is low, it is to avoid process of the later stage to water.The film separation system dewatering efficiency of the present invention is high, and the reaction time is short, production effect
Rate is high, and product esterification yield is high, and triethyl citrate purity is high；The Organic substance in water content removed in the film separation system of the present invention
Less, sewage disposal is simple, and resource recovery is high.
Description of the drawings
Fig. 1 is the method and apparatus that the vapor permeable membrane dehydration technique that the present invention is provided is used for synthesizing citric acid triethyl
Flow chart：1st, reactor；2nd, rectifying column；3rd, overhead condenser；4th, triethyl citrate receives tank；5th, ethanol receives tank；6th, contain
Water-ethanol delivery pump；7th, evaporimeter；8th, infiltration vaporization membrane module；9th, penetrating fluid condenser；10th, permeate flow container；11st, vacuum buffer
Tank；12nd, vavuum pump；13rd, finished product condenser；14th, finished product temporary storage tank；15th, absolute ethyl alcohol delivery pump.
Specific embodiment
The present invention is described in further detail below by specific embodiment.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted concrete skill in embodiment
Art or condition person, are carried out according to the technology or condition described by document in the art or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, be can pass through city available from conventional products.
Using range format expression value should be interpreted as in a flexible way not only include clearly include as scope
The numerical value of limit value, but also including all single numbers or subinterval for covering within the range, just as each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood to not only include what is clearly included
The concentration of about 0.1% to about 5%, also including the single concentration in the range of alluding to（Such as, 1%, 2%, 3% and 4%）And subinterval（Example
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.Heretofore described percentage in the case of without special instruction,
Refer to percentage by weight.
It is addressed in this manual to " one embodiment ", " another embodiment ", " embodiment " etc., refer to
Specific features, structure with reference to embodiment description are included at least one embodiment of the application generality description.
It is not necessarily to refer to same embodiment that statement of the same race occur in multiple places in the description.Furthermore, it is understood that combining arbitrary
When embodiment describes specific features, structure or a feature, to be advocated is realizing this spy with reference to other embodiment
Levy, structure or feature also fall in the application scope of the claimed.
Steam soak dewatering membrane has excellent dewatering, the advantages of water selective is high, in dehydration of organic solvent process
In show good separating property.Steam soak membrane separation technique is considered as a kind of energy-efficient new separation skill
Art, the process mainly utilize dissolving of the organic matter in film and diffusion rate to be less than dissolving and diffusion of the water in film, so as to reality
The removing of moisture in existing organic matter.Vapor permeable membrane dehydration technique is used for into the synthesis of triethyl citrate, mainly with excess
Ethanol is water entrainer, corrosion-free, pollution-free, realizes that the water that esterification reaction process is produced is removed in time, will during subsequently refining
Without the need for processing to water, the conversion ratio of reaction is improved.
The key step of the present invention：1st step, citric acid, ethanol and catalyst are added in reactor carries out esterification；
2nd step, heating is carried out to reaction kettle of the esterification makes part ethanol and water vapor, steam enter rectifying in rectifying column, and steam is in capital
Obtain mainly containing the distillate of second alcohol and water after condensation；3rd step, the distillate of capital are taken off in being re-fed into infiltrating and vaporizing membrane
Water, the material after dehydration（Mainly ethanol）It is back to reactor；4th step, after reaction terminates, is washed with water to reaction mass
Wash, add activated carbon decolorizing, carry out vacuum distillation again, collect distillate and obtain triethyl citrate product.
Catalyst in reaction elects cationic catalysts resin, the concentrated sulfuric acid, p-methyl benzenesulfonic acid, phosphoric acid as；The 2nd described step
In, rectifying column tower top pressure mode of operation elects normal pressure or pressurization, preferred normal pressure as；The reflux ratio that rectifying column tower top is adopted is 0.1
～5.
In the 3rd described step, the gauge pressure of infiltrating and vaporizing membrane feed side is 0～0.6MPa, and the temperature of feed side is 70～160
℃；The absolute pressure of the per-meate side of infiltrating and vaporizing membrane is 100～10000Pa.The film that described Pervaporation membrane separator is adopted is for excellent
First water permeable membrane, can be molecular screen membrane, silicon dioxide film, PVA film, and optimum is molecular screen membrane.In order to improve infiltration evaporation separation
The separation factor of process, can also be located after being first re-fed into using the washing of 5% sodium carbonate liquor using the reactant after terminating to reaction
The mode of reason.
Apparatus structure of the present invention is provided with rectifying on 1 top of reactor as shown in figure 1, include reactor 1
Post 2, the capital of rectifying column 2 pass sequentially through overhead condenser 3, ethanol and receive tank 5, hydrous ethanol delivery pump 6, evaporimeter 7 and ooze
The feed liquid side entrance connection of vaporization membrane module 8 thoroughly；Triethyl citrate is also equipped with the condensate outlet of overhead condenser 3 to connect
Closed cans 4；The per-meate side of infiltration vaporization membrane module 8 is connected with penetrating fluid condenser 9, infiltration flow container 10 successively, in infiltration liquid condensing
Vacuum buffer tank 11 and vavuum pump 12 are disposed with device 9 also；The feed liquid side outlet of infiltration vaporization membrane module 8 is passed sequentially through into
Product condenser 13, finished product temporary storage tank 14, absolute ethyl alcohol delivery pump 15 are connected with reactor 1.Wherein, triethyl citrate receives tank
5 is pass through after reaction terminates triethyl citrate finished product obtained from vacuum distillation for receive.Pacify in infiltration vaporization membrane module 8
Dress is molecular screen membrane, silicon dioxide film or PVA film, preferred molecular sieve film.
In order to post-process to the reactant liquor that reaction is completed, alkali wash water is also provided with reactor 1 and adds tank,
For adding alkali lye in reactor；Water lotion can also be set and add tank, for washing water being added in reactor 1；May be used also
Mouth is added to arrange activated carbon, for activated carbon being added in reactor 1；Can be filled with connecting separation of solid and liquid on reactor 1
Put, carry out leaching activated carbon operation for the reactant liquor after operating activated carbon decolorizing.In addition, can also set on reactor 1
Put washings receive tank, washings receive tank be connected with rectifying column 2 again, for by the ethanol in washings again rectifying, infiltration
Reuse after evaporating and dewatering.
Embodiment 1
The method that Steam soak dehydration technique is used for synthesizing citric acid triethyl, the device of employing is as shown in figure 1, operating process bag
Include the following steps：
By 5 kg citric acids, 6.17kg absolute ethyl alcohols, heating response in 45g p-methyl benzenesulfonic acid input reactor 1, urge in catalyst
Esterification is carried out under change effect, the temperature in reactor is 115 DEG C, and the upflowing vapor in reactor is with descending phegma in essence
Carry out heat and mass transfer in fractional distillation column 2, the control of rectifying column tower top temperature at 78 DEG C or so, the feed liquid that tower top is steamed（Mainly ethanol）
Ethanol is flowed into Jing after overhead condenser 3 is condensed to receive in tank 5, used as phegma, reflux ratio is 1 to a part of overhead distillate, separately
A part is conveyed by hydrous ethanol delivery pump 6 as the material liquid of Steam soak dehydration, Jing after the heating vaporization of evaporimeter 7
Into UF membrane unit 8, UF membrane unit 8 is by 0.12m2Molecular screen membrane, silicon dioxide film or PVA film component（Every grade of membrane module
Area is 0.03 m2）It is in series.Feed liquid lateral pressure is 0.25MPa（Gauge pressure）, osmotic lateral pressure control is in 1000 Pa.Feed liquid
Water and a small amount of ethanol in the solution of side obtains penetrating fluid through infiltrating and vaporizing membrane in vapour form, and per-meate side is in vavuum pump 12
Under suction, the penetrating fluid for obtaining is flowed in infiltration flow container 10 Jing after the condensation of penetrating fluid condenser 9.Coating materials liquid side feed liquid water content leads to
Crossing infiltration evaporation membrane separator significantly can reduce, and obtain absolute ethyl alcohol, and absolute ethyl alcohol is Jing after dehydration finished product condenser 13 is condensed
Flow in finished product temporary storage tank 14, and interior the continuing to participate in of reactor 1 is back to by the conveying of absolute ethyl alcohol delivery pump 15 and react and take out of
The water that reaction is generated.Reaction is carried out to reactor acid number less than stopping reaction after 5 mg (KOH)/g.Afterwards using distillation water washing
Reactant, adds activated carbon decolorizing, and vacuum distillation is carried out after activated carbon is leached, and 160 DEG C of 1 temperature control of reactor is received
Collection distillate obtains triethyl citrate product and collects in triethyl citrate reception tank 4.Triethyl citrate purity is
99.9%, product esterification yield is about 99.5%.
When using different membrane materials, the data such as the penetrating fluid of gained, water flux, reaction time are as shown in table 1.Averagely
The mean value calculation of reaction time, average water flux and penetrating fluid average moisture content according to 10 secondary responses.
Table 1
As can be seen from the table, molecular screen membrane is particularly suitable for the processed of ethanol in triethyl citrate building-up process, institute
Penetrating fluid water content, water flux better than other species membrane material, simultaneously because dehydrating effect is more preferably, the reaction to ethanol
Facilitation effect becomes apparent from, and when reaching same processing requirement, operation hours is shorter.
Embodiment 2
The method that Steam soak dehydration technique is used for synthesizing citric acid triethyl, the device of employing is as shown in figure 1, operating process bag
Include the following steps：
By 5 kg citric acids, a certain amount of 95vol% ethanol or absolute ethyl alcohol, heating in 45g p-methyl benzenesulfonic acid input reactor 1
Reaction, carries out esterification under catalyst effect, and the temperature in reactor is 120 DEG C, the upflowing vapor in reactor
Heat and mass transfer is carried out in rectifying column 2 with descending phegma, rectifying column tower top temperature is controlled at 78 DEG C or so, what tower top was steamed
Feed liquid（Mainly ethanol）Ethanol is flowed into Jing after overhead condenser 3 is condensed to receive in tank 5, a part of overhead distillate is used as backflow
Liquid, reflux ratio are 1, material liquid of the another part as Steam soak dehydration, are conveyed by hydrous ethanol delivery pump 6, and Jing steams
Membrane separator group 8 is entered after sending out the heating vaporization of device 7, UF membrane unit 8 is by 0.12m2Molecular screen membrane（Every grade of membrane module area is
0.03 m2）It is in series.Feed liquid lateral pressure is 0.25MPa（Gauge pressure）, osmotic lateral pressure control is in 1000 Pa.Feed liquid side solution
In water and a small amount of ethanol obtain penetrating fluid, suction of the per-meate side in vavuum pump 12 through infiltrating and vaporizing membrane in vapour form
Under, the penetrating fluid for obtaining is flowed in infiltration flow container 10 Jing after the condensation of penetrating fluid condenser 9.Coating materials liquid side feed liquid water content is by oozing
Vaporization membrane separator significantly can be reduced thoroughly, obtain absolute ethyl alcohol, and absolute ethyl alcohol is flowed into Jing after dehydration finished product condenser 13 is condensed
In finished product temporary storage tank 14, and it is back in reactor 1 by the conveying of absolute ethyl alcohol delivery pump 15 and continues to participate in reaction and take reaction out of
The water of generation.Reaction is carried out to reactor acid number less than stopping reaction after 5 mg (KOH)/g.Distilled water washing reaction is used afterwards
Thing, adds activated carbon decolorizing, and vacuum distillation is carried out after activated carbon is leached, and 140 DEG C of 1 temperature control of reactor obtains lemon
Lemon triethylenetetraminehexaacetic acid ester product is collected and is received in tank 4 in triethyl citrate.Triethyl citrate purity is 99.9%, product esterification yield
About 99.5%.
When the ethanol using different moisture content is used as raw material, the data such as the penetrating fluid of gained, water flux, reaction time are such as
Shown in table 2.The mean value calculation of average reaction time, average water flux and penetrating fluid average moisture content according to 10 secondary responses.
Table 2
As can be seen from the table, reaction can be made to carry out faster using the lower ethanol of water content, while reducing film device
Dehydrating amount, when reaching the same reaction time, required membrane area can be less.
Embodiment 3
The method that Steam soak dehydration technique is used for synthesizing citric acid triethyl, the device of employing is as shown in figure 1, operating process bag
Include the following steps：
By 5 kg citric acids, 6.17kg absolute ethyl alcohols, 45g catalyst（Cationic catalysts resin, the concentrated sulfuric acid, p-methyl benzenesulfonic acid）Throw
Entering heating response in reactor 1, esterification being carried out under catalyst effect, the temperature in reactor is 113 DEG C, reaction
Upflowing vapor in kettle carries out heat and mass transfer in rectifying column 2 with descending phegma, and rectifying column tower top temperature is controlled at 78 DEG C
Left and right, the feed liquid that tower top is steamed（Mainly ethanol）Ethanol is flowed into Jing after overhead condenser 3 is condensed to receive in tank 5, a part of tower
Used as phegma, reflux ratio is 1.5 to top distillate, material liquid of the another part as Steam soak dehydration, by aqueous second
Alcohol delivery pump 6 is conveyed, and Jing after the heating vaporization of evaporimeter 7 enters membrane separator group 8, and UF membrane unit 8 is by 0.18m2Molecular screen membrane
（Every grade of membrane module area is 0.03 m2）It is in series.Feed liquid lateral pressure is 0.3MPa（Gauge pressure）, osmotic lateral pressure control exist
800 Pa.Water and a small amount of ethanol in the solution of feed liquid side obtains penetrating fluid, per-meate side through infiltrating and vaporizing membrane in vapour form
Under the suction of vavuum pump 12, the penetrating fluid for obtaining is flowed in infiltration flow container 10 Jing after the condensation of penetrating fluid condenser 9.Coating materials liquid side
Feed liquid water content significantly can be reduced by infiltration evaporation membrane separator, obtain absolute ethyl alcohol, and absolute ethyl alcohol Jing dehydration finished products are cold
Condenser 13 is flowed into after condensing in finished product temporary storage tank 14, and is back to continuation ginseng in reactor 1 by the conveying of absolute ethyl alcohol delivery pump 15
With the water for reacting and taking out of reaction generation.Reaction carries out to reactor acid number being less than 5 mg (KOH)/g（Deduct sulfuric acid acid number）Afterwards
Stop reaction.Distilled water washing reaction thing is used afterwards, adds activated carbon decolorizing, decompression steaming is carried out after activated carbon is leached
Evaporate, 150 DEG C of 1 temperature control of reactor, obtain triethyl citrate product and collect in triethyl citrate reception tank 4, lemon
Triethylenetetraminehexaacetic acid ester purity is higher than 99.5%.
When using different catalysts, the data such as the product esterification yield of gained, reaction time are as shown in table 3.Average response
Mean value calculation of the time according to 10 secondary responses.
Table 3
Embodiment 4
The method that Steam soak dehydration technique is used for synthesizing citric acid triethyl, the device of employing is as shown in figure 1, operating process bag
Include the following steps：
By 4.8 kg citric acids, 6.56kg absolute ethyl alcohols, heating response in 50g concentrated sulfuric acid catalysts input reactor 1, in catalysis
Carry out esterification under agent catalytic action, the temperature in reactor is 118 DEG C, the upflowing vapor in reactor and descending phegma
Carry out heat and mass transfer in rectifying column 2, the control of rectifying column tower top temperature at 73 DEG C or so, the feed liquid that tower top is steamed（Mainly
Ethanol）Ethanol is flowed into Jing after overhead condenser 3 is condensed to receive in tank 5, a part of overhead distillate as phegma, reflux ratio is
1.3, material liquid of the another part as Steam soak dehydration is conveyed by hydrous ethanol delivery pump 6, and Jing evaporimeters 7 are heated
Membrane separator group 8 is entered after vaporization, UF membrane unit 8 is by 0.36m2Molecular screen membrane（Every grade of membrane module area is 0.03 m2）Series connection
Constitute.Feed liquid lateral pressure is 0.2MPa（Gauge pressure）, osmotic lateral pressure control is in 400 Pa.Water in the solution of feed liquid side and a small amount of
Ethanol obtains penetrating fluid through infiltrating and vaporizing membrane in vapour form, per-meate side under the suction of vavuum pump 12, the penetrating fluid for obtaining
Flow into Jing after penetrating fluid condenser 9 is condensed in infiltration flow container 10.Coating materials liquid side feed liquid water content passes through infiltration evaporation membrane separator
Can significantly reduce, obtain absolute ethyl alcohol, absolute ethyl alcohol is flowed in finished product temporary storage tank 14 Jing after dehydration finished product condenser 13 is condensed,
And the interior water for continuing to participate in reaction and taking reaction generation out of of reactor 1 is back to by the conveying of absolute ethyl alcohol delivery pump 15.React into
Row is less than 5 mg (KOH)/g to reactor acid number（Deduct sulfuric acid acid number）Stop reaction afterwards.Distilled water washing reaction is used afterwards
Thing, obtains the reactant after the washings containing alcohol He other impurity, and washing, then adds activated carbon decolorizing in reactant,
Vacuum distillation is carried out after activated carbon is leached, 146 DEG C of 1 temperature control of reactor obtains triethyl citrate product and collects
Triethyl citrate is received in tank 4, and triethyl citrate purity is higher than 99.5%, product esterification yield 98.0%；In order that washings
In ethanol be recycled utilization, by washings send into 2 rectifying of rectifying column after, distillate is re-fed into UF membrane unit 8 in phase
Separate with the conditions of, recovery obtains the ethanol that purity is 97.2%, per-meate side obtains the infiltration water of ethanol content 12.5%, permeates vapour
Change separation factor 1318 of the film to alcohol water.
Embodiment 5
Difference with embodiment 4 is：Wash for sodium carbonate liquor is additionally used in reactant washing.
The method that Steam soak dehydration technique is used for synthesizing citric acid triethyl, the device of employing was as shown in figure 1, operated
Journey comprises the following steps：
By 4.8 kg citric acids, 6.56kg absolute ethyl alcohols, heating response in 50g concentrated sulfuric acid catalysts input reactor 1, in catalysis
Carry out esterification under agent catalytic action, the temperature in reactor is 118 DEG C, the upflowing vapor in reactor and descending phegma
Carry out heat and mass transfer in rectifying column 2, the control of rectifying column tower top temperature at 73 DEG C or so, the feed liquid that tower top is steamed（Mainly
Ethanol）Ethanol is flowed into Jing after overhead condenser 3 is condensed to receive in tank 5, a part of overhead distillate as phegma, reflux ratio is
1.3, material liquid of the another part as Steam soak dehydration is conveyed by hydrous ethanol delivery pump 6, and Jing evaporimeters 7 are heated
Membrane separator group 8 is entered after vaporization, UF membrane unit 8 is by 0.36m2Molecular screen membrane（Every grade of membrane module area is 0.03 m2）Series connection
Constitute.Feed liquid lateral pressure is 0.2MPa（Gauge pressure）, osmotic lateral pressure control is in 400 Pa.Water in the solution of feed liquid side and a small amount of
Ethanol obtains penetrating fluid through infiltrating and vaporizing membrane in vapour form, per-meate side under the suction of vavuum pump 12, the penetrating fluid for obtaining
Flow into Jing after penetrating fluid condenser 9 is condensed in infiltration flow container 10.Coating materials liquid side feed liquid water content passes through infiltration evaporation membrane separator
Can significantly reduce, obtain absolute ethyl alcohol, absolute ethyl alcohol is flowed in finished product temporary storage tank 14 Jing after dehydration finished product condenser 13 is condensed,
And the interior water for continuing to participate in reaction and taking reaction generation out of of reactor 1 is back to by the conveying of absolute ethyl alcohol delivery pump 15.React into
Row is less than 5 mg (KOH)/g to reactor acid number（Deduct sulfuric acid acid number）Stop reaction afterwards.5% sodium carbonate liquor is used afterwards first
Washing reaction thing, the reactant after alkali cleaning with distillation water washing, obtain the washings containing alcohol He other impurity, and washing again
Reactant afterwards, then activated carbon decolorizing is added in reactant, vacuum distillation, 1 temperature of reactor are carried out after activated carbon is leached
146 DEG C of control, obtains triethyl citrate product and collects in triethyl citrate reception tank 4, and triethyl citrate purity is high
In 99.5%, product esterification yield 98.0%；In order that the ethanol in soda-wash water and washings is recycled utilization, by soda-wash water and
After 2 rectifying of rectifying column is sent into after washings mixing, distillate is re-fed into UF membrane unit 8 and separates under the same conditions, reclaims
The ethanol that purity is 98.9% is obtained, per-meate side obtains the infiltration water of ethanol content 10.1%, separation of the infiltrating and vaporizing membrane to alcohol water
The factor 1581.
Claims (9)
1. a kind of method that Steam soak dehydration technique is used for synthesizing citric acid triethyl, it is characterised in that comprise the steps：
1st step, citric acid, ethanol and catalyst are added in reactor carries out esterification；
2nd step, heating is carried out to reaction kettle of the esterification makes part ethanol and water vapor, steam enter rectifying in rectifying column, and steam exists
Obtain mainly containing the distillate of second alcohol and water after capital condensation；
3rd step, the distillate of capital are dehydrated in being re-fed into infiltrating and vaporizing membrane, and the material ethanol after dehydration is back to reaction
Kettle；
4th step, after reaction terminates, washes to reactant, then activated carbon decolorizing is added in reactant, then carry out decompression steaming
Evaporate, collect distillate and obtain triethyl citrate product.
2. the method that Steam soak dehydration technique according to claim 1 is used for synthesizing citric acid triethyl, its feature exist
In, in the 1st described step, catalyst is cationic catalysts resin, the concentrated sulfuric acid, p-methyl benzenesulfonic acid or phosphoric acid；The 1st described step
In, the reactant ethanol 0.1～10wt.% of water content of input, preferably 0.5～1 wt.%.
3. the method that Steam soak dehydration technique according to claim 1 is used for synthesizing citric acid triethyl, its feature exist
In, in the 2nd described step, rectifying column tower top pressure mode of operation elects normal pressure or pressurization, preferred normal pressure as；Rectifying column tower top is adopted
Reflux ratio be 0.1～5.
4. the method that Steam soak dehydration technique according to claim 1 is used for synthesizing citric acid triethyl, its feature exist
In, in the 3rd described step, the gauge pressure of infiltrating and vaporizing membrane feed side is 0～0.6MPa, and the temperature of feed side is 70～160 DEG C；Ooze
The absolute pressure of the per-meate side of vaporization film is 100～10000Pa thoroughly.
5. the method that Steam soak dehydration technique according to claim 1 is used for synthesizing citric acid triethyl, its feature exist
In, the film that described Pervaporation membrane separator is adopted is preferential water permeable membrane, can for molecular screen membrane, silicon dioxide film or
PVA film, optimum are molecular screen membranes；In the 3rd described step, the material ethanol water content control after dehydration is in 0.03～2wt.%.
6. the method that Steam soak dehydration technique according to claim 1 is used for synthesizing citric acid triethyl, its feature exist
In, in the 4th described step, the temperature of reaction kettle of triethyl citrate vacuum distillation is 100～180 DEG C.
7. a kind of Steam soak dehydration technique is used for the device of synthesizing citric acid triethyl, it is characterised in that include reactor
（1）, in reactor（1）Top is provided with rectifying column（2）, rectifying column（2）Capital pass sequentially through overhead condenser（3）, ethanol
Receive tank（5）, hydrous ethanol delivery pump（6）, evaporimeter（7）With infiltration vaporization membrane module（8）Feed liquid side entrance connection；Tower top
Condenser（3）Condensate outlet on be also equipped with triethyl citrate receive tank（4）；Infiltration vaporization membrane module（8）Infiltration
Side successively with penetrating fluid condenser（9）, infiltration flow container（10）Connection, in penetrating fluid condenser（9）On be also disposed with vacuum
Surge tank（11）And vavuum pump（12）；Infiltration vaporization membrane module（8）Feed liquid side outlet pass sequentially through finished product condenser（13）, into
Product temporary storage tank（14）, absolute ethyl alcohol delivery pump（15）With reactor（1）Connection.
8. Steam soak dehydration technique according to claim 7 is used for the device of synthesizing citric acid triethyl, and its feature exists
In infiltration vaporization membrane module（8）Middle installation is molecular screen membrane, silicon dioxide film or PVA film, preferred molecular sieve film.
9. Steam soak dehydration technique according to claim 7 is used for the device of synthesizing citric acid triethyl, and its feature exists
In in reactor（1）On be also provided with alkali wash water add tank, for adding alkali lye in reactor；Water can also be set
Washing lotion adds tank, for reactor（1）Middle addition washing water；Activated carbon can also be set and add mouth, for reactor（1）
Middle addition activated carbon；Can be with reactor（1）Upper connection equipment for separating liquid from solid, for the reaction after operating to activated carbon decolorizing
Liquid carries out leaching activated carbon operation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611023875.9A CN106518683A (en) | 2016-11-14 | 2016-11-14 | Method and device for synthesizing triethyl citrate by applying vapor permeation dehydration technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611023875.9A CN106518683A (en) | 2016-11-14 | 2016-11-14 | Method and device for synthesizing triethyl citrate by applying vapor permeation dehydration technique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106518683A true CN106518683A (en) | 2017-03-22 |
Family
ID=58352517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611023875.9A Pending CN106518683A (en) | 2016-11-14 | 2016-11-14 | Method and device for synthesizing triethyl citrate by applying vapor permeation dehydration technique |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106518683A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141219A (en) * | 2017-05-31 | 2017-09-08 | 南京威尔药业股份有限公司 | A kind of method that UF membrane coupling esterification prepares triethyl citrate |
| CN108033903A (en) * | 2017-12-28 | 2018-05-15 | 山东汉兴医药科技有限公司 | Synthesis process for D L-p-methylsulfonylphenylserine ethyl ester with water esterification |
| CN108794332A (en) * | 2018-07-26 | 2018-11-13 | 德州绿霸精细化工有限公司 | A kind of method that ion membrane coupling technique prepares diethyl maleate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079704A (en) * | 2011-01-31 | 2011-06-01 | 蚌埠丰原涂山制药有限公司 | Preparation method of triethyl citrate |
| CN104926655A (en) * | 2015-06-11 | 2015-09-23 | 江苏九天高科技股份有限公司 | Technology and device for diethyl oxalate synthesis through vapor permeation dehydration process |
| CN104926653A (en) * | 2015-06-11 | 2015-09-23 | 江苏九天高科技股份有限公司 | Reaction and steam osmotic dehydration coupled ethyl hexanoate synthesizing process and device |
| CN206279107U (en) * | 2016-11-14 | 2017-06-27 | 江苏九天高科技股份有限公司 | A kind of Steam soak dehydration technique is used for the device of synthesizing citric acid triethyl |
-
2016
- 2016-11-14 CN CN201611023875.9A patent/CN106518683A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079704A (en) * | 2011-01-31 | 2011-06-01 | 蚌埠丰原涂山制药有限公司 | Preparation method of triethyl citrate |
| CN104926655A (en) * | 2015-06-11 | 2015-09-23 | 江苏九天高科技股份有限公司 | Technology and device for diethyl oxalate synthesis through vapor permeation dehydration process |
| CN104926653A (en) * | 2015-06-11 | 2015-09-23 | 江苏九天高科技股份有限公司 | Reaction and steam osmotic dehydration coupled ethyl hexanoate synthesizing process and device |
| CN206279107U (en) * | 2016-11-14 | 2017-06-27 | 江苏九天高科技股份有限公司 | A kind of Steam soak dehydration technique is used for the device of synthesizing citric acid triethyl |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141219A (en) * | 2017-05-31 | 2017-09-08 | 南京威尔药业股份有限公司 | A kind of method that UF membrane coupling esterification prepares triethyl citrate |
| CN108033903A (en) * | 2017-12-28 | 2018-05-15 | 山东汉兴医药科技有限公司 | Synthesis process for D L-p-methylsulfonylphenylserine ethyl ester with water esterification |
| CN108794332A (en) * | 2018-07-26 | 2018-11-13 | 德州绿霸精细化工有限公司 | A kind of method that ion membrane coupling technique prepares diethyl maleate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105439855B (en) | A kind of process for purification and device for ethyl acetate lactate synthesis | |
| US4822737A (en) | Process for producing ethanol by fermentation | |
| CN101372442B (en) | Apparatus and method for separating tert-butanol and water using batch fractionating and pervaporation | |
| CN107628946A (en) | The method and device of reactive distillation film device coupling production ethyl acetate in high purity | |
| CN108059597B (en) | Method and device for producing ethyl acetate by integrating reactive distillation and pervaporation | |
| CN106220501A (en) | A kind of water vapour penetration dehydration technique is for the method and apparatus of Synthesis of ethyl lactate | |
| CN106518683A (en) | Method and device for synthesizing triethyl citrate by applying vapor permeation dehydration technique | |
| CN104926653A (en) | Reaction and steam osmotic dehydration coupled ethyl hexanoate synthesizing process and device | |
| WO2013080742A1 (en) | Method for manufacturing monosaccharides, oligosaccharides, and furfurals from biomass | |
| CN108863719A (en) | Steam infiltration-alkaline process coupling prepares the method and device of sodium methoxide | |
| CN206033624U (en) | Vapor permeation dehydration techniques is used for synthetic ethyl lactate's device | |
| CN106542975B (en) | The method of continuous production high-purity triethylene glycol | |
| CN104945249A (en) | Method and device for producing ethyl formate through reactive distillation and steam osmosis membrane coupling | |
| CN104109078A (en) | Method for recovering ethanol in analginum production | |
| CN104193651B (en) | Refining method and device for synthesizing acetonitrile from acetic acid by ammoniation | |
| CN104926655A (en) | Technology and device for diethyl oxalate synthesis through vapor permeation dehydration process | |
| CN206279107U (en) | A kind of Steam soak dehydration technique is used for the device of synthesizing citric acid triethyl | |
| CN208182888U (en) | Reactive distillation-film device coupling production ethyl acetate in high purity device | |
| CN106883209B (en) | A kind of preparation process of dioxolanes | |
| CN108424350A (en) | A kind of technique of purification medicinal ethyl alcohol | |
| CN210237503U (en) | Dividing wall reaction rectification production process device for trioxymethylene | |
| CN106831380B (en) | Method for dehydrating and concentrating formaldehyde solution | |
| CN106187767A (en) | A kind of process for purification and device removing alcohol for the dehydration of packages printing industry ethyl acetate waste liquid | |
| CN204779428U (en) | Reaction rectification - vapor permeation membrane coupling production ethyl formate's device | |
| CN206143094U (en) | Extraction device who gathers methoxy dimethyl ether reactant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170322 |