CN209397147U - A kind of reactive distillation prepares the production system of acetic acid esters - Google Patents
A kind of reactive distillation prepares the production system of acetic acid esters Download PDFInfo
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- CN209397147U CN209397147U CN201821024625.1U CN201821024625U CN209397147U CN 209397147 U CN209397147 U CN 209397147U CN 201821024625 U CN201821024625 U CN 201821024625U CN 209397147 U CN209397147 U CN 209397147U
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Abstract
The utility model provides the production system that a kind of reactive distillation prepares acetic acid esters, comprising: reactive distillation column, water segregator and extractive distillation column；The reactive distillation column is provided with monohydric alcohol feed inlet and acetic acid feed mouth；The reactive distillation column includes conversion zone and rectifying section；The rectifying section is located on the conversion zone；The conversion zone and the rectifying section are using acetic acid feed mouth as boundary；The discharge port of the reactive distillation column is connected with the water segregator feed inlet；The oily phase discharge port of the water segregator is connected with the feed inlet of the extractive distillation column.The utility model uses reactive distillation column, it is arranged by specific position, so that acetic acid and monohydric alcohol carry out esterification by stripping section, acetic acid and monohydric alcohol complete esterification during rectifying column carries out gas-liquid contact on reactive distillation column, raw material is mixed sufficiently, reaction yield is high, consumes energy lower；In conjunction with specific processing sequence, after water segregator removes water, oil mutually enters extractive distillation column, obtains acetic acid esters.
Description
Technical field
The utility model relates to acetic acid esters preparation technical fields, are related to a kind of production system for preparing acetic acid esters, especially relate to
And a kind of reactive distillation prepares the production system of acetic acid esters.
Background technique
Acetic acid esters also known as acetate are a kind of chemical products, characteristic: lighter color, fabulous levelability and flexibility, guarantor
Light colour retention is good, is widely used in the fields such as solvent, plasticizer, surfactant and polymer monomer.It is domestic in recent years
Coating industry is according to the just phased out solvent using high VOC of environmental requirement, such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), and acetic acid
Ester belongs to environment-friendly type solvent, has obtained popularization energetically.In addition to this, acetic acid esters is more mainly used in the bases such as fragrance, solvent
Chemical field, especially high purity product are applied to electronic chemical product field.Thus, acetate product has obtained in the industry extensive
Research and concern.
Acetate product mainly includes ethyl acetate, isopropyl acetate, butyl acetate vinegar, the secondary butyl ester of acid, i-butyl
Ester.As ethyl acetate (EA) there is excellent solvability can be used as quick-drying solvent.There are three types of grades for ethyl acetate: 85%
88%, 99% and 99.5%, general purpose grade 99%.Ethyl acetate is mainly used as coating (paint and enamel paint), ink and adhesive
Active solvent in formula: it also is used as the process solvent of pharmacy and organic chemical synthesis: but because ethyl acetate is to be present in
Native compound in many fruit.Therefore has much can be used as flavoring agent and technique extractant evidence using in the food industry
Statistics.Ethyl acetate is as fine solvent, and it is larger just gradually to substitute some low-grade solvent development potentialities, especially high purity product,
Application space is more extensive.
Usual acetic acid esters is made by acetic acid and monohydric alcohol through esterification, produce acetic acid esters esterification be can be converse
It answers, in order to improve the generation of product, needs to isolate product from reaction system in time.Prior art system is mostly using distillation
Method the water in product is steamed, or product yield is improved using the excessive form of monoreactant, but this mode is not only
Energy consumption is big, and wastage of material is more.And existing process system is mostly acetic acid and monohydric alcohol in a kettle through the concentrated sulfuric acid
Catalytic esterification, then acetic acid esters is prepared by purification, but the concentrated sulfuric acid is larger to the corrosivity of equipment, equipment investment is higher, at waste water
It is big to manage pressure, also has by-product generation, causes high purity product purification difficult.
Therefore, a kind of system for preparing acetic acid esters how is found, solves above-mentioned industrial existing practical problem, further
Improve the purity of acetic acid esters, it has also become many research and development types production firm and a line researcher widely one of focus of attention.
Utility model content
In view of this, the technical problem to be solved by the present invention is to provide a kind of acetic acid esters production systems, especially
A kind of production system of the acetic acid esters of high-purity, production system provided by the utility model, reaction yield is relatively high and stable, purity
Height can satisfy the index request of battery industry application, and energy consumption is lower, and equipment investment is less, economical and practical.
The utility model provides a kind of production system for preparing acetic acid esters, comprising: reactive distillation column, water segregator and extraction
Rectifying column；
The reactive distillation column is provided with monohydric alcohol feed inlet and acetic acid feed mouth；
The reactive distillation column includes conversion zone and rectifying section；
The rectifying section is located on the conversion zone；The conversion zone and the rectifying section are using acetic acid feed mouth as boundary；
The discharge port of the reactive distillation column is connected with the water segregator feed inlet；
The oily phase discharge port of the water segregator is connected with the feed inlet of the extractive distillation column.
Preferably, the conversion zone is conversion zone plate column；
The rectifying section is rectifying section packed tower；
Catalyst is provided on the column plate of the conversion zone plate column.
Preferably, the catalyst includes solid acid catalyst；
The monohydric alcohol is one of methanol, ethyl alcohol and normal propyl alcohol or a variety of；
The discharge port of the reactive distillation column is located at reactive distillation column overhead；
The number of plates of the conversion zone plate column is 6~8 pieces；
The number of segment of the rectifying section packed tower is 1~2 section.
Preferably, the column plate spacing of the conversion zone plate column is 0.6~0.8 meter；
The bed stuffing height of the rectifying section packed tower is 4~6 meters；
Extractant in the extractive distillation column includes glycerine, 1,3-PD, 1,2-PD, 1,4-butanediol,
One of 1,3 butylene glycol, 1,2- butanediol and 2,3- butanediol are a variety of；
The solid acid catalyst includes macroporous type strong-acid ion exchange resin.
Preferably, filler is provided on the column plate of the conversion zone plate column；
The catalyst is supported on the filler of the column plate of conversion zone plate column.
Preferably, the water segregator is additionally provided with the second oily phase discharge port, the oily phase discharge port of the second of the water segregator with
The reactive distillation column overhead reflux import is connected.
Preferably, the production system further includes treating column and/or extractant regeneration tower.
Preferably, the light component discharge port of the extractive distillation column is connected with the feed inlet for the treatment of column；
The heavy constituent discharge port of the extractive distillation column is connected with the feed inlet of the extractant regeneration tower.
Preferably, the heavy constituent discharge port of the treating column is connected with the feed inlet of the extractant regeneration tower；
The heavy constituent discharge port of the extractant regeneration tower is connected with the top extractant import of the extractive distillation column；
The light component discharge port of the extractant regeneration tower is connected with the monohydric alcohol feed inlet of the reactive distillation column.
Preferably, the top extractant feed mouth of the extractive distillation column is away from the extracting rectifying top of tower at least 3 pieces of towers
Plate.
The utility model additionally provides a kind of production technology for preparing acetic acid esters, comprising the following steps:
1) by monohydric alcohol, acetic acid and catalyst in reactive distillation column, after carrying out reactive distillation, reaction mixture is obtained；
2) reaction mixture for obtaining above-mentioned steps obtains crude product after water removal；
3) crude product for obtaining above-mentioned steps obtains acetic acid esters after extracting rectifying.
Preferably, the reactive distillation includes conversion zone and rectifying section；
The conversion zone and rectifying section are using the import of acetic acid as boundary；
The catalyst includes solid acid catalyst；
The mass ratio of the monohydric alcohol and acetic acid is (0.75~0.8): 1；
The mass ratio of the catalyst and the monohydric alcohol is (0.04~0.08): 1；
The monohydric alcohol is one of methanol, ethyl alcohol and normal propyl alcohol or a variety of；
The reaction mixture is by the reactive distillation column top discharge.
Preferably, the solid acid catalyst includes macroporous type strong-acid ion exchange resin；The catalyst is supported on
On filler；
The temperature of the conversion zone is 110~120 DEG C；
The temperature of the rectifying section is 85~110 DEG C.
The tower top temperature of the reactive distillation column is 85~105 DEG C；
The bottom temperature of the reactive distillation column is 120~125 DEG C；
The overhead reflux ratio of the reactive distillation column is 0.2~0.25；
Preferably, the crude product includes crude product A and crude product B；
The crude product A is sent to the reactive distillation column, for flowing back；
The crude product B enters subsequent processing；
The mass ratio of the crude product A and crude product B is (1.8~2.1): 1；
Waste water after the water removal after processing, obtains acetic acid esters and/or monohydric alcohol.
Preferably, the tower top temperature of the extracting rectifying is 70~105 DEG C；
The bottom temperature of the extracting rectifying is 110~120 DEG C；
The extractant of the extracting rectifying includes glycerine, 1,3-PD, 1,2-PD, 1,4-butanediol, and 1,3-
One of butanediol, 1,2- butanediol and 2,3- butanediol are a variety of.
Preferably, the step 3) specifically:
The crude product that above-mentioned steps are obtained obtains light component acetic acid esters semi-finished product and heavy constituent extraction after extracting rectifying
Agent waste liquid；
By the obtained light component acetic acid esters semi-finished product of above-mentioned steps by purification purification after, obtain light component acetic acid esters and
Heavy constituent the second extractant waste liquid；
The heavy constituent extractant waste liquid and heavy constituent the second extractant waste liquid that above-mentioned steps are obtained obtain after regeneration
Heavy constituent regenerating extracting agent and light component mixture；
The heavy constituent regenerating extracting agent is sent to the extracting rectifying process；
The light component mixture is sent into reactive distillation column, is used for reactive distillation.
Preferably, the regenerated bottom temperature is 165~175 DEG C；
The regenerated tower top temperature is 85~100 DEG C.
The utility model provides a kind of production system for preparing acetic acid esters, comprising: reactive distillation column, water segregator and extraction
Rectifying column；The reactive distillation column is provided with monohydric alcohol feed inlet and acetic acid feed mouth；The reactive distillation column includes conversion zone
And rectifying section；The rectifying section is located on the conversion zone；The conversion zone and the rectifying section are using acetic acid feed mouth as boundary；
The discharge port of the reactive distillation column is connected with the water segregator feed inlet；The oily phase discharge port of the water segregator and the extraction
The feed inlet of rectifying column is connected.Compared with prior art, the utility model is directed to existing acetic acid esters production-process systems, exists
Energy consumption is big, and wastage of material is more, and equipment investment is high, and wastewater treatment pressure is big, and high purity product purification difficulty etc. is many to ask
Topic.The utility model is started with from the basic reaction device of reaction process, it is believed that is produced in existing chemical engineering industry, acetic acid esters esterification
Reaction process all carries out in a kettle, although can be realized coming into full contact with for catalyst and raw material by stirring, and due to ester
Changing reaction is reversible reaction, can only excessively improve product yield by acid or alcohol, then in reaction kettle after esterification, then
Carry out subsequent purification.The utility model finds with experiment by long-term research, existing reaction process system, on the one hand, anti-
The material stirring environment of kettle is answered to lead to catalyst breakage or inactivation, on the other hand, esterification yield needs to pass through reaction product
Lasting separation could improve, and the separation energy consumption in reaction kettle is higher.
The utility model creativeness uses reactive distillation column, so that acetic acid and monohydric alcohol are by catalysis stripping section progress
Acid-catalyzed esterification reaction, and catalyst activity component filler is loaded in reactive distillation column, acetic acid and monohydric alcohol are carried out in rectifying column
Catalytic esterification is completed during gas-liquid contact on distillation column reactor section filler, raw material is mixed sufficiently, catalyst
Reaction environment is milder, and catalyst life is longer, and reaction yield is high, consumes energy lower, while completing just separation in rectifying section；It ties again
Specific processing sequence is closed, by reaction mixture after water segregator removes water, oil mutually enters extractive distillation column, through extracting rectifying
Afterwards, product is discharged by tower top, obtains acetic acid esters.
The experimental results showed that the utility model prepares acetic acid esters, purity is higher than 99.99%, and aqueous to be lower than 5ppm, coloration is small
In 5, indices fully meet the index request of lithium-ion battery electrolytes solvent or additive application.
Detailed description of the invention
Fig. 1 is the general flow chart of acetic acid esters production system provided by the utility model.
Specific embodiment
In order to further appreciate that the utility model, carried out below with reference to preferred embodiment of the embodiment to the utility model
Description, but it is to be understood that these descriptions are only to further illustrate the feature and advantage of the utility model rather than to this reality
The limitation required with new patent.
All raw materials of the utility model, are not particularly limited its source, buying on the market or according to this field skill
The preparation of conventional method known to art personnel.
The utility model is raw materials used, its purity is not particularly limited, and the utility model preferably uses technical pure or second
The conventional purity of enester preparation field.
All noun expression of the utility model and abbreviation belong to the expression of this field routine noun and abbreviation, each noun list
Up to be in its related application field with abbreviation it is explicit, those skilled in the art according to noun express and referred to as, energy
It is enough clear accurately uniquely to be understood.
The utility model provides a kind of production system for preparing acetic acid esters, comprising: reactive distillation column, water segregator and extraction
Rectifying column；
The reactive distillation column is provided with monohydric alcohol feed inlet and acetic acid feed mouth；
The reactive distillation column includes conversion zone and rectifying section；
The rectifying section is located on the conversion zone；The conversion zone and the rectifying section are using acetic acid feed mouth as boundary；
The discharge port of the reactive distillation column is connected with the water segregator feed inlet；
The oily phase discharge port of the water segregator is connected with the feed inlet of the extractive distillation column.
Selection and composition of the utility model to required production line in the above-mentioned system for preparing acetic acid esters, and it is corresponding
The selection of corresponding production line and composition in optimum principle, with the aforementioned technique for preparing acetic acid esters, and it is corresponding preferred
Principle can be corresponded to, and this is no longer going to repeat them.
Reactive distillation column described in the utility model preferably includes conversion zone and rectifying section, i.e., the described reactive distillation column preferably wraps
Rectifying section packed tower and conversion zone gasket packing tower are included, the utility model is the performance for being further ensured that final products, described anti-
Answer section and rectifying section particularly preferably using the import of acetic acid as boundary, the rectifying section is located on the conversion zone, i.e., acetic acid into
The above are rectifying sections for mouth, and the following are conversion zones.
In a specific embodiment, using acetic acid feed mouth as boundary, acetic acid feed mouth is the reactive distillation column with upper section
Rectifying section packed tower, using lower section as conversion zone plate column, catalyst is preferably placed on the column plate of the conversion zone plate column, described
Filler is preferably equipped on conversion zone plate column, load has solid acid as catalyst more preferably on filler, and the solid acid is
Macroporous type strong-acid ion exchange resin.In the reactive distillation column, monohydric alcohol is heated by tower reactor and rises to conversion zone plate with gas phase
Formula tower, acetic acid enter conversion zone at normal temperatures and pressures with liquid phase, and acetic acid carries out on conversion zone plate tower packing with monohydric alcohol steam
Adverse current comes into full contact with, and continuous esterification generates acetic acid esters.
In the present invention, in order to further increase the performances of final products, conversion zone described in the utility model is board-like
The number of plates of tower is preferably 6~8 pieces, more preferably 6 pieces, 7 pieces or 8 pieces；The column plate of conversion zone plate column described in the utility model
Spacing is preferably 0.6~0.8 meter, more preferably 0.63~0.78 meter, more preferably 0.65~0.75 meter, more preferably 0.67~
0.73 meter.The number of segment of rectifying section packed tower described in the utility model is preferably 1~2 section, more preferably 1 section or 2 sections.This is practical new
The bed stuffing height of rectifying section packed tower described in type is preferably 4~6 meters, and more preferably 4.3~5.8 meters, more preferably 4.5~
5.5 meters, more preferably 4.7~5.3 meters.
In the process system for preparing acetic acid esters, the discharge port of the reactive distillation column and the water segregator feed inlet phase
Even, i.e., acetic acid esters, water and part monohydric alcohol autoreaction the top of the distillation column of esterification generation are carried out in reactive distillation column
Extraction enters water segregator for tower top discharging, and the stratification in water segregator forms upper oil phase and lower layer's water phase, upper oil phase
Contain a small amount of water based on acetic acid esters and monohydric alcohol, lower layer's water phase contains a small amount of acetic acid esters and monohydric alcohol, lower water based on water
It is mutually water phase discharging as waste water.
The water segregator is not particularly limited in the utility model, with industrial water segregator well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement, this
Water segregator described in utility model is preferably overflow-type oil water separator or Gravity Type Oil separator.
In a specific embodiment, there are three discharge port, i.e., 2 oily phase discharge ports, 1 water phases for the water segregator setting
Discharge port, wherein oily phase discharge port and the second oily phase discharge port be respectively as tower top discharge port and reactive distillation column refluxing opening, i.e.,
The water segregator is additionally provided with oily phase bypass outlet, and the oily phase bypass outlet of the water segregator is connected with the reactive distillation column.
Water phase discharge port described in the utility model as wastewater outlet to wastewater treatment at.
The oily phase discharge port of the tower top of the water segregator is connected with the feed inlet of the extractive distillation column；The water segregator
Oily mutually discharging enters extracting and refining midsection, and mutually discharging is by extracting rectifying for extractant and oil, and light component is from extractive distillation column tower
Output is pushed up, acetic acid esters is obtained, heavy constituent is discharged from extractive distillation column tower reactor.
In a specific embodiment, the herein described production system for preparing acetic acid esters further includes treating column, the extraction
The light component discharge port of rectifying column is taken to be connected with the feed inlet of the treating column；The treating column is known to those skilled in the art
, in a specific embodiment, the treating column is board-like treating column.The utility model produces high-purity from refined tower top
Acetic acid esters.
In a specific embodiment, the process system of the acetic acid esters further includes extractant regeneration tower, the extractant
The heavy constituent discharge port of rectifying column is connected with the feed inlet of the extractant regeneration tower, the bottom heavy constituent discharging of the treating column
Mouthful be connected with the feed inlet of the extractant regeneration tower, heavy constituent (extractant) discharge port of the extractant regeneration tower with it is described
The extractant feed mouth at the top of extractive distillation column is connected, and the light component of the extractant regeneration tower (mainly includes monohydric alcohol, water
With acetic acid esters) discharge port is connected with the monohydric alcohol feed inlet of the reactive distillation column.
In such production system, light component is extracting rectifying column overhead from extracting rectifying top of tower output to treating column
Discharging, heavy constituent are expelled to extractant regeneration tower from extractive distillation column tower reactor, discharge for extractive distillation column tower bottom；Treating column is in tower
Top output light component is high-purity acetic acid esters, is divided into the discharging for the treatment of column tower bottom in the recombination of tower bottom output, heavy constituent enters extraction
Agent regenerator recycles extractant therein, monohydric alcohol；The discharging of extractant rectifying tower bottom contains a large amount of extractants, a large amount of unitary
Alcohol, water and a small amount of acetic acid esters, by extractant regeneration tower distillation process carry out extractant regeneration, regenerating extracting agent from extractant again
Raw tower tower bottom output is back to extractive distillation column extractant feed mouth, and remaining monohydric alcohol, water and acetic acid esters are as extraction regenerator
Reflux raw material enters reactive distillation column tower reactor, realizes extractant regeneration and part material recycling.The application is preferred in embodiment
Treating column and extractant regeneration tower are set, the purity of acetic acid esters can be improved, recycles a small amount of raw material and extractant, improves economic effect
Benefit.
Referring to Fig. 1, Fig. 1 is the general flow chart of acetic acid esters production system provided by the utility model.Wherein, A is reaction essence
Tower is evaporated, B is water segregator, and C is extractive distillation column, and D is extractant regeneration tower, and E is treating column；1 is acetic acid, and 2 be monohydric alcohol, and 3 are
Tower top discharging, 4 be oil phase reflux, and 5 be oil mutually discharging, and 6 be that water phase discharges, and 7 discharge for extractive distillation column tower bottom, and 8 be to extract again
Raw tower reflux raw material, 9 discharge for extracting rectifying column overhead, and 10 discharge for treating column tower bottom, and 11 be acetic acid esters, and 12 be regeneration extraction
Agent.
The utility model additionally provides a kind of production technology for preparing acetic acid esters, comprising the following steps:
1) by monohydric alcohol, acetic acid and catalyst in reactive distillation column, after carrying out reactive distillation, reaction mixture is obtained；
2) reaction mixture for obtaining above-mentioned steps obtains crude product after water removal；
3) crude product for obtaining above-mentioned steps obtains acetic acid esters after extracting rectifying.
The utility model after carrying out reactive distillation, obtains first by monohydric alcohol, acetic acid and catalyst in reactive distillation column
Reaction mixture.
The source of the monohydric alcohol and acetic acid is not particularly limited in the utility model, with well known to those skilled in the art
Preparation method preparation or commercially available purchase, those skilled in the art can be according to practical condition, raw material condition and productions
Product require to be selected and adjusted.The specific choice of the monohydric alcohol is not particularly limited in the utility model, with this field skill
Prepare the monohydric alcohol of conventional acetic acid ester known to art personnel, those skilled in the art can according to practical condition,
Raw material condition and product requirement are selected and are adjusted, and monohydric alcohol described in the utility model is preferably methanol, ethyl alcohol and positive third
One of alcohol is a variety of, more preferably methanol, ethyl alcohol or normal propyl alcohol.
The ratio of the monohydric alcohol and acetic acid is not particularly limited in the utility model, with well known to those skilled in the art
Be used to prepare the conventional ratio of acetic acid esters, those skilled in the art can according to practical condition, raw material condition and
Product requirement is selected and is adjusted, and the mass ratio of monohydric alcohol and acetic acid described in the utility model is preferably (0.75~0.8): 1,
More preferably (0.76~0.79): 1, more preferably (0.77~0.78): 1.
The catalyst is not particularly limited in the utility model, is used to prepare acetic acid with well known to those skilled in the art
The catalyst of ester, those skilled in the art can select according to practical condition, raw material condition and product requirement
It selects and adjusts, the utility model is the reactive mode of complex reaction rectifying, and the catalyst preferably includes solid acid catalyst, more
It is particularly preferred as macroporous type strong-acid ion exchange resin.
The dosage of the catalyst is not particularly limited in the utility model, with well known to those skilled in the art for making
The conventional amount used of standby acetic acid esters, those skilled in the art can want according to practical condition, raw material condition and product
It asks and is selected and adjusted, the mass ratio of catalyst described in the utility model and the monohydric alcohol is preferably (0.04~0.08):
1, more preferably (0.045~0.075): 1, more preferably (0.05~0.07): 1, more preferably (0.055~0.065): 1.
The reactive distillation is not particularly limited in the utility model, with reactive distillation well known to those skilled in the art
Mode, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement
Whole, reactive distillation described in the utility model preferably carries out reactive distillation in reactive distillation column.
Reactive distillation described in the utility model preferably includes conversion zone and rectifying section, i.e., the described reactive distillation column preferably includes
Rectifying section packed tower and conversion zone gasket packing tower, the utility model are the performance for being further ensured that final products, the reaction
Section and rectifying section are particularly preferably using the import of acetic acid as boundary, i.e., the above are rectifying sections for the import of acetic acid, and the following are conversion zones.
The technological parameter of the conversion zone is not particularly limited in the utility model, with well known to those skilled in the art normal
Advise conversion zone parameter, those skilled in the art can according to practical condition, raw material condition and product requirement into
Row selection and adjustment, the utility model are the performance for being further ensured that final products, the temperature of the conversion zone is preferably 110~
120 DEG C, more preferably 112~118 DEG C, more preferably 114~116 DEG C.The pressure of conversion zone described in the utility model is preferably
Normal pressure.
The technological parameter of the rectifying section is not particularly limited in the utility model, with well known to those skilled in the art normal
Advise rectifying section parameter, those skilled in the art can according to practical condition, raw material condition and product requirement into
Row selection and adjustment, the utility model are the performance for being further ensured that final products, the temperature of the rectifying section is preferably 85~
110 DEG C, more preferably 88~108 DEG C, more preferably 90~105 DEG C, more preferably 93~102 DEG C.Essence described in the utility model
The pressure for evaporating section is preferably normal pressure.
The integrated artistic parameter of the reactive distillation is not particularly limited in the utility model, ripe with those skilled in the art
The parameter for the reactive distillation known, those skilled in the art can want according to practical condition, raw material condition and product
It asks and is selected and adjusted, the utility model is the performance for being further ensured that final products, reactive distillation described in the utility model
The pressure of tower is preferably normal pressure.The tower top temperature of reactive distillation column described in the utility model is preferably 85~105 DEG C, more preferably
88~102 DEG C, more preferably 90~100 DEG C, more preferably 93~108 DEG C.The tower reactor of reactive distillation column described in the utility model
Temperature is preferably 120~125 DEG C, more preferably 121~124 DEG C, more preferably 122~123 DEG C.Reaction described in the utility model
The overhead reflux of rectifying column is than preferably 0.2~0.25, more preferably 0.21~0.24, more preferably 0.22~0.23.
The utility model is the performance for being further ensured that final products, preferably improves the effect of reactive distillation, described to urge
Agent is preferably supported on filler, i.e., the described catalyst is preferably supported on the filler of the conversion zone.The utility model is to institute
The type for stating filler is not particularly limited, and with filling kind well known to those skilled in the art, those skilled in the art can
To be selected and be adjusted according to practical condition, raw material condition and product requirement, the kind of filler described in the utility model
Class preferably include wire mesh packing, porcelain ripple packing, metal corrugated packing, wooden-grid packing, Raschig ring, Pall ring, cascade ring,
Helical ring, ceramic ring, steel fill out one of circle, saddle type expectation, quartz and glass spring or a variety of.Filler described in the utility model
Form preferably includes structured packing or random packing.The load capacity of catalyst described in the utility model is preferably 5%~10%, more
Preferably 6%~9%, more preferably 7%~8%.In the present invention, the filling kind in rectifying section packed tower is preferred
Range is identical as above-mentioned filling kind preferred scope.
For the utility model in reactive distillation column, monohydric alcohol enters reactive distillation column, is heated by tower reactor and is risen to instead with gas phase
A section plate column is answered, acetic acid enters conversion zone at normal temperatures and pressures with liquid phase, and acetic acid and monohydric alcohol steam are in conversion zone plate tower packing
Upper progress adverse current comes into full contact with, and continuous esterification generates acetic acid esters.The utility model is after reactive distillation, reaction mixture
It is preferred that being discharged by the reactive distillation top of tower.It may include acetic acid esters, unitary alcohol and water in the reaction mixture.
The reaction mixture that the utility model then obtains above-mentioned steps obtains crude product after water removal.
The mode of the water removal is not particularly limited in the utility model, in a manner of water removal well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement, this
Utility model is to be further ensured that the performance of final products, and the mode of water removal described in the utility model is preferably water segregator water removal.
The utility model has obtained crude product after above-mentioned steps, and the utility model is to advanced optimize and complete process
Process improves the performance parameter of product, and the crude product preferably includes crude product A and crude product B, i.e., the described obtained crude product is divided into two
Point.Crude product A described in the utility model, i.e., a part of crude product are sent to the reactive distillation column, for flowing back；The crude product B, i.e., separately
A part of crude product enters subsequent processing.
The ration of division of the crude product is not particularly limited in the utility model, and those skilled in the art can be according to reality
The condition of production, raw material condition and product requirement are selected and are adjusted, the quality of crude product A and crude product B described in the utility model
Than preferably (1.8~2.1): 1, more preferably (1.85~2.05): 1, more preferably (1.9~2.1): 1, more preferably
(1.95~2.05): 1.
Waste water after water removal described in the utility model, i.e. aqueous-phase material preferably comprise a large amount of water and a small amount of acetic acid esters and one
First alcohol.The processing of the waste water is not particularly limited in the utility model, and those skilled in the art can be according to actual production feelings
Condition, raw material condition and product requirement are selected and are adjusted, the waste water after water removal described in the utility model preferably after processing,
Obtain acetic acid esters and/or monohydric alcohol.
The utility model is reflexive by the acetic acid esters, water and part monohydric alcohol for carrying out esterification generation in reactive distillation column
After answering the top of the distillation column to produce, enter water segregator for tower top discharging, the stratification in water segregator forms upper oil phase and lower layer
Water phase, upper oil phase based on acetic acid esters and monohydric alcohol contain a small amount of water, lower layer's water phase based on water, containing a small amount of acetic acid esters with
Monohydric alcohol, lower layer's water phase are water phase discharging as waste water.
The crude product that the utility model finally obtains above-mentioned steps obtains acetic acid esters after extracting rectifying.
The technological parameter of the extracting rectifying is not particularly limited in the utility model, with well known to those skilled in the art
The parameter of extracting rectifying, those skilled in the art can according to practical condition, raw material condition and product requirement into
Row selection and adjustment, the utility model is the performance for being further ensured that final products, the pressure of extracting rectifying described in the utility model
Power is preferably normal pressure.The tower top temperature of extracting rectifying described in the utility model is preferably 70~105 DEG C, more preferably 75~100
DEG C, more preferably 80~95 DEG C, more preferably 85~90 DEG C.The bottom temperature of extracting rectifying described in the utility model is preferably
110~120 DEG C, more preferably 112~118 DEG C, more preferably 114~116 DEG C.
The extractant of the extracting rectifying is not particularly limited in the utility model, with extraction well known to those skilled in the art
Take the extractant of rectifying, those skilled in the art can according to practical condition, raw material condition and product requirement into
Row selection and adjustment, the utility model is the performance for being further ensured that final products, the extraction of extracting rectifying described in the utility model
Agent is taken to preferably include glycerine, 1,3-PD, 1,2-PD, 1,4-butanediol, 1,3-BDO, 1,2- butanediol and 2,
One of 3- butanediol is a variety of, more preferably glycerine, 1,3-PD, 1,2-PD, 1,4-butanediol, 1,3- fourth
Glycol, 1,2- butanediol or 2,3- butanediol.
The utility model be advanced optimize with complete process process, improve the purity of final products, the utility model institute
Stating step 3) can be preferred are as follows:
The crude product that above-mentioned steps are obtained obtains light component acetic acid esters semi-finished product and heavy constituent extraction after extracting rectifying
Agent waste liquid；
By the obtained light component acetic acid esters semi-finished product of above-mentioned steps by purification purification after, obtain light component acetic acid esters and
Heavy constituent the second extractant waste liquid；
The heavy constituent extractant waste liquid and heavy constituent the second extractant waste liquid that above-mentioned steps are obtained obtain after regeneration
Heavy constituent regenerating extracting agent and light component mixture；
The heavy constituent regenerating extracting agent is sent to the extracting rectifying process；
The light component mixture is sent into reactive distillation column, is used for reactive distillation.
The technological parameter of the purification purification is not particularly limited in the utility model, with well known to those skilled in the art
Refine purification parameter, those skilled in the art can according to practical condition, raw material condition and product requirement into
Row selection and adjustment.
The technological parameter of the extractant regeneration is not particularly limited in the utility model, known to those skilled in the art
Extractant regeneration parameter, those skilled in the art can want according to practical condition, raw material condition and product
It asks and is selected and adjusted, the utility model is the performance for being further ensured that final products, and extractant described in the utility model is again
Raw pressure is preferably normal pressure.The tower top temperature of extractant regeneration described in the utility model is preferably 85~100 DEG C, more preferably
88~98 DEG C, more preferably 90~95 DEG C.The bottom temperature of extractant regeneration described in the utility model is preferably 165~175 DEG C,
More preferably 167~173 DEG C, more preferably 169~171 DEG C.
The utility model is directed in existing acetic acid esters production technology, is existed and is urged using the concentrated sulfuric acid in reaction kettle progress acid alcohol
To change in esterification reaction process, the concentrated sulfuric acid has stronger corrosivity, and equipment investment is larger, meanwhile, sulphuric acid catalysis esterification
A large amount of acid waste waters can be generated, the problems such as environmental protection pressure is larger；And reaction of the current solid acid as catalyst, although will not
Environmental protection pressure is generated to reaction kettle, but solid acid catalyst can be during reaction kettle catalytic esterification, due to stirring cause, catalysis
Agent physicochemical property will receive influence, and catalyst life shortens.The utility model is creative to be loaded to solid acid catalyst instead
It answers in rectifying column, casts out the whipping process of reaction kettle, Acetic Acid In Liquid Phase is inversely contacted with monohydric alcohol gas phase, realizes acid alcohol esterification
Reactive distillation processes, reaction environment locating for catalyst is more stable, lasts a long time, and realizes continuous and stable production.
The utility model realizes the preparation of acetic acid esters using reactive distillation column, water segregator and extractive distillation column, by negative
It is loaded with the reactive distillation column of solid acid catalyst, casts out the whipping process of reaction kettle, Acetic Acid In Liquid Phase carries out inverse with monohydric alcohol gas phase
To contact, acid alcohol esterification reaction rectification process is realized, it is often more important that, catalyst is supported on filler, is arranged in conversion zone
At plate column, locating reaction environment is more stable, lasts a long time, and realizes continuous and stable production；In conjunction with specific processing sequence, lead to
The purification for realizing acetic acid esters using water segregator and extractive distillation column is crossed, keeps the purity of acetic acid esters higher；Further through the essence of setting
Tower processed and extractant recovery tower realize the recycling of the further purification and extractant of acetic acid esters, realize continuous-stable metaplasia
It produces, improves economic benefit.The utility model discloses a kind of production technology and production system for preparing acetic acid esters, the technique and
System can be such that raw material comes into full contact with catalyst, not only extend catalyst life, but also keep reaction yield high, consume energy lower.
The experimental results showed that the utility model prepares acetic acid esters, purity is higher than 99.99%, and aqueous to be lower than 5ppm, coloration is small
In 5, indices fully meet the index request of lithium-ion battery electrolytes solvent or additive application.
In order to further illustrate the utility model, a kind of acetic acid is prepared to provided by the utility model with reference to embodiments
The production system of ester is described in detail, but it is to be understood that these embodiments are before being with technical solutions of the utility model
It puts and is implemented, the detailed implementation method and specific operation process are given, only to further illustrate the utility model
Feature and advantage, rather than the limitation to the utility model claims, the protection scope of the utility model are also not necessarily limited to down
The embodiment stated.
Embodiment 1
The production system of acetic acid esters, comprising: reactive distillation column, water segregator, extractive distillation column, treating column and extractant regeneration
Tower.
Reactive distillation column is provided with monohydric alcohol feed inlet and acetic acid feed mouth, reactive distillation column include conversion zone plate column and
Rectifying section packed tower, rectifying section are located on the conversion zone, and conversion zone and the rectifying section are using acetic acid feed mouth as boundary.Its
In, the discharge port of reactive distillation column overhead is connected with water segregator feed inlet, the oily phase discharge port and the extracting rectifying of water segregator
The feed inlet of tower is connected.
Wherein, the number of plates of conversion zone plate column is 6~8 pieces, and column plate spacing is 0.6~0.8 meter；Conversion zone plate column
Filler is provided on column plate, macroporous type strongly acidic ion-exchange resin catalyst is supported on the filler of the column plate of conversion zone plate column
On；The number of segment of rectifying section packed tower is 1~2 section, and bed stuffing height is 4~6 meters.Water segregator is additionally provided with the second oil and mutually discharges
Mouthful, the oily phase discharge port of the second of water segregator is connected with reactive distillation column overhead reflux import.
Wherein, the light component discharge port of extractive distillation column is connected with the feed inlet for the treatment of column, the heavy constituent of extractive distillation column
Discharge port is connected with the feed inlet of extractant regeneration tower.The charging of the heavy constituent discharge port for the treatment of column and the extractant regeneration tower
Mouth is connected, and the heavy constituent discharge port of extractant regeneration tower is connected with the top extractant import of the extractive distillation column；Extractant
The light component discharge port of regenerator is connected with the monohydric alcohol feed inlet of the reactive distillation column.Meanwhile the top of extractive distillation column
Extractant feed mouth is away from the extracting rectifying top of tower at least 3 blocks of column plates.
Referring to Fig. 1, Fig. 1 is the general flow chart of acetic acid esters production system provided by the utility model.Wherein, A is reaction essence
Tower is evaporated, B is water segregator, and C is extractive distillation column, and D is extractant regeneration tower, and E is treating column；1 is acetic acid, and 2 be monohydric alcohol, and 3 are
Tower top discharging, 4 be oil phase reflux, and 5 be oil mutually discharging, and 6 be that water phase discharges, and 7 discharge for extractive distillation column tower bottom, and 8 be to extract again
Raw tower reflux raw material, 9 discharge for extracting rectifying column overhead, and 10 discharge for treating column tower bottom, and 11 be acetic acid esters, and 12 be regeneration extraction
Agent.
The acetic acid esters of the utility model embodiment preparation is detected, the results showed that, the utility model prepares acetic acid esters,
Purity be higher than 99.99%, it is aqueous be lower than 5ppm, coloration less than 5, indices fully meet lithium-ion battery electrolytes solvent or
The index request of additive application.
Detailed Jie has been carried out to a kind of production system that reactive distillation prepares acetic acid esters provided by the utility model above
It continues, specific case used herein is expounded the principles of the present invention and embodiment, and above embodiments are said
The bright method and its core concept for being merely used to help understand the utility model, including best mode, and but also this field
Any technical staff can practice the utility model.It should be pointed out that for those skilled in the art,
Without departing from the principle of this utility model, several improvements and modifications can be made to this utility model, these improvement
It is also fallen into the protection scope of the utility model claims with modification.The range of the utility model patent protection is wanted by right
Ask to limit, and may include those skilled in the art it is conceivable that other embodiments.If these other embodiments have not
It is the structural element different from claim character express, or if they include the character express with claim without essence
The equivalent structural elements of difference, then these other embodiments should also be included in the scope of the claims.
Claims (10)
1. a kind of production system for preparing acetic acid esters characterized by comprising reactive distillation column, water segregator and extractive distillation column；
The reactive distillation column is provided with monohydric alcohol feed inlet and acetic acid feed mouth；
The reactive distillation column includes conversion zone and rectifying section；
The rectifying section is located on the conversion zone；The conversion zone and the rectifying section are using acetic acid feed mouth as boundary；
The discharge port of the reactive distillation column is connected with the water segregator feed inlet；
The oily phase discharge port of the water segregator is connected with the feed inlet of the extractive distillation column.
2. production system according to claim 1, which is characterized in that the conversion zone is conversion zone plate column；
The rectifying section is rectifying section packed tower；
Catalyst is provided on the column plate of the conversion zone plate column.
3. production system according to claim 2, which is characterized in that the discharge port of the reactive distillation column is located at reaction essence
Evaporate column overhead；
The number of plates of the conversion zone plate column is 6~8 pieces；
The number of segment of the rectifying section packed tower is 1~2 section.
4. production system according to claim 3, which is characterized in that the column plate spacing of the conversion zone plate column is 0.6
~0.8 meter；
The bed stuffing height of the rectifying section packed tower is 4~6 meters.
5. production system according to claim 2, which is characterized in that be provided with and fill out on the column plate of the conversion zone plate column
Material；
The catalyst is supported on the filler of the column plate of conversion zone plate column.
6. production system according to claim 2, which is characterized in that the water segregator is additionally provided with the second oil and mutually discharges
Mouthful, the oily phase discharge port of the second of the water segregator is connected with the reactive distillation column overhead reflux import.
7. production system according to claim 1, which is characterized in that the production system further includes treating column and/or extraction
Take agent regenerator.
8. production system according to claim 7, which is characterized in that the light component discharge port and essence of the extractive distillation column
The feed inlet of tower processed is connected；
The heavy constituent discharge port of the extractive distillation column is connected with the feed inlet of the extractant regeneration tower.
9. production system according to claim 7, which is characterized in that the heavy constituent discharge port of the treating column and the extraction
The feed inlet of agent regenerator is taken to be connected；
The heavy constituent discharge port of the extractant regeneration tower is connected with the top extractant import of the extractive distillation column；
The light component discharge port of the extractant regeneration tower is connected with the monohydric alcohol feed inlet of the reactive distillation column.
10. production system according to claim 1, which is characterized in that the top extractant feed of the extractive distillation column
At least there are 3 blocks of column plates apart from the extracting rectifying top of tower in mouth.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644556A (en) * | 2020-12-21 | 2022-06-21 | 山东石大胜华化工集团股份有限公司 | Device and process method for preparing propionate |
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2018
- 2018-06-29 CN CN201821024625.1U patent/CN209397147U/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644556A (en) * | 2020-12-21 | 2022-06-21 | 山东石大胜华化工集团股份有限公司 | Device and process method for preparing propionate |
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