CN107473966A - A kind of production method of dimethyl maleate - Google Patents
A kind of production method of dimethyl maleate Download PDFInfo
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- CN107473966A CN107473966A CN201710756008.4A CN201710756008A CN107473966A CN 107473966 A CN107473966 A CN 107473966A CN 201710756008 A CN201710756008 A CN 201710756008A CN 107473966 A CN107473966 A CN 107473966A
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- dimethyl maleate
- esterification
- cis
- butenedioic anhydride
- production method
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- 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
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- 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
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- 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
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- 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
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of production method of dimethyl maleate, be specifically it is a kind of be the cis-butenedioic anhydride in solvent absorption mixed gas containing cis-butenedioic anhydride using dimethyl maleate after obtained mixing liquid as raw material, method that esterification production dimethyl maleate is carried out with methanol.The dimethyl maleate that the mixed gas containing cis-butenedioic anhydride after heat exchange tentatively cools down enters absorption tower bottom and tower top spray carries out counter current contacting and is absorbed liquid.Esterification column filling solid acid esterification catalyst filler, absorbing liquid is pumped into from esterification tower top reacts with the methanol steam contact at esterification column bottom.Bottom of towe obtains dimethyl maleate crude product, obtains dimethyl maleate product by distillation, partly returns for spray-absorption cis-butenedioic anhydride.The isolated first alcohol and water of tower top aqueous methanol steam rectifying, methanol are returned for esterification.
Description
Technical field
The invention provides a kind of production method of dimethyl maleate, be specifically it is a kind of using dimethyl maleate as
The mixing liquid obtained after cis-butenedioic anhydride in solvent absorption mixed gas containing cis-butenedioic anhydride is raw material, and esterification production horse is carried out with methanol
Carry out the method for dimethyl phthalate.
Background technology
Dimethyl maleate is being commonly called as dimethyl maleate (DMM), colourless viscous liquid, molecular formula C6H8O4,
200.4 DEG C of boiling point (101.3kPa), -19.0 DEG C of fusing point, relative density 1.146.Dimethyl maleate is a kind of important organic
Industrial chemicals, the raw material as plasticizer, the preservative of fatty oils and organic synthesis.Dimethyl maleate is urged by different
Change hydrogenation process to be used to produce BDO, tetrahydrofuran, gamma-butyrolacton, dimethyl succinate etc., BDO and fourth
Acid dimethyl can continue on for producing complete biodegradable plastics poly butylene succinate（PBS）.
Aoxidize to obtain the high-temperature gas mixture containing cis-butenedioic anhydride after about 50% cis-butenedioic anhydride is withdrawn in preliminary cooling by raw material of benzene, it is remaining
Gas mainly carries out the recovery of cis-butenedioic anhydride, i.e. Water Sproading and organic solvent recovery using 2 kinds of methods at present.
The advantages of water recovery process is that have the big spy of chemical absorbing speed as absorbent using water cheap and easy to get
Point.But the azeotropic distillation of entrainer is made using dimethylbenzene or substantial amounts of water is sloughed from absorbing liquid using film evaporation method and
A small amount of product is obtained, energy consumption is big, while cis-butenedioic anhydride blocks with water reaction generation maleic acid and fumaric acid, easy etching apparatus
Pipeline, reduces product quality, and yield is relatively low.
Organic solvent absorption process can effectively overcome that energy consumption existing for water absorption method is big, equipment is easily corroded, yield of maleic anhydride is low
The shortcomings of, oneself gradually substitutes main flow of the Water Sproading method as maleic anhydride production.The organic solvent of use is different, widely used
It is dibutyl phthalate (DBP), hexahydrophthalic acid dibutyl ester and hexahydrophthalic acid diisobutyl ester (D IBE),
The HUNTSMAN in the maleic anhydride production business U.S. and the SISAS in West Europe of maximum are to use DBP as solvent in the world at present.Using having
Solvent is absorbed for expanding the scale of production, has obvious advantage in terms of continuous production, reduction energy consumption, but solvent price is
The key of production cost is influenceed, while the chemical stability under operating condition need to be improved.
Either absorbed using water or organic solvent absorbs, be required for by the isolated cis-butenedioic anhydride of rectificating method.Using
Dimethyl maleate is solvent, bigger to the solubility of cis-butenedioic anhydride compared with dibutyl phthalate, while does not need rectifying point
Production dimethyl maleate is directly used in from cis-butenedioic anhydride, part dimethyl maleate is returned for absorbing cis-butenedioic anhydride.
Cis-butenedioic anhydride can obtain dimethyl maleate with methanol esterification reaction.Traditional production method be using cis-butenedioic anhydride as raw material,
Esterification is carried out with methanol under the catalytic action of sulfuric acid, although the catalytic activity of the production technology catalyst sulfuric acid is high, valency
Lattice are cheap, but side reaction multi-product be present and be easily isomerizated into dimethyl fumarate, equipment corrosion are serious, subsequent treatment is complicated etc.
Shortcoming.Sulfuric acid is substituted using solid acid esterification catalyst, can effectively solve the problem that above mentioned problem.
The content of the invention
The problem of existing for above-mentioned recovery of Maleic Anhydride and esterification process, the invention provides a kind of life of dimethyl maleate
Production method.
The technical scheme is that：
A kind of production method of dimethyl maleate, its technological process of production are：
The mixed gas containing cis-butenedioic anhydride after heat exchange tentatively cools down enters absorption tower bottom and the maleic acid two of tower top spray
Methyl esters carries out counter current contacting and is absorbed liquid.Esterification column filling solid acid esterification catalyst filler, absorbing liquid from esterification tower top pump
Enter and reacted with the methanol steam contact at esterification column bottom, bottom of towe obtains dimethyl maleate crude product, maleic acid is obtained by distillation
Dimethyl ester product, partly return for spray-absorption cis-butenedioic anhydride.The isolated first alcohol and water of tower top aqueous methanol steam rectifying, methanol
Return and be used for esterification.
The mixed gas temperature containing cis-butenedioic anhydride after heat exchange tentatively cools down is 130 DEG C~170 DEG C, and cis-butenedioic anhydride contains
Measure as 0.4mol%~0.7mol%.
The solid acid esterification catalyst is that solid acid esterification catalyst is 732 storng-acid cation exchange resins, D001
One kind in macropore strong acid cation exchanger resin, HZSM-5 molecular sieves.
The esterification condition is：Temperature 50 C~90 DEG C, residence time are 2h~6h.
Advantages of the present invention：
1. substituting conventional organic solvents using dimethyl maleate absorbs cis-butenedioic anhydride, the bigger assimilation effect of solubility more preferably, while nothing
Need rectifying to separate cis-butenedioic anhydride, be directly used in esterification；
2. substituting convention acidic catalyst such as hydrochloric acid, sulfuric acid etc. using solid acid esterification catalyst, product is easily separated, equipment corrosion
Small, no acidic waste water produces；
Continue on for absorbing mixed gas containing cis-butenedioic anhydride 3. gained dimethyl maleate product section returns, aqueous methanol passes through rectifying
Obtained methanol can continue on for esterification.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
In figure：1- gas lines, 2- absorption towers, 3- solvent lines, 4- absorption towers circulating pump, 5- exhaust pipes, 6- absorb
Liquid storage tank, 7- esterification columns, 8- absorbing liquid pipelines, 9- methanol steam pipelines, 10- aqueous methanol steam pipe lines, 11- maleic acid diformazans
Ester crude product pipeline.
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.
Embodiment 1
1. absorption technique
The reaction generation gas of benzene oxidatoin method production cis-butenedioic anhydride first passes through heat exchange and tentatively cooled down, and cis-butenedioic anhydride contains in the gas after cooling
Measure as 0.5mol %.Cooling gas is fed by gas line 1 from the bottom of absorption tower 2, and dimethyl maleate passes through solvent line 3
Fed from the top of absorption tower 2, both counter current contactings in absorption tower 2, dimethyl maleate is absorbed and cooled down to cis-butenedioic anhydride.Inhale
Receive absorbing liquid obtained by the bottom of tower 2 and be again introduced into the top of absorption tower 2 progress cyclic absorption by absorption tower circulating pump 4, absorption tower 2 is pushed up
The tail gas of portion's discharge enters exhaust treatment system through exhaust pipe 5.
Gas temperature is 130 DEG C after preliminary cooling, and dimethyl maleate feeding temperature is 40 DEG C, and dimethyl maleate is gentle
The mass ratio of body is 0.04:1.The tower bottom pressure of absorption tower 2 is 35KPa, and temperature is 60 DEG C, and the tower top pressure of absorption tower 2 is 10KPa,
Temperature is 50 DEG C.Stop cyclic absorption when cis-butenedioic anhydride concentration reaches 60% in gained absorbing liquid after cyclic absorption, absorbing liquid is discharged into suction
Liquid storage tank 6 is received, esterification is standby.
2. esterification technique
Esterification is carried out in esterification column 7, and esterification column is packed tower, and the solid acid esterification catalyst of filling is strong for D001 macropores
Acid cation exchange resin.Absorbing liquid is fed by absorbing liquid pipeline 8 from esterification column top, and methanol passes through methanol steam pipeline
9 feed from esterification column bottom, and both carry out contact reaction on esterification tower packing.Discharge gas is containing water beetle at the top of esterification column
Alcohol steam, absolute methanol is prepared again into methanol rectifying system through aqueous methanol steam pipe line 10.Esterification tower bottom is Malaysia
Dimethyl phthalate crude product, enter distilling apparatus by dimethyl maleate crude product pipeline 11, maleic acid two is obtained by being evaporated under reduced pressure
Methyl esters product.
Packed tower temperature is 65 DEG C, and residence time of the absorbing liquid in packed tower is 4h, and cis-butenedioic anhydride esterification completely is maleic acid
Dimethyl ester, no mono-esterification product.Dimethyl maleate crude product GC testing results are：Dimethyl maleate 98.3%, methanol 1.4%,
Water 0.3%.It is evaporated under reduced pressure after purification, dimethyl maleate content is 99.6%.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
For personnel it should be appreciated that the present invention is not limited to the above embodiments, that described in above-described embodiment and specification is only the present invention
Preference, be not intended to limit the present invention, without departing from the spirit and scope of the present invention, the present invention also have it is various
Changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by institute
Attached claims and its equivalent thereof.
Claims (7)
1. it is a kind of using dimethyl maleate as solvent absorption mixed gas containing cis-butenedioic anhydride in cis-butenedioic anhydride after obtained mixing liquid be former
Material, the method that esterification production dimethyl maleate is carried out with methanol, it is characterised in that：Its technological process of production is：By
The mixed gas containing cis-butenedioic anhydride after heat exchange tentatively cooling enters absorption tower bottom and the dimethyl maleate of tower top spray is carried out
Counter current contacting is absorbed liquid；Esterification column filling solid acid esterification catalyst filler, absorbing liquid are pumped into and are esterified from esterification tower top
The methanol steam contact reaction of bottom of towe；Bottom of towe obtains dimethyl maleate crude product, and maleic acid diformazan is obtained by vacuum distillation
Ester product, partly return for spray-absorption cis-butenedioic anhydride；The isolated first alcohol and water of tower top aqueous methanol steam rectifying, methanol return
For esterification.
2. the production method of dimethyl maleate according to claim 1, it is characterised in that：Absorb in gaseous mixture containing cis-butenedioic anhydride
Cis-butenedioic anhydride used by solvent be dimethyl maleate.
3. the production method of dimethyl maleate according to claim 1, it is characterised in that：The temperature of mixed gas containing cis-butenedioic anhydride
For 130 DEG C~170 DEG C, cis-butenedioic anhydride content is 0.4mol%~0.7mol%.
4. the production method of dimethyl maleate according to claim 1, it is characterised in that：Dimethyl maleate is suitable with containing
The mass ratio of acid anhydride mixed gas is 0.01:1~0.1:1, preferably 0.03:1~0.05:1.
5. the production method of dimethyl maleate according to claim 1, it is characterised in that：Esterification device is esterification
Packed tower, filling solid acid esterification catalyst filler.
6. the production method of dimethyl maleate according to claim 1, it is characterised in that：Solid acid esterification catalyst is
One kind in 732 storng-acid cation exchange resins, D001 macropore strong acid cations exchanger resin, HZSM-5 molecular sieves.
7. the production method of dimethyl maleate according to claim 1, it is characterised in that：Esterification condition is：Temperature
50 DEG C~90 DEG C of degree, residence time are 2h~6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710756008.4A CN107473966B (en) | 2017-08-29 | 2017-08-29 | Production method of dimethyl maleate |
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| CN201710756008.4A CN107473966B (en) | 2017-08-29 | 2017-08-29 | Production method of dimethyl maleate |
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| CN107473966A true CN107473966A (en) | 2017-12-15 |
| CN107473966B CN107473966B (en) | 2021-01-05 |
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| CN201710756008.4A Active CN107473966B (en) | 2017-08-29 | 2017-08-29 | Production method of dimethyl maleate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218698A (en) * | 2018-05-15 | 2018-06-29 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of dibutyl maleate |
| WO2022166540A1 (en) * | 2021-02-08 | 2022-08-11 | 窦和瑞 | Process method for preparing glycol maleate |
| CN115322092A (en) * | 2022-09-14 | 2022-11-11 | 上海赛斯格恩化学技术有限公司 | Method for preparing dimethyl maleate by using maleic anhydride tail gas |
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| US3979443A (en) * | 1972-08-25 | 1976-09-07 | Petro-Tex Chemical Corporation | Process for the preparation of esters of maleic acid with monohydric alcohols |
| EP1056708A1 (en) * | 1998-02-13 | 2000-12-06 | Basf Aktiengesellschaft | Method for separating maleic anhydride from maleic anhydride-containing mixtures by stripping |
| CN1280558A (en) * | 1997-11-13 | 2001-01-17 | 巴斯福股份公司 | Process for preparing gamma-butyrolactone, butane-1, 4-diol and tetrahydrofuran |
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| US3979443A (en) * | 1972-08-25 | 1976-09-07 | Petro-Tex Chemical Corporation | Process for the preparation of esters of maleic acid with monohydric alcohols |
| CN1280558A (en) * | 1997-11-13 | 2001-01-17 | 巴斯福股份公司 | Process for preparing gamma-butyrolactone, butane-1, 4-diol and tetrahydrofuran |
| EP1056708A1 (en) * | 1998-02-13 | 2000-12-06 | Basf Aktiengesellschaft | Method for separating maleic anhydride from maleic anhydride-containing mixtures by stripping |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218698A (en) * | 2018-05-15 | 2018-06-29 | 山东泰和水处理科技股份有限公司 | A kind of synthetic method of dibutyl maleate |
| WO2022166540A1 (en) * | 2021-02-08 | 2022-08-11 | 窦和瑞 | Process method for preparing glycol maleate |
| CN115322092A (en) * | 2022-09-14 | 2022-11-11 | 上海赛斯格恩化学技术有限公司 | Method for preparing dimethyl maleate by using maleic anhydride tail gas |
| CN115322092B (en) * | 2022-09-14 | 2024-05-07 | 上海赛斯格恩化学技术有限公司 | Method for preparing dimethyl maleate by using maleic anhydride tail gas |
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