CN102432464A - Continuous production process of dimethyl fumarate - Google Patents
Continuous production process of dimethyl fumarate Download PDFInfo
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- CN102432464A CN102432464A CN2011104177473A CN201110417747A CN102432464A CN 102432464 A CN102432464 A CN 102432464A CN 2011104177473 A CN2011104177473 A CN 2011104177473A CN 201110417747 A CN201110417747 A CN 201110417747A CN 102432464 A CN102432464 A CN 102432464A
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- dimethyl fumarate
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- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 title claims abstract description 20
- 229960004419 dimethyl fumarate Drugs 0.000 title claims abstract description 19
- 238000010924 continuous production Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 22
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 20
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000001530 fumaric acid Substances 0.000 claims abstract description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 230000008676 import Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- -1 parabens Chemical compound 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003260 anti-sepsis Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A continuous production process of dimethyl fumarate comprises the following steps: uniformly filling a strong acid cation exchange resin catalyst into a reaction column, and heating to 60-100 ℃; adding reaction raw materials of fumaric acid and methanol solution into a reaction column from an inlet of the fixed reaction column, adjusting the flow rate of a flow pump to ensure that the raw materials stay in the reaction column for 4-8h, and collecting a reaction product at an outlet; introducing the reaction product into cold water, stirring, and separating out a large amount of white crystals; filtering, adding 8-10% Na into filter cake2CO3Washing the solution; filtering again, washing the filter cake to be neutral by using distilled water, and then drying at room temperature to obtain the product. The invention adopts the strong acid cation exchange resin, does not corrode reaction equipment, does not pollute the environment, can be repeatedly utilized and is a good environment-friendly catalyst. The catalyst is fixed in the reaction column, and continuous feeding and discharging are realized, so that the continuous operation of the reaction can be realized, the reaction condition is simple, and the operation is convenient.
Description
Technical field
The present invention relates to a kind of continuous production processes of dimethyl fumarate.
Background technology
Dimethyl fumarate is called for short DMF; The formal name used at school dimethyl fumarate, popular name fumaric acid dimethyl ester is a kind of good antisepsis antistaling agent that grows up in the 80's of 20th century; Overcome the deficiency of phenylformic acid, propionic acid, parabens, Sorbic Acid etc.; Have wide spectrum, efficient, low toxicity, characteristics such as economical and practical, many moulds are had special inhibition effect, and have fungal resistance.Dimethyl fumarate can be widely used in the fresh-keeping and anticorrosion desinsection of food, vegetables, fruit; But also can be used for industries such as leather, makeup, textiles, pharmacy; And continually developing new Application Areas; Be a kind of new food preservative of future of great use, caused the great attention of domestic and international food, feedstuff industry.Food and drug administration classifies dimethyl fumarate as foodstuff additive and with its widespread use, China also begins to pay close attention to the replacement problem of dimethyl fumarate, para Toluic Acid's sodium etc. at the beginning of the 90's, and China applies as mould inhibitor at present.
At present the suitability for industrialized production of dimethyl fumarate mainly is to be catalyzer with the vitriol oil, with fumaric acid and methyl alcohol be raw material (Zhang Jianjun. Hebei chemical industry, 2001 (2): 26～28); Horse is gone away for some great undertakings. print 2005,19 (4): 18～19) during chemical industry; Perhaps maleic anhydride and methyl alcohol be raw material (Ma Xinqi etc. chemical research, 2002,13 (4): 24～26); Perhaps toxilic acid and methyl alcohol be raw material (yellow Yongming etc. chemistry world; 1989, (3): 102～104), wherein the consumption of the catalyzer vitriol oil is about 10 % of raw material.Though traditional working method technical maturity, sulfuric acid is easy to get, and corrodibility is strong, and side reaction is many, and reaction is after operations such as neutralization, washing produce a large amount of waste liquids, contaminate environment.At present, the mankind are being faced with serious environmental problem, and wherein most all relevant with the pollution of chemical substance, Green Chemistry has been mentioned agenda.Paying attention to environment protection is the important topic of current chemical industry considered.At present both at home and abroad many scholars develop, study that some are nontoxic, do not have corrosion; Separable solid acid catalyst; To replace conventional catalysts; Though the report of the synthetic fumaric acid of catalysis such as more existing employing talcum molecular sieve immobilized phosphotungstic acid catalyzer, molecular sieve, tin tetrachloride, complicated operation and productive rate are not high.
Summary of the invention
Technical problem:The present invention is directed to above-mentioned technical problem, a kind of continuous production processes of dimethyl fumarate is provided, the employing strongly acidic cationic exchange resin is a catalyzer; The fixed bed continuous reaction; Simple to operate, yield is high, is particularly suitable for the industriallization continuous production, enhance productivity.
Technical scheme:A kind of continuous production processes of dimethyl fumarate comprises the steps:
(1), strong acid cation exchange resin catalyst evenly is filled in the reaction column, Heating temperature is 60-100 ℃;
(2), the import from the fixation reaction post of reaction raw materials fumaric acid and methanol solution is joined the reaction column, regulate the flow velocity of flow pumps, the adding speed of control raw material makes that the residence time of raw material in reaction column is 4 ~ 8h, the outlet collecting reaction product;
(3), reaction product is passed in the cold water, stir, have a large amount of white crystals to separate out;
(4), filter, filter cake is with 8-10 %Na
2CO
3Solution washing; Filter once more, filter cake is washed with distilled water to neutrality, the at room temperature dry then product that gets.
Said strong acid cation exchange resin catalyst is 732 or D-61 or D-72 type polystyrolsulfon acid type Zeo-karb.
Heating temperature is 75-88 ℃ in the said step (1).
The mol ratio of reaction raw materials fumaric acid and methyl alcohol is in the said step (2): 1:4 ~ 1:8.
Beneficial effect:
(1), the present invention adopts strongly acidic cationic exchange resin, and is inexpensive, be easy to get, and do not corrode conversion unit, free from environmental pollution, be not easy to cause side reaction, and can reuse, be a kind of good environment-friendly catalyst.
(2), the present invention with catalyzer fixing with reaction column in, successive charging and discharging, continuous operation that can realization response, reaction conditions is simple, is convenient to operation.
Description of drawings
Fig. 1 is the continuous reaction apparatus synoptic diagram, wherein: 1-raw cylinder, 2-fresh feed pump, 3-opening for feed, 4-reaction column, 5-catalyzer, 6-discharge port.
Embodiment
Embodiment 1:
A kind of continuous production processes of dimethyl fumarate, as shown in Figure 1, with 732 type polystyrolsulfon acid type Zeo-karbs (available from Shanghai be lost the song Industrial Co., Ltd.), evenly be filled in the reaction column 4, be heated to 70-75 ℃; With the reaction raw materials fumaric acid and the methanol solution that place raw cylinder 1; Mol ratio is: 1:5 through fresh feed pump 2, joins the reaction column 4 from the opening for feed 3 of fixation reaction post; Regulate the flow velocity of flow pumps; The adding speed of control raw material makes that the residence time of raw material in reaction column is 4h, discharge port 6 collecting reaction products; Reaction product is passed in the cold water, stirs, have a large amount of white crystals to separate out; Filter, filter cake is with 8 %Na
2CO
3Solution washing; Filter once more, filter cake is washed with distilled water to neutrality, the at room temperature dry then product that gets.Productive rate is 89.6%.
Embodiment 2:
A kind of continuous production processes of dimethyl fumarate, as shown in Figure 1, with D-61 type polystyrolsulfon acid type Zeo-karb (available from Shanghai be lost the song Industrial Co., Ltd.), evenly be filled in the reaction column 4, be heated to 75-80 ℃; With the reaction raw materials fumaric acid and the methanol solution that place raw cylinder 1; Mol ratio is: 1:8; Join the reaction column 4 from the opening for feed 3 of fixation reaction post, regulate the flow velocity of flow pumps, the adding speed of control raw material; Make that the residence time of raw material in reaction column is 8h, discharge port 6 goes out collecting reaction product; Reaction product is passed in the cold water, stirs, have a large amount of white crystals to separate out; Filter, filter cake is with 9%Na
2CO
3Solution washing; Filter once more, filter cake is washed with distilled water to neutrality, the at room temperature dry then product that gets.Productive rate is 94.3%.
Embodiment 3:
A kind of continuous production processes of dimethyl fumarate, with D-72 type polystyrolsulfon acid type Zeo-karb (available from Shanghai be lost the song Industrial Co., Ltd.), evenly be filled in the reaction column 4, be heated to 82-88 ℃; With the reaction raw materials fumaric acid and the methanol solution that place raw cylinder 1; Mol ratio is: 1:6; Join the reaction column from the opening for feed 3 of fixation reaction post, regulate the flow velocity of flow pumps, the adding speed of control raw material; Make that the residence time of raw material in reaction column is 6h, discharge port 6 place's collecting reaction products; Reaction product is passed in the cold water, stirs, have a large amount of white crystals to separate out; Filter, filter cake is with 10 %Na
2CO
3Solution washing; Filter once more, filter cake is washed with distilled water to neutrality, the at room temperature dry then product that gets.Productive rate is 95.7%.
Claims (4)
1. the continuous production processes of a dimethyl fumarate comprises the steps:
(1), strong acid cation exchange resin catalyst evenly is filled in the reaction column, Heating temperature is 60-100 ℃;
(2), the import from the fixation reaction post of reaction raw materials fumaric acid and methanol solution is joined the reaction column, regulate the flow velocity of flow pumps, making the residence time of raw material in reaction column is 4-8h, the outlet collecting reaction product;
(3), reaction product is passed in the cold water, stir, have a large amount of white crystals to separate out;
(4), filter, filter cake is with 8-10%Na
2CO
3Solution washing; Filter once more, filter cake is washed with distilled water to neutrality, the at room temperature dry then product that gets.
2. the continuous production processes of a kind of dimethyl fumarate according to claim 1 is characterized in that: said strong acid cation exchange resin catalyst is 732 or D-61 or D-72 type polystyrolsulfon acid type Zeo-karb.
3. the continuous production processes of a kind of dimethyl fumarate according to claim 1 is characterized in that: Heating temperature is 75-88 ℃ in the said step (1).
4. the continuous production processes of a kind of dimethyl fumarate according to claim 1 is characterized in that: the mol ratio of reaction raw materials fumaric acid and methyl alcohol is in the said step (2): 1:4 ~ 1:8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104177473A CN102432464A (en) | 2011-12-14 | 2011-12-14 | Continuous production process of dimethyl fumarate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104177473A CN102432464A (en) | 2011-12-14 | 2011-12-14 | Continuous production process of dimethyl fumarate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102432464A true CN102432464A (en) | 2012-05-02 |
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Family Applications (1)
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|---|---|---|---|
| CN2011104177473A Pending CN102432464A (en) | 2011-12-14 | 2011-12-14 | Continuous production process of dimethyl fumarate |
Country Status (1)
| Country | Link |
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| CN (1) | CN102432464A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766050A (en) * | 2012-08-10 | 2012-11-07 | 太仓市运通化工厂 | Method for synthesizing dimethyl fumarate |
| CN103848739A (en) * | 2014-03-20 | 2014-06-11 | 徐晓宁 | Production method of high-purity dimethyl fumarate |
| CN104483344A (en) * | 2015-01-07 | 2015-04-01 | 重庆民泰香料化工有限责任公司 | Fast judging method for DMF of mildew preventive |
| CN104761453A (en) * | 2015-04-22 | 2015-07-08 | 河南中帅医药科技股份有限公司 | Dimethyl fumarate crystal form and preparation method thereof |
| US9422226B2 (en) | 2011-06-08 | 2016-08-23 | Biogen Ma Inc. | Process for preparing high purity and crystalline dimethyl fumarate |
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|---|---|---|---|---|
| CN1103398A (en) * | 1993-11-30 | 1995-06-07 | 张治明 | Process for producing dimethyl fumarate with cis-butanedioic anhydride |
| US20060089505A1 (en) * | 2004-10-20 | 2006-04-27 | Eternal Chemical Co., Ltd. | Cyclobutanetetracarboxylate compound and preparation method thereof |
-
2011
- 2011-12-14 CN CN2011104177473A patent/CN102432464A/en active Pending
Patent Citations (2)
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| CN1103398A (en) * | 1993-11-30 | 1995-06-07 | 张治明 | Process for producing dimethyl fumarate with cis-butanedioic anhydride |
| US20060089505A1 (en) * | 2004-10-20 | 2006-04-27 | Eternal Chemical Co., Ltd. | Cyclobutanetetracarboxylate compound and preparation method thereof |
Non-Patent Citations (5)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9422226B2 (en) | 2011-06-08 | 2016-08-23 | Biogen Ma Inc. | Process for preparing high purity and crystalline dimethyl fumarate |
| CN102766050A (en) * | 2012-08-10 | 2012-11-07 | 太仓市运通化工厂 | Method for synthesizing dimethyl fumarate |
| CN103848739A (en) * | 2014-03-20 | 2014-06-11 | 徐晓宁 | Production method of high-purity dimethyl fumarate |
| CN104483344A (en) * | 2015-01-07 | 2015-04-01 | 重庆民泰香料化工有限责任公司 | Fast judging method for DMF of mildew preventive |
| CN104483344B (en) * | 2015-01-07 | 2017-05-10 | 重庆民泰香料化工有限责任公司 | Fast judging method for DMF of mildew preventive |
| CN104761453A (en) * | 2015-04-22 | 2015-07-08 | 河南中帅医药科技股份有限公司 | Dimethyl fumarate crystal form and preparation method thereof |
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Application publication date: 20120502 |