CN1061031C - Tech. for prodn. of dimethyl oxalate - Google Patents
Tech. for prodn. of dimethyl oxalate Download PDFInfo
- Publication number
- CN1061031C CN1061031C CN97109131A CN97109131A CN1061031C CN 1061031 C CN1061031 C CN 1061031C CN 97109131 A CN97109131 A CN 97109131A CN 97109131 A CN97109131 A CN 97109131A CN 1061031 C CN1061031 C CN 1061031C
- Authority
- CN
- China
- Prior art keywords
- benzene
- dimethyl oxalate
- esterification
- oxalic acid
- methyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 118
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005886 esterification reaction Methods 0.000 claims abstract description 25
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract 2
- 230000032050 esterification Effects 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000006210 lotion Substances 0.000 claims description 9
- 239000010413 mother solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001555 benzenes Chemical class 0.000 claims description 5
- 238000000998 batch distillation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000001117 sulphuric acid Substances 0.000 abstract 2
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 229960005404 sulfamethoxazole Drugs 0.000 description 6
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 3
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical class CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 1
- YAGHEUQOAPDHKS-UHFFFAOYSA-N dimethyl oxalate;methanol Chemical compound OC.COC(=O)C(=O)OC YAGHEUQOAPDHKS-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a technology for producing dimethyl oxalate, which is characterized in that oxalic acid and methanol are used as raw materials, benzene or homologous compounds of benzene are used as extraction agents, sulphuric acid is used as a catalyst, and finally, dimethyl oxalate is prepared through esterification reaction, layering, distillation, crystallization, filtration and washing. The technology has the advantages that because of being washed with methanol, the dimethyl oxalate prepared through crystallization has good quality, the technological requirements of sufisomezole production can be satisfied, and methanol, oxalic acid, benzene and sulphuric acid all carry out closed cycle; therefore, the yield of oxalic acid is as high as more than 95%, and the cost of dimethyl oxalate can be reduced. In the technological process, no three-waste is discharged except for waste water containing alcohol.
Description
The present invention relates to a kind of production process of chemical product, relate in particular to a kind of dimethyl oxalate production technique.
As everyone knows, sulfamethoxazole is a kind of novel sulfa drug, has characteristics such as determined curative effect, antibiotic wide spectrum, toxic side effect be little, becomes large medicine of clinical use.At present, each producer of domestic production sulfamethoxazole all is that starting raw material is produced with the oxalic acid diethyl ester, but because the oxalic acid diethyl ester cost of material is higher, makes the cost of sulfamethoxazole improve, and is unfavorable for market competition.If produce sulfamethoxazole and substitute oxalic acid diethyl ester, its cost is greatly reduced with dimethyl oxalate.But the domestic producer that does not also have the suitability for industrialized production dimethyl oxalate up to the present.
The dimethyl oxalate production technique that purpose of the present invention is invented out at above-mentioned existing issue just, this processing method is simple, and is easy to implement, yield height, gained dimethyl oxalate superior product quality.
The objective of the invention is to realize by following measure:
This dimethyl oxalate production technique is to be raw material with oxalic acid and methyl alcohol, with benzene or substituted benzene is extraction agent, with sulfuric acid is catalyzer, through esterification, static layering, the methyl alcohol washing lotion that the upper strata reaction solution is added methyl alcohol or last consignment of retention is distilled concentrated, the benzene alcohol azeotropic liquid that distills out is waited until the next batch reaction and is used, concentrated solution is cooled to crystallization, filter, crystalline mother solution is ready for use on the next batch esterification, and the filter cake that filters out is the xln methanol wash, the methyl alcohol washing lotion is waited until next batch distillation usefulness, is dimethyl oxalate of the present invention after the xln drying after the washing; Isolated lower floor reaction solution adds oxalic acid and the benzene or the substituted benzene temperature raising distillation of next batch after the esterification, carry out benzene for water, discharge contains pure waste water, and crystalline mother solution and benzene alcohol distillate that remaining liq adds last consignment of carry out the next round esterification, move in circles.
In the present invention, the required temperature of esterification is 65 ℃～75 ℃, and the time is 1～6 hour; The injected volume first of required above-mentioned raw materials is: per 0.5 mole oxalic acid adds methyl alcohol 20～100mml, benzene or toluene 20～100ml, the vitriol oil 10～50ml.
One of process characteristic of the present invention is with the crystallization of methanol wash dimethyl oxalate, can satisfy the processing requirement that sulfamethoxazole is produced with the quality that guarantees dimethyl oxalate; Two of characteristics are that the methyl alcohol washing lotion with above-mentioned gained joins in the benzene extraction liquid of esterification and carries out component distillation, the condensing crystal dimethyl oxalate; Three of characteristics are to add next batch oxalic acid and benzene or toluene or substituted benzene in lower floor's layering liquid after esterification to carry out benzene and operate for water, remove water and oxalic acid crystal water that esterification produces, add benzene alcohol azeotropic liquid and the crystalline mother solution that the last consignment of reaction distillation goes out then and carry out the next batch esterification.
The invention has the advantages that: because the dimethyl oxalate methanol wash that crystallization goes out, quality better, can satisfy the processing requirement that sulfamethoxazole is produced, and methyl alcohol, oxalic acid, benzene, and sulfuric acid all carry out closed cycle, therefore yield height can reduce the cost of dimethyl oxalate, and this technological process is except containing pure waste water, discharge compliance with environmental protection requirements without any other three wastes.
The present invention does below in conjunction with embodiment and describes in further detail:
Embodiment 1
In reaction flask, add oxalic acid 63 grams (0.5 mole), methyl alcohol 50ml, benzene 50ml, the vitriol oil (90%) 10ml, backflow was carried out esterification 2 hours, standing demix, upper strata benzene liquid is poured matrass into, and the methyl alcohol washing lotion that adds last consignment of is (if produce first, then add methanol solution) concentrate, distillation, distillate is that benzene alcohol azeotropic liquid is waited until the next batch esterification, is cooled to 10 ℃ of crystallizations, filters, crystalline mother solution is ready for use on the next batch esterification, filter cake methanol wash, washing lotion are ready for use on the next batch distillation, and packing is product of the present invention after the gained dimethyl oxalate drying.After the esterification, lower floor's mother liquor of layering gained adds next batch oxalic acid 63 grams, benzene 50ml, temperature raising distillation, carrying out benzene operates for water, after benzene is finished for water benzene steamed the crystalline mother solution and the benzene alcohol azeotropic liquid that add last consignment of again and carries out esterification, so cyclical operation, dimethyl oxalate to the oxalic acid yield more than 95%, in the whole production technology, methyl alcohol, oxalic acid, benzene, and sulfuric acid all carry out closed cycle, except containing pure waste water, discharge without any other three wastes.
Embodiment 2
In reaction flask, add oxalic acid 630 grams (0.5 mole), methyl alcohol 500ml, benzene 500ml, the vitriol oil (90%) 100ml, backflow was carried out esterification 3 hours, standing demix, upper strata benzene liquid is poured matrass into, and the methyl alcohol washing lotion that adds last consignment of is (if produce first, then add methanol solution) concentrate, distillation, distillate is that benzene alcohol azeotropic liquid is waited until the next batch esterification, is cooled to 10 ℃ of crystallizations, filters, crystalline mother solution is ready for use on the next batch esterification, filter cake methanol wash, washing lotion are ready for use on the next batch distillation, and packing is product of the present invention after the gained dimethyl oxalate drying.After the esterification, lower floor's mother liquor of layering gained adds next batch oxalic acid 630 grams, benzene 500ml, temperature raising distillation, carrying out benzene operates for water, after benzene is finished for water benzene steamed the crystalline mother solution and the benzene alcohol azeotropic liquid that add last consignment of again and carries out esterification, so cyclical operation, dimethyl oxalate to the oxalic acid yield more than 95%, in the whole production technology, methyl alcohol, oxalic acid, benzene, and sulfuric acid all carry out closed cycle, except containing pure waste water, discharge without any other three wastes.
Claims (3)
1, a kind of dimethyl oxalate production technique, it is characterized in that: it is to be raw material with oxalic acid and methyl alcohol, with benzene or substituted benzene is extraction agent, with sulfuric acid is catalyzer, through esterification, static layering, the methyl alcohol washing lotion that the upper strata reaction solution is added methyl alcohol or last consignment of retention is distilled concentrated, azeotrope benzene alcohol distillate is told and is waited until next batch reaction usefulness, concentrated solution is cooled to crystallization, after filtration, crystalline mother solution is ready for use on the next batch esterification, the filter cake that filters out is the xln methanol wash, and the methyl alcohol washing lotion is waited until next batch distillation usefulness, is dimethyl oxalate of the present invention after the xln drying after the washing; Isolated lower floor reaction solution adds oxalic acid and benzene or substituted benzene temperature raising distillation after the esterification, carries out benzene for water, discharges to contain pure waste water, and crystalline mother solution and benzene alcohol distillate that remaining liq adds last consignment of carry out the next round esterification, move in circles.
2, dimethyl oxalate production technique according to claim 1 is characterized in that: the required temperature of esterification is 65 ℃～75 ℃, and the time is 1～6 hour.
3, dimethyl oxalate production technique according to claim 1 is characterized in that: the injected volume first of above-mentioned raw materials is: per 0.5 mole oxalic acid adds methyl alcohol 20～100ml, benzene or toluene 20～100ml, the vitriol oil 10～50ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97109131A CN1061031C (en) | 1997-06-04 | 1997-06-04 | Tech. for prodn. of dimethyl oxalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97109131A CN1061031C (en) | 1997-06-04 | 1997-06-04 | Tech. for prodn. of dimethyl oxalate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1165809A CN1165809A (en) | 1997-11-26 |
| CN1061031C true CN1061031C (en) | 2001-01-24 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97109131A Expired - Fee Related CN1061031C (en) | 1997-06-04 | 1997-06-04 | Tech. for prodn. of dimethyl oxalate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1061031C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542997B (en) * | 2016-11-14 | 2019-04-16 | 山东汇海医药化工有限公司 | A kind of method that modified graphene catalyzes and synthesizes diethy-aceto oxalate |
| CN111875496A (en) * | 2020-08-22 | 2020-11-03 | 鄄城天拓生物科技有限公司 | Method for inhibiting dimethyl oxalate acid reversion |
| CN114146625A (en) * | 2021-11-16 | 2022-03-08 | 杨翠萍 | A kind of dimethyl oxalate synthesis system |
| EP4478042A4 (en) * | 2022-04-26 | 2025-06-04 | China Shenhua Coal to Liquid and Chemical Co., Ltd | METHOD FOR DETERMINING THE OXALIC ACID CONTENT OF DIMETHYL OXALATE |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742654A (en) * | 1980-08-26 | 1982-03-10 | Ube Ind Ltd | Preparation of dimethyl oxalate |
| JPH0764783A (en) * | 1993-08-27 | 1995-03-10 | Hitachi Ltd | Source code correction method |
-
1997
- 1997-06-04 CN CN97109131A patent/CN1061031C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742654A (en) * | 1980-08-26 | 1982-03-10 | Ube Ind Ltd | Preparation of dimethyl oxalate |
| JPH0764783A (en) * | 1993-08-27 | 1995-03-10 | Hitachi Ltd | Source code correction method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1165809A (en) | 1997-11-26 |
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| C14 | Grant of patent or utility model | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |