CN101824627B - Method for preparing dimethyl succinate - Google Patents
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- CN101824627B CN101824627B CN201010172847XA CN201010172847A CN101824627B CN 101824627 B CN101824627 B CN 101824627B CN 201010172847X A CN201010172847X A CN 201010172847XA CN 201010172847 A CN201010172847 A CN 201010172847A CN 101824627 B CN101824627 B CN 101824627B
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- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 395
- 239000000463 material Substances 0.000 claims abstract description 211
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 132
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000005886 esterification reaction Methods 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 43
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 36
- 230000009467 reduction Effects 0.000 claims abstract description 35
- 238000001704 evaporation Methods 0.000 claims abstract description 32
- 230000008020 evaporation Effects 0.000 claims abstract description 32
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 21
- 238000001953 recrystallisation Methods 0.000 claims abstract description 21
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 40
- 230000032050 esterification Effects 0.000 claims description 36
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 32
- -1 monomethyl cis-butenedioic acid Chemical compound 0.000 claims description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 24
- 238000009833 condensation Methods 0.000 claims description 18
- 230000005494 condensation Effects 0.000 claims description 18
- 239000007792 gaseous phase Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- 239000007790 solid phase Substances 0.000 claims description 18
- 238000011084 recovery Methods 0.000 claims description 17
- 238000000746 purification Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000005518 electrochemistry Effects 0.000 claims description 10
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- JDRMYOQETPMYQX-UHFFFAOYSA-M 4-methoxy-4-oxobutanoate Chemical compound COC(=O)CCC([O-])=O JDRMYOQETPMYQX-UHFFFAOYSA-M 0.000 claims description 2
- JDRMYOQETPMYQX-UHFFFAOYSA-N butanedioic acid monomethyl ester Natural products COC(=O)CCC(O)=O JDRMYOQETPMYQX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 13
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005202 decontamination Methods 0.000 abstract 1
- 230000003588 decontaminative effect Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000011343 solid material Substances 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 39
- 239000001384 succinic acid Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XWWUYEBFDGCJEF-UHFFFAOYSA-N CC(C(C(=O)O)C)C(=O)O.C(CCC(=O)OC)(=O)OC Chemical compound CC(C(C(=O)O)C)C(=O)O.C(CCC(=O)OC)(=O)OC XWWUYEBFDGCJEF-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 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)
Abstract
The invention relates to a method for preparing dimethyl succinate, which comprises the following steps that: (1) dehydration and decontamination: methanol and alkali-earth metal oxide are mixed, dehydrated and decontaminated; (2) separation of solid and liquid; (3) monoesterification reaction: maleic anhydride is added in the liquid-phase material which is obtained in the previous step; (4) vacuum distillation; (5) 2-esterification reaction; (6) evaporation; (7) mixing of oil and water; (8) separation of oil and water; (9) re-eesterification; (10) evaporation; (11) mixing of oil and water; (12)separation of oil and water; (13) electrochemical reduction: hydrogen is introduced to reduce dimethyl maleate to dimethyl succinate; (14) cooling and crystallization; (15) separation of solid and liquid: solid material enters the next step; (6) re-crystallization and separation: the product dimethyl succinate is obtained. The method is simple, and has reasonable process, low preparation cost, high product purity and good quality.
Description
Technical field
The present invention relates to a kind of method for preparing dimethyl succinate, particularly a kind of is the method for feedstock production dimethyl succinate with MALEIC ANHYDRIDE and methyl alcohol, belongs to the fine chemical technology field.
Background technology
Dimethyl succinate (Dimethyl Succinate) also claims Succinic acid dimethylester.CAS number is 106-65-0, and molecular formula is C
4H
10O
4, molecular weight is 146.14, is generally colourless crystallization or liquid, 19 ℃ of fusing points, and 196.4 ℃ of boiling points, 90 ℃ of flash-points, proportion 1.1198, specific refractory power 1.4197 is soluble in ether, methyl alcohol, ethanol and acetone and other organic solvent, is slightly soluble in water.Be widely used in industries such as food, spices, daily-use chemical industry, medicine, coating, rubber, plastics, be used for synthetic photostabilizer, high-grade paint, sterilant, medicine intermediate, be a kind of important chemical intermediate, be widely used in the raw material that the number of chemical product are produced.The Technology of existing preparation dimethyl succinate is a raw material with Succinic Acid and methyl alcohol mainly, adopts acid to obtain dimethyl succinate for catalyzer through esterification, and chemical equation is:
The main raw material of existing preparation dimethyl succinate is a Succinic Acid.Industrial synthesizing succinic acid mainly contains chemical method, biotransformation method and electrolytic process etc.
(1) oxidation style: paraffin generates the mixture of various carboxylic acids through deep oxidation, can get Succinic Acid after separating step through wet distillation and crystallization etc. again;
(2) hydrogenation method: MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE be hydrogenation reaction under catalyst action, generates Succinic Acid, obtains finished product through separation then.Usually catalyzer is nickel or precious metal, and temperature of reaction is about 130-140 ℃;
(3) vinylformic acid oxo synthesis: vinylformic acid and carbon monoxide generate Succinic Acid under catalyst action;
(4) acetylene method: acetylene and carbon monoxide and water are in the presence of catalyzer, and reaction can get Succinic Acid in acidic medium, and temperature of reaction 80-250 ℃, pressure 2.94-49.03MPa;
(5) biological fermentation process: compare with the traditional chemical method, the Production by Microorganism Fermentation succsinic acid has plurality of advantages: production cost has competitive power; Utilize reproducible agricultural resource to comprise carbonic acid gas, avoided dependence petrochemical material as raw material; Reduced the pollution of chemical synthesis process to environment.
(6) electrolytic reduction: cis-butenedioic anhydride and sulfuric acid and water by a certain percentage, electrolysis in electrolyzer can get Succinic Acid.Electrolytic process synthetic raw material is maleic acid or cis-butenedioic anhydride, and cathode and anode liquid aqueous sulfuric acid is separated by cationic membrane, and cathode and anode is generally all used stereotype, and is synthetic with the plate and frame electrolyzer usually.
Main raw material of the present invention is a MALEIC ANHYDRIDE.MALEIC ANHYDRIDE (Maleic Anhydride) claims cis-butenedioic anhydride again, maleic anhydride, and apple anhydride dehydration (MA):
Molecular formula is C
4H
2O
3, molecular weight is 98.06, white, needle-shaped crystals, and inflammable, easy distillation, fusing point is 52.8 ℃, boiling point is 202 ℃,
103 ℃ of flash-points.Be soluble in ethanol, ether, acetone, chloroform, be dissolved in alcohol or ester, be slightly soluble in CCl
4In gasoline, easy formation maleic acid soluble in water.Cis-butenedioic anhydride is the five-membered cyclic acid anhydrides that contains unsaturated link(age), because two key C=C and two kinds of functional groups of two carbonyls in its molecule, and two carbonyls and C=C pair of key conjugation, so its reactive behavior height, can carry out addition reaction, esterification, amidate action, polyreaction etc., and another functional group also can continue reaction after the functional group reactions in the acid anhydrides, and range of application is very wide.
Existing Succinic Acid and the methyl alcohol of adopting is that raw material makes dimethyl succinate through esterification, and Succinic Acid is to be that raw material obtains through chemistry or electrochemical hydrogenation reduction with the MALEIC ANHYDRIDE, and the technology of this preparation dimethyl succinate has mainly had problems:
(1) esterification of Succinic Acid and methyl alcohol than the esterification difficulty of MALEIC ANHYDRIDE and methyl alcohol and slowly many.Because the two key C=C in the MALEIC ANHYDRIDE molecule and two kinds of functional groups of two carbonyls, and two carbonyls and C=C pair of key conjugation, so its reactive behavior height, can carry out esterification, addition reaction etc., in esterification reaction process, Succinic Acid is more faster than the chemical reaction velocity of MALEIC ANHYDRIDE.
(2) the raw material Succinic Acid of prior art employing is to obtain Succinic Acid by MALEIC ANHYDRIDE through chemistry or electrochemical hydrogenation reduction, the speed of response of Succinic Acid that obtains and methyl alcohol reaction synthesis of dimethyl succinate is slow, reaction is difficult to carry out thoroughly make the separation and purification difficulty of product;
(3) the raw material Succinic Acid of existing Technology employing is to obtain Succinic Acid by MALEIC ANHYDRIDE through chemistry or electrochemical hydrogenation reduction.The raw material of its essence also is a MALEIC ANHYDRIDE, and MALEIC ANHYDRIDE obtains Succinic Acid through hydrogenating reduction, and Succinic Acid and methyl alcohol carry out esterification and gets dimethyl succinate then.This operational path exists main lack be that Succinic Acid and methyl alcohol carry out that the speed of response of esterification synthesis of dimethyl succinate is slow, reaction is difficult to carry out thorough, makes the separation and purification difficulty of product.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide that a kind of technology is reasonable, the preparation method is simple, production cost is low, product purity is high, the measured method for preparing dimethyl succinate of matter.
The technical scheme that realizes above-mentioned purpose is: a kind of method for preparing dimethyl succinate is to be that feedstock production goes out dimethyl succinate with MALEIC ANHYDRIDE and methyl alcohol, and described method steps is as follows:
(1) dehydrating and removing impurities: methyl alcohol is added in the dehydrating and impurity-removing device, and the adding alkaline earth metal oxide mixes and carries out the dehydrating and removing impurities operation;
(2) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid separation, and liquid phase material enters next step, and the alkaline earth metal oxide as previous step after the solid-phase material drying processed recycles;
(3) single-esterification: add MALEIC ANHYDRIDE in the liquid phase material that previous step obtains, MALEIC ANHYDRIDE and methyl alcohol generation single-esterification generate the monomethyl cis-butenedioic acid product;
(4) vacuum distilling: the material that previous step is obtained carries out the vacuum distilling operation, and the material of removing methyl alcohol through vacuum distilling enters next step, and the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation is as the recycle of the first step methanol feedstock;
(5) two esterifications reaction: add catalyzer and methyl alcohol in the material after previous step vacuum distilling, two esterifications reaction takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(6) evaporation: the material that obtains after the previous step reaction is evaporated, and the material that evaporation is removed behind the methyl alcohol enters next step, the Methanol Recovery utilization that the gaseous phase materials of evaporation obtains through condensation;
(7) oil-water mixes: the material that water and previous step are obtained adds in oil-water mixing equipment, carries out oil-water married operation, and the add-on of water is 2～20 times of MALEIC ANHYDRIDE quality in the raw material;
(8) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the previous step recycle, and oil phase material enters next step resterification reaction;
(9) resterification reaction: add anhydrous methanol and catalyzer in the oil phase material that previous step obtains, esterification further takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(10) evaporation: the previous step product is evaporated, and the dimethyl maleate material of removing methyl alcohol after the evaporation enters next step, the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation;
(11) oil-water mixes: water and the reacted material of previous step resterification are added in oil-water mixing equipment, carry out oil-water married operation, the add-on of water is 4～20 times of MALEIC ANHYDRIDE quality in the raw material;
(12) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the 7th step recycle, and oil phase material enters next step;
(13) electrochemical reduction: in the electrochemical reducting reaction device, dimethyl maleate product, water and sulfuric acid that the adding previous step obtains carry out the electrochemical hydrogenation reduction reaction, the dimethyl maleate hydrogenating reduction is a dimethyl succinate, and material enters next step after the electrochemical hydrogenation reduction reaction;
(14) crystallisation by cooling: previous step is obtained the material operation that cools, and dimethyl succinate crystallization from solution is separated out;
(15) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid lock out operation, and solid-phase material enters next step further separation and purification, and the aqueous sulfuric acid that the water material directly returns as the 13 one-step electrochemistry reduction reaction recycles;
(16) recrystallization separates: in the recrystallization separating device, the dimethyl succinate solid-phase material that previous step is obtained carries out recrystallizing and refining, obtains the dimethyl succinate product.
Further, described alkaline earth metal oxide is any one in calcium oxide, magnesium oxide, barium oxide or the strontium oxide, and the consumption of alkaline earth metal oxide is 1%～5% of a methanol quality.
Further, the mol ratio of MALEIC ANHYDRIDE and methyl alcohol is 1: 1.05～2.2 in described the 3rd step single-esterification, and the operation temperature is 20 ℃～60 ℃.
Further, the operation absolute pressure of described the 4th step vacuum distilling is 0.01MPa～0.06MPa, and service temperature is 20 ℃～60 ℃.
Further, described the 5th step two esterifications reaction and the 9th step resterification reacting middle catalyst are any one in sulfuric acid or the hydrochloric acid.
Further, in described the 5th step two esterifications reaction, the add-on of catalyzer is to add 1.0%～5.0% of MALEIC ANHYDRIDE quality in the material quantity, and the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.2～2.2, and the operation temperature is 60 ℃～80 ℃.
Further, in described the 9th step resterification reaction, the add-on of catalyzer is to add 1.0%～5.0% of MALEIC ANHYDRIDE quality in the material quantity, and the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.0～1.6, and the operation temperature is 60 ℃～100 ℃.
Further, in described the 13 one-step electrochemistry reductive electrolytic solution, the vitriolic volumetric molar concentration is 0.5mol/L～4.0mol/L, and the service temperature of reaction is 20 ℃～60 ℃, and the current density of operation is 500A/m
2～2000A/m
2
Further, the organic solvent of described the 16 step recrystallization separation and purification is any one in methyl alcohol or the ethanol, and the mol ratio of organic solvent and monomethyl succinate is 10～100: 1.
Further, the electrochemical reducting reaction device is ordinary flat type electrochemical reactor or three-dimensional electrochemical reactor in described the 13 one-step electrochemistry reduction, and the anolyte compartment and the cathode compartment of electrochemical reducting reaction device are isolated by barrier film, barrier film preferred cationic film.
Realize that the main technique equipment that the present invention needs is: chemical reactor, solid-liquid tripping device, oil-water separation device, electrochemical reducting reaction device, recrystallizing and refining device etc.
Chemical equation of the present invention is:
Adopt the benefit of technique scheme to be:
(1) utilize two carbonyls and C=C pair of key conjugation in the MALEIC ANHYDRIDE molecule to have the high characteristics of reactive behavior, at first carrying out MALEIC ANHYDRIDE and methyl alcohol and carry out esterification generation dimethyl maleate, is that raw material adopts the Technology of electrochemical hydrogenation reduction technique with the reduction of the C=C double-bond hydrogenation in dimethyl maleate preparation dimethyl succinate then with the dimethyl maleate.
(2) in MALEIC ANHYDRIDE and methyl alcohol prepared in reaction monomethyl cis-butenedioic acid reaction process, utilize the singularity of MALEIC ANHYDRIDE and anhydrous methanol prepared in reaction monomethyl cis-butenedioic acid reaction process, the reaction process that MALEIC ANHYDRIDE and anhydrous methanol esterification generate monomethyl cis-butenedioic acid does not need catalyzer just can carry out rapidly for 20 ℃～60 ℃ in service temperature, and under this operational condition, the growing amount of by product FUMARIC ACID TECH GRADE mono-methyl is few, under the excessive situation of methyl alcohol, MALEIC ANHYDRIDE transforms fully in this reaction process.
(3) in the process of monomethyl cis-butenedioic acid and methyl alcohol prepared in reaction dimethyl maleate, having made full use of in the reaction process by-product water and esterification and hydrolysis reaction is the characteristic of reversible reaction.In the process of monomethyl cis-butenedioic acid and methyl alcohol prepared in reaction dimethyl maleate, in order to improve the transformation efficiency of reaction, reduce and produce cost, simplify sepn process, adopt the processing method of substep esterification, carry out in the two esterification processes at monomethyl cis-butenedioic acid and methyl alcohol, adopt the method that adds entry in monomethyl cis-butenedioic acid and the reacted material of methyl alcohol, adopt the method for oil-water sepn that the water in the material is effectively removed, the a small amount of monomethyl cis-butenedioic acid that exists in the last two esterification reaction process reacts with methyl alcohol again, the method that in reacted material, adds entry then, adopt the method for oil-water sepn that the water in the material is effectively removed, the monomethyl cis-butenedioic acid reaction is carried out thoroughly.
(4) in dimethyl maleate electrochemical hydrogenation reduction preparation dimethyl succinate reaction process, made full use of dimethyl maleate have certain dissolubility in aqueous sulfuric acid, easily carried out the electrochemical cathode hydrogenation reduction and dimethyl maleate hydrogenating reduction product is the characteristic of single dimethyl succinate product, adopting the electrochemical hydrogenation reduction technique that the two keys in the dimethyl maleate are carried out hydrogenating reduction is singly-bound.Adopt the electrochemical hydrogenation reduction technique to have to have that the equipment suitability is strong, flexible operation, remarkable advantages such as speed of response is fast, process is safe and reliable, easy to operate, electrochemical hydrogenation reduzate selectivity height.
(5) in the reacted feed separation treating process of maleic acid diacid methyl esters electrochemical hydrogenation reduction preparation dimethyl succinate, made full use of that dimethyl succinate is dissolved in alcohol organic solvent and under the low condition of temperature water-fast characteristic, adopt the method for the succinate product that the recrystallization method separation and purification obtains.
(6) in the reacted feed separation treating process of dimethyl maleate electrochemical hydrogenation reduction preparation dimethyl succinate, because in dimethyl maleate electrochemical hydrogenation reduction preparation dimethyl succinate reaction process, do not consume sulfuric acid, so adopt the isolating method of solid-liquid that the liquid phase material aqueous sulfuric acid that obtains is directly recycled, no waste acid water solution discharging.
Technology of the present invention is reasonable, the preparation method is simple, and production cost is low, and product purity height, the quality of preparation are good, the yield height, and preparation feedback is quick, is convenient to realize heavy industrialization.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Realize that the main technique equipment that the present invention needs is: chemical reactor, solid-liquid tripping device, oil-water separation device, electrochemical reducting reaction device, recrystallization separation and purification device etc.
Embodiment one
The chemical reactor of main technique tables of equipment esterification reaction of organic acid and two esterification reactions and resterification reaction is that the still formula stirs chemical reactor, the solid-liquid tripping device is a decanter type solid-liquid tripping device, oil-water separation device is the decanter type oil-water separator, the electrochemical reducting reaction device is an ordinary flat type electrochemical reactor, the anolyte compartment and the cathode compartment of electrochemical reducting reaction device are isolated by barrier film, barrier film preferred cationic film.
As shown in the figure, a kind of method for preparing dimethyl succinate is to be that feedstock production goes out the butyric acid dimethyl ester with MALEIC ANHYDRIDE and methyl alcohol, and described method steps is as follows:
(1) dehydrating and removing impurities: methyl alcohol is added in the dehydrating and impurity-removing device, and the adding alkaline earth metal oxide mixes and carries out the dehydrating and removing impurities operation, and alkaline earth metal oxide is a calcium oxide, and the consumption of calcium oxide is 1% of a methanol quality;
(2) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid separation in decanter type solid-liquid tripping device, liquid phase material enters next step, and the alkaline earth metal oxide as previous step after the solid-phase material drying processed recycles;
(3) single-esterification: add MALEIC ANHYDRIDE in the liquid phase material that previous step obtains, MALEIC ANHYDRIDE and methyl alcohol generation single-esterification generate the monomethyl cis-butenedioic acid product.The mol ratio of MALEIC ANHYDRIDE and methyl alcohol is 1: 1.05 in the single-esterification, and the single-esterification service temperature is 60 ℃;
(4) vacuum distilling: the material that previous step is obtained carries out the vacuum distilling operation, and the material of removing methyl alcohol through vacuum distilling enters next step, and the methyl alcohol that the gaseous phase materials that steams obtains through condensation is as the recycle of the first step methanol feedstock.The operation absolute pressure of vacuum distilling is 0.06MPa, and service temperature is 60 ℃;
(5) two esterifications reaction: add catalyzer and methyl alcohol in the material after previous step vacuum distilling, the add-on of catalyzer is to add 1.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.2, the operation temperature is 60 ℃, and catalyzer is a sulfuric acid.Two esterifications reaction takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(6) evaporation: the material that obtains after the previous step reaction is evaporated, and the material that evaporation is removed behind the methyl alcohol enters next step, the Methanol Recovery utilization that the gaseous phase materials of evaporation obtains through condensation;
(7) oil-water mixes: the material that water and previous step are obtained adds in oil-water mixing equipment, carries out oil-water married operation, and the add-on of water is 2 times of MALEIC ANHYDRIDE quality in the raw material;
(8) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the previous step recycle, and oil phase material enters next step resterification reaction;
(9) resterification reaction: in the oil phase material that previous step obtains, add anhydrous methanol and catalyzer, the add-on of catalyzer is to add 1.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.0, the operation temperature is 60 ℃, and catalyzer is a sulfuric acid.Esterification further takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(10) evaporation: the previous step product is evaporated, and the dimethyl maleate material of removing methyl alcohol after the evaporation enters next step, the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation;
(11) oil-water mixes: water and the reacted material of previous step resterification are added in oil-water mixing equipment, carry out oil-water married operation, the add-on of water is 4 times of MALEIC ANHYDRIDE quality in the raw material;
(12) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the 7th step recycle, and oil phase material enters next step;
(13) electrochemical reduction: in the electrochemical reducting reaction device, dimethyl maleate product, water and sulfuric acid that the adding previous step obtains carry out the electrochemical hydrogenation reduction reaction, the dimethyl maleate hydrogenating reduction is a dimethyl succinate, and material enters next step after the electrochemical hydrogenation reduction reaction.In the electrolytic solution of electrochemical reduction, the vitriolic volumetric molar concentration is 0.5mol/L, and the service temperature of reaction is 20 ℃, and the current density of operation is 500A/m
2
(14) crystallisation by cooling: previous step is obtained the material operation that cools, and dimethyl succinate crystallization from solution is separated out;
(15) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid lock out operation, and solid-phase material enters next step further separation and purification, and the aqueous sulfuric acid that the water material directly returns as the 13 one-step electrochemistry reduction reaction recycles;
(16) recrystallization separates: in the recrystallization separating device, the dimethyl succinate solid-phase material that previous step is obtained carries out recrystallizing and refining, obtains the dimethyl succinate product.The organic solvent of recrystallization separation and purification is a methyl alcohol, and the mol ratio of organic solvent and dimethyl succinate is 10: 1.
Embodiment two
The chemical reactor of reaction of main technique tables of equipment methyl esters and two esterification reactions and resterification reaction is a tubular chemical reactor, the solid-liquid tripping device is a filtering type solid-liquid tripping device, oil-water separation device is centrifugal oil-water separator, the electrochemical reducting reaction device is a three-dimensional electrochemical reactor, the anolyte compartment and the cathode compartment of electrochemical reducting reaction device are isolated by barrier film, barrier film preferred cationic film.
As shown in the figure, a kind of method for preparing dimethyl succinate is to be that feedstock production goes out dimethyl succinate with MALEIC ANHYDRIDE and methyl alcohol, and described method steps is as follows:
(1) dehydrating and removing impurities: methyl alcohol is added in the dehydrating and impurity-removing device, and the adding alkaline earth metal oxide mixes and carries out the dehydrating and removing impurities operation, and alkaline earth metal oxide is a magnesium oxide, and magnesian consumption is 3% of a methanol quality;
(2) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid separation in filtering type solid-liquid tripping device, liquid phase material enters next step, and the alkaline earth metal oxide as previous step after the solid-phase material drying processed recycles;
(3) single-esterification: add MALEIC ANHYDRIDE in the liquid phase material that previous step obtains, MALEIC ANHYDRIDE and methyl alcohol generation single-esterification generate the monomethyl cis-butenedioic acid product.The mol ratio of MALEIC ANHYDRIDE and methyl alcohol is 1: 1.5 in the single-esterification, and the single-esterification service temperature is 40 ℃;
(4) vacuum distilling: the material that previous step is obtained carries out the vacuum distilling operation, and the material of removing methyl alcohol through vacuum distilling enters next step, and the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation is as the recycle of the first step methanol feedstock.The operation absolute pressure of vacuum distilling is 0.03MPa, and service temperature is 40 ℃;
(5) two esterifications reaction: add catalyzer and methyl alcohol in the material after previous step vacuum distilling, the add-on of catalyzer is to add 2.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.5, the operation temperature is 65 ℃, and catalyzer is a hydrochloric acid.Two esterifications reaction takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(6) evaporation: the material that obtains after the previous step reaction is evaporated, and the material that evaporation is removed behind the methyl alcohol enters next step, the Methanol Recovery utilization that the gaseous phase materials of evaporation obtains through condensation;
(7) oil-water mixes: the material that water and previous step are obtained adds in oil-water mixing equipment, carries out oil-water married operation, and the add-on of water is 10 times of MALEIC ANHYDRIDE quality in the raw material;
(8) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the previous step recycle, and oil phase material enters next step resterification reaction;
(9) resterification reaction: in the oil phase material that previous step obtains, add anhydrous methanol and catalyzer, the add-on of catalyzer is to add 2.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.2, the operation temperature is 70 ℃, and catalyzer is a hydrochloric acid.Esterification further takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(10) evaporation: the previous step product is evaporated, and the dimethyl maleate material of removing methyl alcohol after the evaporation enters next step, the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation;
(11) oil-water mixes: water and the reacted material of previous step resterification are added in oil-water mixing equipment, carry out oil-water married operation, the add-on of water is 10 times of MALEIC ANHYDRIDE quality in the raw material;
(12) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the 7th step recycle, and oil phase material enters next step;
(13) electrochemical reduction: in the electrochemical reducting reaction device, dimethyl maleate product, water and sulfuric acid that the adding previous step obtains carry out the electrochemical hydrogenation reduction reaction, the dimethyl maleate hydrogenating reduction is a dimethyl succinate, and material enters next step after the electrochemical hydrogenation reduction reaction.In the electrolytic solution of electrochemical reduction, the vitriolic volumetric molar concentration is 2.0mol/L, and the service temperature of reaction is 40 ℃, and the current density of operation is 1000A/m
2
(14) crystallisation by cooling: previous step is obtained the material operation that cools, and dimethyl succinate crystallization from solution is separated out;
(15) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid lock out operation, and solid-phase material enters next step further separation and purification, and the aqueous sulfuric acid that the water material directly returns as the 13 one-step electrochemistry reduction reaction recycles;
(16) recrystallization separates: in the recrystallization separating device, the dimethyl succinate solid-phase material that previous step is obtained carries out recrystallizing and refining, obtains the dimethyl succinate product.The organic solvent of recrystallization separation and purification is an ethanol, and the mol ratio of organic solvent and dimethyl succinate is 50: 1.
Embodiment three
The chemical reactor of reaction of main technique tables of equipment methyl esters and two esterification reactions and resterification reaction is a static mixer, the solid-liquid tripping device is centrifugal solid-liquid tripping device, oil-water separation device is efficient oil-water separator, the electrochemical reducting reaction device is an ordinary flat type electrochemical reactor, the anolyte compartment and the cathode compartment of electrochemical reducting reaction device are isolated by barrier film, barrier film preferred cationic film.
As shown in the figure, a kind of method for preparing dimethyl succinate is to be that feedstock production goes out dimethyl succinate with MALEIC ANHYDRIDE and methyl alcohol, and described method steps is as follows:
(1) dehydrating and removing impurities: methyl alcohol is added in the dehydrating and impurity-removing device, and the adding alkaline earth metal oxide mixes and carries out the dehydrating and removing impurities operation, and alkaline earth metal oxide is a barium oxide, and barytic consumption is 4% of a methanol quality;
(2) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid separation in centrifugal solid-liquid tripping device, liquid phase material enters next step, and the alkaline earth metal oxide as previous step after the solid-phase material drying processed recycles;
(3) single-esterification: add MALEIC ANHYDRIDE in the liquid phase material that previous step obtains, MALEIC ANHYDRIDE and methyl alcohol generation single-esterification generate the monomethyl cis-butenedioic acid product.The mol ratio of MALEIC ANHYDRIDE and methyl alcohol is 1: 1.8 in the single-esterification, and the single-esterification service temperature is 50 ℃;
(4) vacuum distilling: the material that previous step is obtained carries out the vacuum distilling operation, and the material of removing methyl alcohol through vacuum distilling enters next step, and the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation is as the recycle of the first step methanol feedstock.The operation absolute pressure of vacuum distilling is 0.04MPa, and service temperature is 50 ℃;
(5) two esterifications reaction: add catalyzer and methyl alcohol in the material after previous step vacuum distilling, the add-on of catalyzer is to add 3.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.8, the operation temperature is 70 ℃, and catalyzer is a sulfuric acid.Two esterifications reaction takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(6) evaporation: the material that obtains after the previous step reaction is evaporated, and the material that evaporation is removed behind the methyl alcohol enters next step, the Methanol Recovery utilization that the gaseous phase materials of evaporation obtains through condensation;
(7) oil-water mixes: the material that water and previous step are obtained adds in oil-water mixing equipment, carries out oil-water married operation, and the add-on of water is 15 times of MALEIC ANHYDRIDE quality in the raw material;
(8) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the previous step recycle, and oil phase material enters next step resterification reaction;
(9) resterification reaction: in the oil phase material that previous step obtains, add anhydrous methanol and catalyzer, the add-on of catalyzer is to add 3.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.5, the operation temperature is 80 ℃, and catalyzer is a sulfuric acid.Esterification further takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(10) evaporation: the previous step product is evaporated, and the dimethyl maleate material of removing methyl alcohol after the evaporation enters next step, the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation;
(11) oil-water mixes: water and the reacted material of previous step resterification are added in oil-water mixing equipment, carry out oil-water married operation, the add-on of water is 15 times of MALEIC ANHYDRIDE quality in the raw material;
(12) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the 7th step recycle, and oil phase material enters next step;
(13) electrochemical reduction: in the electrochemical reducting reaction device, dimethyl maleate product, water and sulfuric acid that the adding previous step obtains carry out the electrochemical hydrogenation reduction reaction, the dimethyl maleate hydrogenating reduction is a dimethyl succinate, and material enters next step after the electrochemical hydrogenation reduction reaction.In the electrolytic solution of electrochemical reduction, the vitriolic volumetric molar concentration is 3.0mol/L, and the service temperature of reaction is 50 ℃, and the current density of operation is 1500A/m
2
(14) crystallisation by cooling: previous step is obtained the material operation that cools, and dimethyl succinate crystallization from solution is separated out;
(15) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid lock out operation, and solid-phase material enters next step further separation and purification, and the aqueous sulfuric acid that the water material directly returns as the 13 one-step electrochemistry reduction reaction recycles;
(16) recrystallization separates: in the recrystallization separating device, the dimethyl succinate solid-phase material that previous step is obtained carries out recrystallizing and refining, obtains the dimethyl succinate product.The organic solvent of recrystallization separation and purification is a methyl alcohol, and the mol ratio of organic solvent and dimethyl succinate is 80: 1.
Embodiment four
The chemical reactor of reaction of main technique tables of equipment methyl esters and two esterification reactions and resterification reaction is that the still formula stirs chemical reactor, the solid-liquid tripping device is a vane-type solid-liquid tripping device, oil-water separation device is the decanter type oil-water separator, the electrochemical reducting reaction device is a three-dimensional electrochemical reactor, the anolyte compartment and the cathode compartment of electrochemical reducting reaction device are isolated by barrier film, barrier film preferred cationic film.
As shown in the figure, a kind of method for preparing dimethyl succinate is to be that feedstock production goes out dimethyl succinate with MALEIC ANHYDRIDE and methyl alcohol, and described method steps is as follows:
(1) dehydrating and removing impurities: methyl alcohol is added in the dehydrating and impurity-removing device, and the adding alkaline earth metal oxide mixes and carries out the dehydrating and removing impurities operation, and alkaline earth metal oxide is a strontium oxide, and the consumption of strontium oxide is 5% of a methanol quality;
(2) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid separation in vane-type solid-liquid tripping device, liquid phase material enters next step, and the alkaline earth metal oxide as previous step after the solid-phase material drying processed recycles;
(3) single-esterification: add MALEIC ANHYDRIDE in the liquid phase material that previous step obtains, MALEIC ANHYDRIDE and methyl alcohol generation single-esterification generate the monomethyl cis-butenedioic acid product.The mol ratio of MALEIC ANHYDRIDE and methyl alcohol is 1: 2.2 in the single-esterification, and the single-esterification service temperature is 20 ℃;
(4) vacuum distilling: the material that previous step is obtained carries out the vacuum distilling operation, and the material of removing methyl alcohol through vacuum distilling enters next step, and the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation is as the recycle of the first step methanol feedstock.The operation absolute pressure of vacuum distilling is 0.01MPa, and service temperature is 20 ℃;
(5) two esterifications reaction: add catalyzer and methyl alcohol in the material after previous step vacuum distilling, the add-on of catalyzer is to add 5.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 2.2, the operation temperature is 80 ℃, and catalyzer is a hydrochloric acid.Two esterifications reaction takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(6) evaporation: the material that obtains after the previous step reaction is evaporated, and the material that evaporation is removed behind the methyl alcohol enters next step, the Methanol Recovery utilization that the gaseous phase materials of evaporation obtains through condensation;
(7) oil-water mixes: the material that water and previous step are obtained adds in oil-water mixing equipment, carries out oil-water married operation, and the add-on of water is 20 times of MALEIC ANHYDRIDE quality in the raw material;
(8) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the previous step recycle, and oil phase material enters next step resterification reaction;
(9) resterification reaction: in the oil phase material that previous step obtains, add anhydrous methanol and catalyzer, the add-on of catalyzer is to add 5.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.6, the operation temperature is 100 ℃, and catalyzer is a hydrochloric acid.Esterification further takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(10) evaporation: the previous step product is evaporated, and the dimethyl maleate material of removing methyl alcohol after the evaporation enters next step, the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation;
(11) oil-water mixes: water and the reacted material of previous step resterification are added in oil-water mixing equipment, carry out oil-water married operation, the add-on of water is 20 times of MALEIC ANHYDRIDE quality in the raw material;
(12) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the 7th step recycle, and oil phase material enters next step;
(13) electrochemical reduction: in the electrochemical reducting reaction device, dimethyl maleate product, water and sulfuric acid that the adding previous step obtains carry out the electrochemical hydrogenation reduction reaction, the dimethyl maleate hydrogenating reduction is a dimethyl succinate, and material enters next step after the electrochemical hydrogenation reduction reaction.In the electrolytic solution of electrochemical reduction, the vitriolic volumetric molar concentration is 4.0mol/L, and the service temperature of reaction is 60 ℃, and the current density of operation is 2000A/m
2
(14) crystallisation by cooling: previous step is obtained the material operation that cools, and dimethyl succinate crystallization from solution is separated out;
(15) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid lock out operation, and solid-phase material enters next step further separation and purification, and the aqueous sulfuric acid that the water material directly returns as the 13 one-step electrochemistry reduction reaction recycles;
(16) recrystallization separates: in the recrystallization separating device, the dimethyl succinate solid-phase material that previous step is obtained carries out recrystallizing and refining, obtains the dimethyl succinate product.The organic solvent of recrystallization separation and purification is an ethanol, and the mol ratio of organic solvent and dimethyl succinate is 100: 1.
Remove the various embodiments described above, embodiment of the present invention also have a lot, and the technical scheme that all employings are equal to or equivalence is replaced is all within protection scope of the present invention.
Claims (10)
1. method for preparing dimethyl succinate is to be that feedstock production goes out dimethyl succinate with MALEIC ANHYDRIDE and methyl alcohol, it is characterized in that described method steps is as follows:
(1) dehydrating and removing impurities: methyl alcohol is added in the dehydrating and impurity-removing device, and the adding alkaline earth metal oxide mixes and carries out the dehydrating and removing impurities operation;
(2) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid separation, and liquid phase material enters next step, and the alkaline earth metal oxide as previous step after the solid-phase material drying processed recycles;
(3) single-esterification: add MALEIC ANHYDRIDE in the liquid phase material that previous step obtains, MALEIC ANHYDRIDE and methyl alcohol generation single-esterification generate the monomethyl cis-butenedioic acid product;
(4) vacuum distilling: the material that previous step is obtained carries out the vacuum distilling operation, and the material of removing methyl alcohol through vacuum distilling enters next step, and the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation is as the recycle of the first step methanol feedstock;
(5) two esterifications reaction: add catalyzer and methyl alcohol in the material after previous step vacuum distilling, two esterifications reaction takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(6) evaporation: the material that obtains after the previous step reaction is evaporated, and the material that evaporation is removed behind the methyl alcohol enters next step, the Methanol Recovery utilization that the gaseous phase materials of evaporation obtains through condensation;
(7) oil-water mixes: the material that water and previous step are obtained adds in oil-water mixing equipment, carries out oil-water married operation, and the add-on of water is 2～20 times of MALEIC ANHYDRIDE quality in the raw material;
(8) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the previous step recycle, and oil phase material enters next step resterification reaction;
(9) resterification reaction: add anhydrous methanol and catalyzer in the oil phase material that previous step obtains, esterification further takes place and generates the dimethyl maleate product in monomethyl cis-butenedioic acid and methyl alcohol, and reacting rear material enters next step;
(10) evaporation: the previous step product is evaporated, and the dimethyl maleate material of removing methyl alcohol after the evaporation enters next step, the Methanol Recovery utilization that the gaseous phase materials that steams obtains through condensation;
(11) oil-water mixes: water and the reacted material of previous step resterification are added in oil-water mixing equipment, carry out oil-water married operation, the add-on of water is 4～20 times of MALEIC ANHYDRIDE quality in the raw material;
(12) oil-water sepn: the material that previous step is obtained carries out oil-water sepn operation, and the water material returns the 7th step recycle, and oil phase material enters next step;
(13) electrochemical reduction: in the electrochemical reducting reaction device, dimethyl maleate product, water and sulfuric acid that the adding previous step obtains carry out the electrochemical hydrogenation reduction reaction, the dimethyl maleate hydrogenating reduction is a dimethyl succinate, and material enters next step after the electrochemical hydrogenation reduction reaction;
(14) crystallisation by cooling: previous step is obtained the material operation that cools, and dimethyl succinate crystallization from solution is separated out;
(15) solid-liquid separates: the material that previous step is obtained carries out the solid-liquid lock out operation, and solid-phase material enters next step further separation and purification, and the aqueous sulfuric acid that the water material directly returns as the 13 one-step electrochemistry reduction reaction recycles;
(16) recrystallization separates: in the recrystallization separating device, the dimethyl succinate solid-phase material that previous step is obtained carries out recrystallizing and refining, obtains the dimethyl succinate product.
2. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: described alkaline earth metal oxide is any one in calcium oxide, magnesium oxide, barium oxide or the strontium oxide, and the consumption of alkaline earth metal oxide is 1%～5% of a methanol quality.
3. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: the mol ratio of MALEIC ANHYDRIDE and methyl alcohol is 1: 1.05～2.2 in described the 3rd step single-esterification, and the operation temperature is 20 ℃～60 ℃.
4. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: the operation absolute pressure of described the 4th step vacuum distilling is 0.01MPa～0.06MPa, and service temperature is 20 ℃～60 ℃.
5. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: described the 5th step two esterifications reaction and the 9th step resterification reacting middle catalyst are any one in sulfuric acid or the hydrochloric acid.
6. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: in described the 5th step two esterifications reaction, the add-on of catalyzer is to add 1.0%～5.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.2～2.2, and the operation temperature is 60 ℃～80 ℃.
7. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: in described the 9th step resterification reaction, the add-on of catalyzer is to add 1.0%～5.0% of MALEIC ANHYDRIDE quality in the material quantity, the mol ratio that adds MALEIC ANHYDRIDE in the add-on of methyl alcohol and the material quantity is 1: 1.0～1.6, and the operation temperature is 60 ℃～100 ℃.
8. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: in described the 13 one-step electrochemistry reductive electrolytic solution, the vitriolic volumetric molar concentration is 0.5mol/L～4.0mol/L, and the service temperature of reaction is 20 ℃～60 ℃, and the current density of operation is 500A/m
2～2000A/m
2
9. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: the organic solvent of described the 16 step recrystallization separation and purification is any one in methyl alcohol or the ethanol, and the mol ratio of organic solvent and monomethyl succinate is 10～100: 1.
10. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: the electrochemical reducting reaction device is ordinary flat type electrochemical reactor or three-dimensional electrochemical reactor in described the 13 one-step electrochemistry reduction, and the anolyte compartment and the cathode compartment of electrochemical reducting reaction device are isolated by barrier film.
Priority Applications (1)
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| CN104163761B (en) * | 2014-08-06 | 2016-04-13 | 中建安装工程有限公司 | A kind of method of rectified purified dimethyl succinate |
| CN112609201B (en) * | 2020-12-11 | 2023-09-19 | 万华化学(四川)有限公司 | Method for synthesizing carbonic acid diester and sebacic acid diester in pair |
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