CN102746149B - Method for preparing monoester succinate by esterification of ammonium succinate - Google Patents
Method for preparing monoester succinate by esterification of ammonium succinate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 title claims abstract description 27
- 230000032050 esterification Effects 0.000 title claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 16
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 239000001384 succinic acid Substances 0.000 claims description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- JDRMYOQETPMYQX-UHFFFAOYSA-N butanedioic acid monomethyl ester Natural products COC(=O)CCC(O)=O JDRMYOQETPMYQX-UHFFFAOYSA-N 0.000 claims description 19
- JDRMYOQETPMYQX-UHFFFAOYSA-M 4-methoxy-4-oxobutanoate Chemical group COC(=O)CCC([O-])=O JDRMYOQETPMYQX-UHFFFAOYSA-M 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007791 dehumidification Methods 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 13
- 150000001733 carboxylic acid esters Chemical class 0.000 description 10
- -1 organic acid ammonium salt Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960002097 dibutylsuccinate Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010242 baoji Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing monoester succinate by esterification of ammonium succinate. The method adopts reaction distillation, a gaseous product is subjected to condensation reaction, ammonia is recovered by the aid of a gas-liquid separator, the condensed esterifying agent and water are subjected to a drying system for absorbing water generated in the reaction, and the dried esterifying agent is refluxed into a reaction kettle. By the method, the esterifying agent is effectively used, the production process is clean, environmental protection is facilitated, consumption of raw materials is lowered, and production cost is lowered. In addition, the method for preparing the monoester succinate by the esterification of the ammonium succinate is high in product purity and yield, good in product quality and convenient to realize large-scale industrial production.
Description
Technical field
The invention belongs to chemical field, relate to a kind of method of being prepared succinate monoester by succinic acid two ammonium esterifications.
Background technology
Monomethyl succinate (claiming again monomethyl succinate) is for No. CAS 3878-55-5, molecular formula C
5h
8o
4, molecular weight 132.11, is white crystal under normal temperature, and fusing point is 56-59 ℃, and boiling point is 151 ℃, is dissolved in the organic solvents such as alcohol, ether and benzene, water insoluble.Monomethyl succinate is the synthetic intermediate of organic synthesis and medicine, is also the substrate material of producing colour candle, has the advantages such as burning is smokeless, odorless.
The synthetic method of monomethyl succinate mainly contains: succinic acid and dimethyl succinate be warm altogether; Soduxin is processed dimethyl succinate; Succinic acid and three kinds of methods of methyl alcohol reaction.But existing method exists operation and controls difficulty, poor product quality, production cost be high, be difficult to the drawbacks such as heavy industrialization.
Under the organic solvent condition that contains esterifying agent, carrying out thermolysis from succinic acid di-ammonium salts is a kind of method that obtains succinate monoester.The people such as Cockrem (US6291708B1) have studied mixture preparation acid, the ester of fast pyrogenation organic acid ammonium salt and alcohol, and its unreacted product is steam.But the people such as Cockrem can not separate the product acid of unreacted ammonium salt and generation with ester, and its temperature of reaction and reaction pressure all higher, be generally 150 ~ 280 ℃, approximately 6 ~ 120 normal atmosphere of 100 ~ 1800psig().
The people such as Filachione (US2565487) have studied the method for preparing carboxylicesters from organic acid basic salt, by at backflow alcohol, particularly in the situation that containing the catalyzer such as ammonium sulfate and alcohol, heat carboxylic acid and make the complex fluid product mixtures of carboxylicesters, water, alcohol and unreacted carboxylate salt.The product liquid mixture obtaining needs follow-up distilation steps to obtain carboxylicesters.
WO9823579A1 discloses a kind of novel process that adopts permeable membrane esterification bio-based ammonium salt, but esterification yield is lower than 40%.Result shows, this method is not a kind of excellent process of preparing carboxylicesters.
The people such as E. I. Du Pont de Nemours and Co Gallacher you (CN101087750B) have studied ammonium carboxylate salt is prepared carboxylicesters method by alcoholysis, alcohol is preheating to 140-300 ℃, then contact with the ammonium carboxylate salt aqueous solution, hot alcohol is as esterifying agent, and steam product phase carboxylicesters component is shifted out from reactor with stripping gas, thus needed ester products in reactor is separated from water.From steam product, reclaim subsequently carboxylicesters.The alcohol reclaiming can again pass in hot alcohol steam feed stream and carry out recycle.
US2009/0137825A1 has reported that a kind of succinic acid two ammoniums and esterified by butyl alcohol prepare dibutyl succinate, and dibutyl succinate is the novel process for tetrahydrofuran (THF) by Hydrogenation.The method adopts reactive distillation process in Esterification Stage, and the yield of dibutyl succinate is 80%-100%.
Summary of the invention
For ammonium carboxylate salt esterification prepare carboxylicesters yield low, separate difficult shortcoming, the invention provides the novel method that carboxylicesters is prepared in a kind of ammonium carboxylate salt esterification, the advantage of the method is that the yield of carboxylicesters is high, by product is few, product purity is high.
Particularly, the invention provides a kind of method of being prepared succinate monoester by succinic acid two ammonium esterifications, the method comprises the following steps:
(1) first succinic acid two aqueous ammoniums are joined in reactor together with the mol ratio of 1:2 to 1:10 with esterifying agent, and pass into nitrogen in reactor;
(2) at the temperature of 65 ℃-120 ℃, make succinic acid two ammoniums in reactor carry out esterification, reaction is carried out 8 ~ 14 hours;
(3) in above-mentioned reaction process, the gas-phase product on reactor top is obtained to ammonia, esterifying agent and water through condenser and gas-liquid separator separates, ammonia is passed into Ammonia recovery system, and esterifying agent and water are removed to the water that dereaction generates by dehumidification system, dried esterifying agent is back in reactor;
(4) after above-mentioned reaction finishes, the still bottom product in reactor is led to azeotropic and rise in rectifying tower, and add entrainer to distill, thereby obtain product succinate monoester,
Wherein, the concentration of described succinic acid two aqueous ammoniums is 10wt% to 90wt%, is preferably 10wt% to 70wt%, more preferably 40wt% to 70wt%.
Described esterifying agent is C1 ~ C6 alkyl alcohol of straight or branched, is preferably methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or the trimethyl carbinol, more preferably methyl alcohol,
Described entrainer is the one in chloroform, tetracol phenixin, benzene, toluene, acetonitrile, Virahol, pyridine, n-propyl alcohol, ethyl acetate, is preferably ethyl acetate,
In above-mentioned steps (1), the mol ratio of described succinic acid two aqueous ammoniums and esterifying agent is preferably 1:5 to 1:10, more preferably 1:10.
In above-mentioned steps (2), temperature of reaction is preferably 70 ℃ ~ 75 ℃, more preferably 75 ℃.
In above-mentioned steps (2), the reaction times is preferably 8 ~ 10 hours, more preferably 10 hours.
In above-mentioned steps (4), the stage number that described azeotropic is risen rectifying tower is 5-40, is preferably 12-18.
In above-mentioned steps (4), described reflux ratio is 0.5-3, is preferably 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.
Prepared in the method for succinate monoester by succinic acid two ammonium esterifications provided by the invention, utilize succinic acid two aqueous ammoniums to react with esterifying agent generation self-catalytic esterification and generate succinate monoester, in reaction process, removed in time the ammonia G&W producing in reaction.Method provided by the invention has improved the gamma value of succinic acid two ammoniums, has guaranteed that the yield of succinate monoester reaches 75-100%, has suppressed the generation of by product simultaneously, and in product, the content of nitrogen element is below 1wt%.
Compared with the conventional method, the method for preparing succinate monoester provided by the invention has the following advantages: speed of response is fast, and by product is few, the cost of raw material is minimum, and reaction is easy to control, and energy consumption of reaction is low, reaction product is easy to separate, and product purity is high, and the safety coefficient of equipment used is high.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrum of monomethyl succinate prepared in accordance with the present invention.
Embodiment
Below by embodiment, the present invention will be further described, but scope of the present invention is not only limited to the scope that embodiment covers.
Starting material succinic acid two ammoniums that use in following examples are all purchased from Baoji precious jade Chemical Co., Ltd..
Embodiment 1
7.6g succinic acid two ammoniums are added in 11.4 water, and the solution that the concentration that obtains 19g succinic acid two ammoniums is 40wt%, joins this solution and 20ml methyl alcohol stream in reactor, in reactor, passes into nitrogen, makes reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 70 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 1.
Embodiment 2
7.6g succinic acid two ammoniums are added in 7.6 water, obtain the solution that 15.2g succinic acid two ammonium concentrations are 50wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 70 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 1.
Embodiment 3
7.6g succinic acid two ammoniums are added in 5.1 water, obtain the solution that 12.7g succinic acid two ammonium concentrations are 60wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 70 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 1.
Embodiment 4
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 70 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 1.
The result of table 1 embodiment 1-embodiment 4
Embodiment 5
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 65 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 2.
Embodiment 6
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 70 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 2.
Embodiment 7
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 75 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 2.
Embodiment 8
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 80 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 2.
The result of table 2 embodiment 5-embodiment 8
Embodiment 9
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 75 ℃, and the reaction times is 8h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 3.
Embodiment 10
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 75 ℃, and the reaction times is 10h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 3.
Embodiment 11
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 75 ℃, and the reaction times is 12h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 3.
Embodiment 12
7.6g succinic acid two ammoniums are added in 3.3 water, obtain the solution that 10.9g succinic acid two ammonium concentrations are 70wt%, this solution and 20ml methyl alcohol stream are joined in reactor, in reactor, pass into nitrogen, make reacting kettle inner pressure be promoted to 1atm.Temperature of reaction is 75 ℃, and the reaction times is 14h.
The stage number of succinate azeotropy rectification column is 15, adds 16g ethyl acetate as entrainer, and reflux ratio is 1, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.The nuclear magnetic spectrum of the monomethyl succinate obtaining as shown in Figure 1.Experimental result sees below table 3.
The result of table 3 embodiment 9-embodiment 12
As can be seen from the above results, when succinic acid two aqueous ammonium concentration are 20wt%, temperature of reaction is 75 ℃, and the reaction times, while being 10 hours, the by product that method of the present invention obtains was few, and the cost of raw material is low, and product purity is high.
Claims (10)
1. a method of being prepared succinate monoester by succinic acid two ammonium esterifications, the method comprises the following steps:
(1) first succinic acid two aqueous ammoniums are joined in reactor together with the mol ratio of 1:2 to 1:10 with esterifying agent, and pass into nitrogen in reactor;
(2) at the temperature of 65 ℃-120 ℃, make succinic acid two ammoniums in reactor carry out esterification, reaction is carried out 8～14 hours;
(3) in above-mentioned reaction process, the gas-phase product on reactor top is obtained to ammonia, esterifying agent and water through condenser and gas-liquid separator separates, ammonia is passed into Ammonia recovery system, and esterifying agent and water are removed to the water that dereaction generates by dehumidification system, dried esterifying agent is back in reactor;
(4) after above-mentioned reaction finishes, the still bottom product in reactor is led to azeotropic and rise in rectifying tower, and add entrainer to distill, thereby obtain product succinate monoester,
Wherein, the concentration of described succinic acid two aqueous ammoniums is 10wt% to 90wt%, C1～C6 alkyl alcohol that described esterifying agent is straight or branched, and described entrainer is ethyl acetate.
2. method according to claim 1, wherein, described esterifying agent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol or the trimethyl carbinol.
3. method according to claim 1, wherein, described esterifying agent is methyl alcohol, described succinate monoester is monomethyl succinate.
4. method according to claim 1, the concentration of wherein said succinic acid two aqueous ammoniums is 10wt% to 70wt%.
5. method according to claim 1, wherein, the temperature of reaction of described step (2) is 70 ℃～75 ℃.
6. method according to claim 1, wherein, the reaction times of described step (2) is 8～10 hours.
7. method according to claim 1, the concentration of wherein said succinic acid two aqueous ammoniums is 40wt% to 70wt%.
8. method according to claim 1, wherein, the temperature of reaction of described step (2) is 75 ℃.
9. method according to claim 1, wherein, the reaction times of described step (2) is 10 hours.
10. method according to claim 1, wherein, the reflux ratio in described step (4) is 0.5-3, and tower top temperature is 68-70 ℃, and column bottom temperature is 90-100 ℃.
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| US6583310B1 (en) * | 2002-02-22 | 2003-06-24 | The United States Of America As Represented By The United States Department Of Energy | Direct esterification of ammonium salts of carboxylic acids |
| CN1520392A (en) * | 2001-05-07 | 2004-08-11 | μ | Process for preparing carboxylic acids and derivatives thereof |
| CN101223126A (en) * | 2005-07-27 | 2008-07-16 | 丰田自动车株式会社 | Method for preparing lactate |
| CA2625511A1 (en) * | 2008-03-13 | 2009-09-13 | Dilum Dunuwila | Process for the direct production of esters of carboxylic acids from fermentation broths |
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2012
- 2012-07-19 CN CN201210252021.3A patent/CN102746149B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1520392A (en) * | 2001-05-07 | 2004-08-11 | μ | Process for preparing carboxylic acids and derivatives thereof |
| US6583310B1 (en) * | 2002-02-22 | 2003-06-24 | The United States Of America As Represented By The United States Department Of Energy | Direct esterification of ammonium salts of carboxylic acids |
| CN101223126A (en) * | 2005-07-27 | 2008-07-16 | 丰田自动车株式会社 | Method for preparing lactate |
| CA2625511A1 (en) * | 2008-03-13 | 2009-09-13 | Dilum Dunuwila | Process for the direct production of esters of carboxylic acids from fermentation broths |
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