CN1225919A - Synthesizing method for dimethyl ester of mixed acid of butane diacid, glutaric acid and hexane diacid - Google Patents
Synthesizing method for dimethyl ester of mixed acid of butane diacid, glutaric acid and hexane diacid Download PDFInfo
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- CN1225919A CN1225919A CN 98123245 CN98123245A CN1225919A CN 1225919 A CN1225919 A CN 1225919A CN 98123245 CN98123245 CN 98123245 CN 98123245 A CN98123245 A CN 98123245A CN 1225919 A CN1225919 A CN 1225919A
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Abstract
The method for preparing dimethyl ester by using direct esterification of AGS acid mixture (A is oxalic acid, G is glutaric acid and S is adipic acid) and methyl alcohol is characterized by adding 0.5-2.5g stannous oxide or stannous chloride in per mol AGS or adding 3.0-8.0 strong acid type cation exchange resin as catalyst, making them produce reaction for 3-4 hr at 120-150 deg.C and 0.3-1.0 MPa, then taking out 200-220 deg.C fraction and dimethyl ester product. Said method possesses the advantages of high yield of dimethyl ester and good product quality, and is extensively used in the fields of chemical industry, specially applicable to recovery and utilization of AGS acid as additional product produced by using cyclohexane to prepare cyclohexanone and cyclohexanol
Description
The present invention relates to a kind of synthetic method of AGS dimethyl phthalate, especially relate to a kind of method that contains the cyclohexane oxidation by product of hexanodioic acid (Adipic acid), pentanedioic acid (Glutaric acid) and Succinic Acid (Succinic acid) mixture with the synthetic AGS dimethyl phthalate of methyl alcohol direct esterification.
In the prior art, in the technological process with cyclohexane oxidation preparing cyclohexanone, hexalin, can produce a large amount of by products, its major ingredient is AGS acid, it generally contains hexanodioic acid (A) 40%～60%, pentanedioic acid (G) 20%～30%, Succinic Acid (S) 10%～20%, also contain a spot of hydroxycaproic acid, valeric acid, butyric acid and caproic acid etc., AGS acid in the past is sent to waste disposal plant mostly and burns.In recent years, the synthetic method of dibasic acid dimethyl ester generally is to make with methanol esterification under the sulphuric acid catalysis effect with diprotic acid, and this method has problems such as etching apparatus, aftertreatment difficulty and contaminate environment.Independent method with the hexanodioic acid Dimethyl Adipate Catalyzed is also arranged in the prior art, " ion-exchange and absorption " magazine (1995,11 (6), 550～553) a kind of Zeo-karb D72 that uses is disclosed, the method of D61 and HZSM-5 sieve peg-raking catalyst synthesizing adipic acid diformazan (second) ester, its ester yield is lower, only reaches about 90%." fine chemistry industry " (1996, VB (2), 44～46) disclose the synthetic C of a kind of solid acid H catalysis
4～6The synthetic method of mixed dibasic acid dimethyl ester is the method that adopts the synthetic AGS dimethyl phthalate of methanol esterification AGS acid, carries out normal pressure esterification, though its dibasic acid dimethyl ester transformation efficiency can reach more than 96%, its esterification time is longer, generally needed 5 hours or more than.
The object of the present invention is to provide a kind of synthetic method of AGS dimethyl phthalate, be convenient to reclaim the by product AGS acid of cyclohexane oxidation preparing cyclohexanone and hexalin, with convenient environment protection and quicken fat speed, improve the utility value of by product.
The objective of the invention is to realize by the following technical solutions, with containing hexanodioic acid, raw material is made in the mixture AGS acid of pentanedioic acid and Succinic Acid arbitrary proportion, the mixture as catalyst that adds a kind of or its arbitrary proportion of 0.5～2.0g tin protoxide or tin protoxide by every molAGS acid (in pentanedioic acid), or add 3.0～8.0g strongly acidic cation-exchange and make catalyzer, reach at 120～150 ℃ and (react 3～4 hours under 1.3～1.0MPa pressure to acid number≤1mgKOH/g stopped reaction, unreacted methanol and the water mixture that is generated 5A molecular sieve or anhydrous MgSO with q.s after condensation
4Adsorption dewatering, methanol loop use, and reaction solution is after filtration, deionized water washing, oil reservoir be through distillation, gets 200～220 ℃ of fractions, the product dimethyl ester.
In implementing process of the present invention, should be noted that stannous oxide catalyst or tin protochloride or described exchange resin add-on will be suitably, when its add-on is too high, then production cost height, waste are big, therefore there is no need to add this class catalyzer too much, but when its add-on is very few, reactive behavior is poor, speed of response is slow, long reaction time, usually, every molAGS acid adds 0.5～2.0g tin protoxide or tin protochloride, or add 3.0～8.0g strongly acidic cation-exchange and make catalyzer, its amount is comparatively suitable.
In implementing process of the present invention, it is also noted that by reaction pressure and come control reaction temperature that when reaction pressure raise, then the methyl alcohol boiling point increased, the corresponding raising of esterification temperature, speed of response quickening; Cross when low when reaction pressure, then esterification temperature is low, and speed of response is slow, has prolonged the production cycle, influences throughput.Therefore, reaction pressure is controlled at 0.3～1.0MPa, and its relevant temperature is 120～150 ℃, and the reaction times, its esterification acid number can reach below the 1mg/gKOH generally at 3～4 hours.
In implementing process of the present invention, to notice that also dewatering agent 5A molecular sieve or anhydrous magnesium sulfate consumption want enough, if need not or its use quantity not sufficient, then the water of reaction generation takes off endless, is unfavorable for the carrying out of esterification, its esterification yield is on the low side.
The present invention's technical scheme preferably is: adopt the accessory substance AGS acid of cyclohexane oxidation system cyclohexanone or hexalin to synthesize dimethyl ester for raw material, this raw material mainly contains hexanodioic acid (A), pentanedioic acid (G) and Succinic Acid (S), contain a spot of hydroxyl organic acids such as acid, valeric acid, butyric acid, caproic acid simultaneously, prepare dimethyl ester by aforesaid optimization reaction conditions and method and methyl alcohol direct esterification, can reach splendid effect, its esterification yield can reach more than 98%.
Compared with prior art, the present invention has following tangible advantage:
1, the invention provides the recoverying and utilizing method for preparing the accessory substance AGS acid of pimelinketone and hexalin with cyclohexane oxidation, reclaimed all diprotic acid, both protected environment, also improved economic benefit.
2, the present invention has adopted the reaction pressure of 0.3～1.0MPa and has adopted the adsorption method dehydration, improved the transformation efficiency of reaction, its esterification yield reaches more than 98%, and esterification is foreshortened to 3～4 hours by about 8 hours of prior art, thereby recovering effect is good and the reaction times short.
3, the present invention adopts 5A molecular sieve and anhydrous magnesium sulfate, the water that generates in the reaction can be separated effectively, has promoted the synthetic of ester, and product dimethyl ester quality height, its acid number are below 1mgKOH/g, and its product industrial application is wide.
Below be embodiments of the invention:
Example 1 is got 1.0molAGS acid (molecular weight is 132), adds the 3.0mol anhydrous methanol, and adds the 1.0gSnO catalyzer in autoclave pressure, uses N
2Behind the air still is sealed close in the displacement still, restir, heat temperature raising to pressure is 0.5MPa, regulates heater voltage and keeps the still temperature at 120～150 ℃, and pressure-stabilisation is at 0.3～1.0MPa, reflux, emit the methanol-water mixed solution from water trap, dewater with the 5A molecular sieve adsorption of q.s, methanol eddy is to reactor, reacted 4 hours, cooling, reaction solution is emitted in release, dioctyl phthalate washs once with the aqueous sodium carbonate of 2% concentration, with the deionized water washing, then the dimethyl ester oil reservoir is distilled in still kettle again, get 200～220 ℃ of fractions and get product, calculate through weighing, AAGS dimethyl phthalate yield is 97.8%.
Example 2～9
AGS acid is the accessory substance of cyclohexane oxidation system cyclohexanone and hexanaphthene, its main component is a hexanodioic acid (A) 40%～60%, pentanedioic acid (G) 20%～30%, Succinic Acid (S) 10%～20%, contain a small amount of other organic acid composition, reaction process be the preparation method with example 1, catalyzer and consumption see Table 1, dewatering agent sees Table 1, and technology controlling and process and dimethyl ester yield see Table 1.
Table 1 embodiment 1～11 technology controlling and process table look-up
Annotate: 732 resins are the strong acid ion exchange resin that Shanghai Resin Factory produces in the table, the large porous strong acid type ion exchange resin that example 9 used " macroporous cation " is produced for Tianjin Nankai University.
| Embodiment | Catalyzer | Processing condition | AAGS dimethyl phthalate transformation efficiency (%) | |||
| Title | Add (g) | Pressure MPa | Time (h) | Dewatering agent | ||
| 1 | ?SnO | ????2.0 | ????0.5 | ????4 | The 5A molecular sieve | ??97.8 |
| 2 | ?SnCL 2 | ????1.0 | ????0.3 | ????4 | Anhydrous MgSO 4 | ??96.8 |
| 3 | ?SnO | ????0.5 | ????1.0 | ????3 | The 5A molecular sieve | ??96.4 |
| 4 | ?SnO-SnCL 2 | ????1.0 | ????0.5 | ????4 | The 5A molecular sieve | ??97.1 |
| 5 | ?SnCL 2 | ????1.0 | ????0.5 | ????4 | The 5A molecular sieve | ??95.4 |
| 6 | ?SnCL 2 | ????1.0 | ????1.0 | ????4 | The 5A molecular sieve | ??96.1 |
| 7 | 732 resins | ????3.0 | ????0.5 | ????3 | The 5A molecular sieve | ??93.7 |
| 8 | 732 resins | ????8.0 | ????0.5 | ????4 | The 5A molecular sieve | ??95.2 |
| 9 | Macroporous cation | ????6.0 | ????1.0 | ????4 | The 5A molecular sieve | ??98.2 |
Claims (2)
1, a kind of synthetic method of AGS dimethyl phthalate, use hexanodioic acid, the mixture of pentanedioic acid and Succinic Acid arbitrary proportion is made raw material, under the effect of heating and catalyzer, directly carry out esterification and make dimethyl ester with methyl alcohol, the invention is characterized in: with AGS acid is raw material, the mixture as catalyst that adds a kind of or its arbitrary proportion of 0.5～2.0g tin protoxide or tin protoxide by every molAGS acid (in pentanedioic acid), or add 3.0～8.0g strongly acidic cation-exchange and make catalyzer, under 120～150 ℃ and 0.3～1.0MPa pressure, react 3～4 hours to acid number≤1mgKOH/g stopped reaction, unreacted methanol and the water mixture that generated after condensation with the 5A molecular sieve or the anhydrous MgSO of q.s
4Adsorption dewatering, methanol loop use, and reaction solution is after filtration, deionized water washing, oil reservoir be through distillation, gets 200～220 ℃ of fractions, the product dimethyl ester.
2, synthetic method according to claim 1 is characterized in that: the by product AGS acid of adopting cyclohexane oxidation preparing cyclohexanone and hexalin mainly contains hexanodioic acid, pentanedioic acid and Succinic Acid for raw material in the by product, contain other organic acid composition simultaneously.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 98123245 CN1225919A (en) | 1998-12-02 | 1998-12-02 | Synthesizing method for dimethyl ester of mixed acid of butane diacid, glutaric acid and hexane diacid |
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| CN 98123245 CN1225919A (en) | 1998-12-02 | 1998-12-02 | Synthesizing method for dimethyl ester of mixed acid of butane diacid, glutaric acid and hexane diacid |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735049A (en) * | 2009-12-18 | 2010-06-16 | 沈阳工业大学 | Method and equipment for producing C4-C6 diacid low-carbon alcohol ester |
| CN101265184B (en) * | 2007-03-12 | 2010-09-01 | 中国石油天然气股份有限公司 | Method for preparing dibasic acid ester |
| CN102432460A (en) * | 2011-10-12 | 2012-05-02 | 潍坊市元利化工有限公司 | Method for purifying diacid dimethyl esters by plate distillation separation |
| CN105884611A (en) * | 2016-05-26 | 2016-08-24 | 西南大学 | Circular reaction water phase organic acid esterifying device and organic acid esterifying method thereof |
| CN106045856A (en) * | 2016-05-26 | 2016-10-26 | 西南大学 | Method for directly esterifying malic acid aqueous solution to produce malate |
| CN110563579A (en) * | 2019-09-23 | 2019-12-13 | 上海申越生物科技有限公司 | Preparation method of dimethyl nylon acid |
| CN110862333A (en) * | 2019-11-29 | 2020-03-06 | 万华化学集团股份有限公司 | Mixed dibasic acid dihydrazide and preparation method and application thereof |
| CN112121817A (en) * | 2020-09-22 | 2020-12-25 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
| CN115322090A (en) * | 2022-07-16 | 2022-11-11 | 江西益普生药业有限公司 | Method for preparing ethyl oleate |
-
1998
- 1998-12-02 CN CN 98123245 patent/CN1225919A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265184B (en) * | 2007-03-12 | 2010-09-01 | 中国石油天然气股份有限公司 | Method for preparing dibasic acid ester |
| CN101735049A (en) * | 2009-12-18 | 2010-06-16 | 沈阳工业大学 | Method and equipment for producing C4-C6 diacid low-carbon alcohol ester |
| CN101735049B (en) * | 2009-12-18 | 2013-04-24 | 沈阳工业大学 | Method and equipment for producing C4-C6 diacid low-carbon alcohol ester |
| CN102432460A (en) * | 2011-10-12 | 2012-05-02 | 潍坊市元利化工有限公司 | Method for purifying diacid dimethyl esters by plate distillation separation |
| CN102432460B (en) * | 2011-10-12 | 2014-01-08 | 山东元利科技股份有限公司 | Method for purifying diacid dimethyl esters by plate distillation separation |
| CN106045856A (en) * | 2016-05-26 | 2016-10-26 | 西南大学 | Method for directly esterifying malic acid aqueous solution to produce malate |
| CN105884611A (en) * | 2016-05-26 | 2016-08-24 | 西南大学 | Circular reaction water phase organic acid esterifying device and organic acid esterifying method thereof |
| CN106045856B (en) * | 2016-05-26 | 2019-04-30 | 西南大学 | The method of aqueous solution of malic acid direct esterification production malate |
| CN110563579A (en) * | 2019-09-23 | 2019-12-13 | 上海申越生物科技有限公司 | Preparation method of dimethyl nylon acid |
| CN110862333A (en) * | 2019-11-29 | 2020-03-06 | 万华化学集团股份有限公司 | Mixed dibasic acid dihydrazide and preparation method and application thereof |
| CN110862333B (en) * | 2019-11-29 | 2022-11-08 | 万华化学集团股份有限公司 | Mixed dibasic acid dihydrazide and preparation method and application thereof |
| CN112121817A (en) * | 2020-09-22 | 2020-12-25 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
| CN112121817B (en) * | 2020-09-22 | 2022-04-26 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
| CN115322090A (en) * | 2022-07-16 | 2022-11-11 | 江西益普生药业有限公司 | Method for preparing ethyl oleate |
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