CN105837436A - Method for synthesizing hydroxyacetate through reactive rectification catalyzed by solid acid - Google Patents
Method for synthesizing hydroxyacetate through reactive rectification catalyzed by solid acid Download PDFInfo
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Abstract
A synthetic method for producing hydroxyacetate comprises: taking glycolic acid and alkanol as raw materials, taking 732-type and D001-type cation exchange resins as a solid acid catalyst, and using a reactive rectification column consisting of a rectification section, a stripping section, and a middle multi-kettle gas-liquid phase in sequence for continuous preparation of hydroxyacetate. The conversion rate and yield in an esterification process of hydroxyacetate is improved through controlling technical operation conditions, such as the mass ratio of glycolic acid to alkanol, the reaction temperature, and the consumption of the catalyst, in feeding. In a reactive rectification device, the operation conditions are that the mass ratio of alkanol to glycolic acid is 5:1, and each reactor has the reaction temperature being 70-80 DEG C, the column temperature being 90-110 DEG C, and the column top reflux ration being 0.3-0.5. The esterification conversion rate (based on hydroxyacetate) can reach more than 91%, and the yield of hydroxyacetate can normally reach more than 90%. Compared with a batch tank stirring esterification device in the prior art, the device in the method has large processing capacity and operational convenience, and is suitable for massive industrial production.
Description
Technical field
The present invention relates to the synthetic method of a kind of glycolic acid esters, with alkane chain alcohol and hydroxyacetic acid as raw material, under the catalytic action of the cation exchange resiies such as 732 types, D001 type, the method of continuous reaction rectification synthesis of hydroxy acetas in board-like (or filler) tower section with the reactive distillation equipment of many stills liquid phase tandem reactor composition, this area belongs to reactive distillation and separates and technical field.
Background technology
Glycolic acid esters, including hydroxy methyl acetate, hydroxyl ethyl acetate, hydroxyacetic acid (different) propyl ester, Butyl Glycolate etc., they have important application in fine synthesis field.Such as hydroxy methyl acetate, also known as hydroxacetic acid methyl ester, glycolic acid methyl ester etc., has that corrosivity is low, volatility is low, it is inflammable to be difficult to, odorless, hypotoxicity, Biodegradable are strong, metal-chelating is good, water solublity advantages of higher；The molecular structure of glycolic acid esters is more special simultaneously, has more functional group, such as the α-H contained, there is faintly acid, substitution reaction, hydroxy functional group-OH can occur in the basic conditions, can occur to replace the multiple reactions such as addition cancellation, be important organic synthesis intermediate.Additionally, glycolic acid esters also has an ester functional groups-COO (CH2)xCH3, (x=0,1,2,3 ...), the most easily hydrolyze, it also occur that alcoholysis (or ester exchange) reaction generates other Ester in the presence of having alcohols.Multiple functional group just because of yl acetate, make it have more active chemical property, it is susceptible to various chemical reaction and makes it have use value widely, particularly at anticancer aspect, can be used to synthesize cancer therapy drug, such as the synthesis of isoharringtonin He its derivant, they have the strongest curative effect in terms of leukemia.In addition, glycolic acid esters is also widely used at other medicine intermediates, industrial chemicals, lubricant, dyestuff, the aspect such as pesticide.Hydroxyacetic acid esters can be with synthesizing glycol under hydroconversion condition, and ethylene glycol is a kind of conventional organic solvent, can be used to prepare polyester, hygroscopic agent, plasticizer etc., is also a kind of chemical substance indispensable in cosmetics.Under heating state, hydroxyacetic acid esters material can occur hydrolysis, generates hydroxyacetic acid and corresponding alkanol.Hydroxyacetic acid can also generate Acetic acid, hydroxy-, bimol. cyclic ester under heating, and then can manufacture polyglycolic acid by autohemagglutination.Polyglycolic acid is the good macromolecular material of biocompatibility, in biomedicine, can be used to make medical degradable material, such as without the medical operation suture thread of dismounting, fracture fixator etc..Hydroxyacetic acid esters material also ammonolysis can prepare glycine.Glycine is a kind of aminoacid necessary to human body, can be used not only as food flavor, stabilizer, moreover it is possible to deliver to human body as nutrient input；And glycine is also one of important source material producing herbicide glyphosate.
Currently, the synthetic method of hydroxyacetic acid esters material has:
1. the neutralization esterification process with halogenated acetic acids as raw material.Such as Chinese patent CN89105014.0(1989) in monoxone through in sodium carbonate and after obtain hydroxyacetic acid, then with ethanol concentrated sulphuric acid be catalyst, benzene or chloroform etc. for azeotropic azeotropic agent effect under carry out esterification, generate hydroxyl ethyl acetate.
2. the direct esterification as raw material with hydroxyacetic acid and alcohol.As Chen Dongliang [gas chemical industry, 2005,25 (5): 5-7] withFor catalyst, carrying out hydroxyacetic acid and methanol-fueled CLC hydroxy methyl acetate, be 5:1 at molar ratio of alcohol to acid in the four-hole boiling flask of laboratory belt stirring, under conditions of reaction 6h, the yield of hydroxy methyl acetate is up to 89.5%.
3. it is that raw material synthesizes hydroxy methyl acetate/methoxy menthyl acetate through carbonylation under elevated pressure with methyl formate etc. and formaldehyde (or metaformaldehyde, paraformaldehyde).Such as Chinese patent CN97107692.8(1997) with methyl formate and formaldehyde as raw material, with sulphuric acid carbonyl compound as catalyst, carry out coupling and alcoholysis reaction, separated after obtain hydroxy methyl acetate.Chinese patent CN97112201.6(1997), CN200510021146.5(2005), CN200610022389.5(2006) the most respectively with heteropoly acid etc., sulfamic acid, p-methyl benzenesulfonic acid/metal halide as catalyst, many (or three) polyformaldehyde and methanol are synthesized hydroxy methyl acetate and methoxy menthyl acetate.United States Patent (USP) US4824997(1989) report is with formaldehyde, carbon monoxide, hydrogen and methanol as raw material, and under the catalyst action that sulphuric acid and subgroup IB metallic compound form, synthesis obtains hydroxy acid and methyl ester thereof.United States Patent (USP) US6376723(2002) it is reported in homogeneously or under heterogeneous acid catalyst effect, with formaldehyde, hydrogen and carbon monoxide as raw material, can synthesize through carbonylation and obtain hydroxy acid and ester type compound thereof.United States Patent (USP) US4602102(1986) report with formaldehyde and dimethoxymethane as raw material, can synthesis of hydroxy methyl acetate or ethyl ester through carbonylation.
4. with coal based synthetic gas as raw material, the intermediate product hydroxy methyl acetate of synthesizing glycol, i.e. obtain ethylene glycol after its hydrogenation.Chinese patent CN200910061855.4(2009) in synthesis, use double kind catalyst Pd/ α-Al2O3And Cu-SiO2 /Or Cu-Cr2O3Or on Cu-Zn-Al methanol synthesis catalyst, CO, hydrogen, methanol, oxygen and nitric oxide carry out nitrosation reaction respectively, carbonylation, hydrogenation reaction, rectification separate etc., and step obtains hydroxy methyl acetate and ethylene glycol, wherein CO and the conversion ratio of hydrogen and selectivity can respectively reach 99.9% and more than 98%.
5. with dimethyl oxalate. as raw material, hydrogenated catalytic reaction obtains glycolic acid esters.United States Patent (USP) US4440873(1984), US4585890(1986) respectively report employing SiO2The metallic copper catalyst of load prepares glycolic acid esters and ethylene glycol.United States Patent (USP) US5455372(1995) with SiO2The Ni metal of even load, Ag or Cu-Cr are catalyst, and Hydrogenation of Dimethyl Oxalate can get glycolic acid esters or ethylene glycol.
6. the esterification process of formaldehyde hydrocyanic acid addition product hydroxyacetonitrile hydrolyzed solution.The additive reaction under low temperature and catalyst action of formaldehyde and hydrocyanic acid generates hydroxyacetonitrile, and then hydroxyacetonitrile hydrolysis under sulphuric acid/or phosphoric acid etc. act on generates hydroxyacetic acid and ammonium sulfate/ammonium phosphate；With alkane chain alcohol as solvent, rapidly and efficiently separating of hydroxyacetic acid and ammonium sulfate/or ammonium phosphate can be realized, preferably solving the problem that hydroxyacetonitrile acid hydrolysis liquid is difficult to separate, this is at Chinese patent CN200910048806.7(2009) in done detailed report.With this alcohol analysis liquid as raw material, under acidic catalyst effect, carry out esterification, corresponding hydroxyacetic acid esters material can be prepared.
In the preparation method of above glycolic acid esters, method 1. because of use halogenated acetic acids be raw material, the product of gained contains a certain amount of halogen species more or less, such as chloride ion, limits the application scenario of its follow-up product hydroxy acetic acid.Employing method 3. methyl formate and formaldehyde are the hydrogenation reaction of raw material, because using highly acid homogeneous or heterogeneous catalysis, building-up process is typically carried out under higher temperature (usual 100 ~ 120 DEG C), higher pressure (1.0MPa ~ 50.0MPa), strong to the corrosivity of consersion unit, require height, the conversion ratio of raw material is not the highest with the selectivity of purpose product.Method 4. with method 5. in raw material or product hydroxy acetas essence be the intermediate product that synthesis gas prepares ethylene glycol, the purification process of synthetic raw gas and equipment are complicated, and technological process is long, limits application and the development of this method to a certain extent.Method defect 2. is that sterling hydroxyacetic acid source is less, and the conversion ratio of one way esterification is not the highest.
Summary of the invention
It is an object of the invention to utilize catalytic reaction rectification technology, for the alcohol analysis liquid obtained after the hydrolyzed solution separation of hydroxyacetonitrile, in the reactive distillation equipment being made up of board-like tower section (or packing tower section) and multiple phase cascade reaction stills, alcohol is analysed liquid be esterified, obtain pure hydroxyacetic acid esters material, highly purified hydroxyacetic acid can be prepared after its hydrolysis, provide raw material sources and technical method for being further processed into its dimer (Acetic acid, hydroxy-, bimol. cyclic ester).
Accompanying drawing illustrates:
Accompanying drawing, solid superacid as catalyst reaction and rectification device sketch
In figure, 1-tower reactor (four-hole boiling flask)；2-electric heating cover；3-tower reactor discharging storage bottle；4-tower reactor feed liquid discharging cooler；5-mercurial thermometer；6,17-sieve plate distillation column section；The most super constant temperature water bath groove；8,9,10,11,12-150mL jacketed kettle reactor；Water knockout drum/discharging opening between 13-tower；Discharging storage tank in the middle part of 14-tower；15-tower top material liquid feed storage tank；16-tower top charging dosing pump；18-overhead condenser；19-reflux ratio regulation controller；20-tower top discharge collector；20-tower lower feed liquid feed storage tank；16-tower bottom charging dosing pump；23-input and output material regulation cock.
The technical solution of the present invention is as follows:
Reaction of the present invention is to be carried out continuously in the reactive distillation equipment that board-like tower section (or packing tower section) and reactor are connected, see accompanying drawing, wherein the tower body temperature of this tower is by circulating water temperature control, generally at 75-80 DEG C, alkane chain alcohol and hydroxyacetic acid mol ratio 5:1 in alcohol analysis liquid, inlet amount 2mL/min, catalyst is 732 types, 201 type cation exchange resiies etc., useful load therein is the 5% ~ 50% of reactor volume, preferably 20% ~ 30%.
It is characteristic of the invention that the reactive distillation device structure of use is novel, continuous operation, can apply to large-scale production.Catalyst uses the catalyst such as 732 types, D001 type cation exchange resin, easily separates with product, and little to the corrosivity of equipment, the conversion ratio (in terms of hydroxyacetic acid) of process and the yield of glycolic acid esters are the highest.
Detailed description of the invention
Hydroxyacetic acid conversion ratio and the yield of glycolic acid esters defined in following example are respectively as follows:
Gas chromatographic analysis methanol and the condition of moisture: chromatograph GC1102 (Shanghai analytical tool factory)；Chromatographic column is Φ 3mm × stainless steel column of 2m, interior filling 60 ~ 80 mesh 401 organic white silanization monomer, aging 24h at 250 DEG C in advance；Detector is conductance cell (TCD), bridge electric current 150mA；Carrier gas H2, flow 30mL/min；Furnace temperature 70 DEG C；Temperature of vaporization chamber 160 DEG C.
The analysis method of glycolic acid esters in esterifying liquid: use saponification method analyze glycolic acid esters concentration [Chen Shuanli etc. the iodine number of edible oil, acid number, the mensuration of saponification number and health assessment. Liaoning chemical industry. 2011, (5): 2 ~ 4.].
Embodiment 1
The pure methanol solution of 500mL is added in 1000mL tower reactor (four-hole boiling flask 1), 100mL hydroxyacetic acid methanol alcohol analysis liquid it is separately added in the jacketed reactor (8,9,10,11,12) of 5 150mL, wherein methanol/glycolic acid molar ratio example is 5:1, then is separately added into treated and dried 732 type cation exchange resiies (processing method can be found in the conventional acid alkali treatment method that ion exchange resin is general) 50g in 5 reactors as solid acid catalyst.Open the condensed water valve of overhead condenser 18, be passed through cooling water；Open tower reactor electric jacket 2 heating power supply, carry out tower reactor 1 feed liquid and heat up；Opening super constant temperature water bath groove 7 power supply to heat, conciliation water bath temperature is the most constant at about 80 DEG C.Can first make in experiment about whole reactive distillation column intermittent reaction 3h, overhead reflux is than the reflux ratio distributor regulation controlled by electromagnetic valve 19, and the present embodiment 1 is set as 0.3.The aqueous methanol on tower top is by water knockout drum between tower 13 and discharging opening 23 extraction, and is stored in discharging storage bottle 14, and water content therein can be detected by gas chromatograph or karl Fischer moisture test apparatus.Overhead condensation liquid is substantially pure methanol through gas chromatographic analysis, tower top discharging is collected in catcher 20, can directly return tower reactor 1 continue to use as feedstock circulation by opening cock, the fresh methanol supplemented can be fed dosing pump 22 above the stripping section of tower charging aperture entrance tower by methanol storage tank 21.
After question response carries out 3h, the operation of whole reactive distillation column is the most stable, now opens alcohol analysis liquid dosing pump 16, with the speed of 2mL/min between tower below water knockout drum 13 charging aperture alcohol analysed liquid pump enter rectifying column.Treating that tower bottoms meets or exceeds 2/3 position of its cubical content, slowly open tower reactor discharging cock, feed liquid is collected in still liquid storage bottle 3 after tower reactor cooler 4 cools down；Needing to keep tower reactor liquid level stabilizing in whole experimentation, still Wen Yi maintains 85 DEG C ~ 90 DEG C simultaneously, and water knockout drum 13 feed liquid carries out gas chromatographic analysis every between 30min extraction tower bottoms and tower.Reactive distillation column is hydroxyacetic acid content 3.85mol/L, molar ratio of alcohol to acid 5: 1, reflux ratio 0.3 in alcohol analysis liquid initial charge, and in reaching the 5h after stable operation during inlet amount 2mL/min, continuous experimental result is listed in embodiment 1 subordinate list 1.
Embodiment 1 table 1, reactive distillation column reach continuous experimental result * of 5h after stable operation
* steady state operation: hydroxyacetic acid content 3.85mol/L, molar ratio of alcohol to acid 5: 1, reflux ratio 0.3, inlet amount 2mL/min in initial charge
After reaction terminates, feed liquid total feed is 600mL, wherein quality 175.8g of hydroxyl acetic acid.Tower reactor total load 522.4g(volume 481mL), wherein contain hydroxyacetic acid 0.2106mol/L, hydroxy methyl acetate 4.543mol/L, can be calculated the conversion ratio of hydroxyacetic acid for 95.62% with this, the yield of hydroxy methyl acetate is 94.48%.
Through distillation and tower kettle product is collected the fraction of 150 DEG C, and available pure hydroxy methyl acetate, is 1.165g/L through density bottle its density of method Accurate Determining, with literature value 1.167g/L numerical value closely.
Embodiment 2
Experimental raw and experiment condition are same as in Example 1, and catalyst changes into D001 type cation exchange resin, and after reaction terminates, feed liquid total feed is 600mL, wherein quality 175.8g of hydroxyl acetic acid.Tower reactor total load 514.5g(volume 490mL), wherein contain hydroxyacetic acid 0.3677mol/L, hydroxy methyl acetate 4.227mol/L, can be calculated the conversion ratio of hydroxyacetic acid for 92.21% with this, the yield of hydroxy methyl acetate is 89.56%.
Embodiment 3
Used catalyst is 732 type cation exchange resiies, and experimental raw is alcohol chromatography liquid, and other experiment conditions are similar with embodiment 1, and after reaction terminates, feed liquid total feed is 600mL, wherein quality 163.2g of hydroxyl acetic acid.Tower reactor total load 520.8g(volume 496mL), wherein contain hydroxyacetic acid 0.2913mol/L, hydroxyl ethyl acetate 4.032mol/L, can be calculated the conversion ratio of hydroxyacetic acid for 93.27% with this, the yield of hydroxyl ethyl acetate is 93.15%.
Embodiment 4
Used catalyst is D001 type ion exchange resin, and experimental raw is alcohol chromatography liquid, and other experiment conditions are same as in Example 3, and after reaction terminates, feed liquid total feed is 600mL, wherein quality 163.2g of hydroxyl acetic acid.Tower reactor total load 530.3g(volume 505mL), wherein contain hydroxyacetic acid 0.3707mol/L, hydroxyl ethyl acetate 3.712mol/L, can be calculated the conversion ratio of hydroxyacetic acid for 91.28% with this, the yield of hydroxyl ethyl acetate is 87.31%.
Embodiment 5
Used catalyst is 732 type cation exchange resiies, and experimental raw is that liquid analysed by isopropanol alcohol, and other experiment conditions are similar with embodiment 1, and after reaction terminates, feed liquid total feed is 620mL, wherein quality 173.2g of hydroxyl acetic acid.Tower reactor total load 581.4g(volume 570mL), wherein contain hydroxyacetic acid 0.2823mol/L, hydroxyacetic acid isopropyl ester 3.669mol/L, can be calculated the conversion ratio of hydroxyacetic acid for 92.94% with this, the yield of hydroxyacetic acid isopropyl ester is 91.76%.
Embodiment 6
Used catalyst is D001 type ion exchange resin, and experimental raw is that liquid analysed by isopropanol alcohol, and other experiment conditions are same as in Example 5, and after reaction terminates, feed liquid total feed is 620mL, wherein quality 173. 2g of hydroxyl acetic acid.Tower reactor total load 598.7g(volume 587mL), wherein contain hydroxyacetic acid 0.3836mol/L, hydroxyacetic acid isopropyl ester 3.833mol/L, can be calculated the conversion ratio of hydroxyacetic acid for 90.12% with this, the yield of hydroxyacetic acid isopropyl ester is 89.72%.
Embodiment 7
Used catalyst is 732 type cation exchange resiies, and experimental raw is that liquid analysed by n-butyl alcohol alcohol, and other experiment conditions are similar with embodiment 1, and after reaction terminates, feed liquid total feed is 630mL, wherein quality 165.7g of hydroxyl acetic acid.Tower reactor total load 581.5g(volume 580mL), wherein contain hydroxyacetic acid 0.2326mol/L, hydroxyacetic acid N-butyl 3.460mol/L, can be calculated the conversion ratio of hydroxyacetic acid for 93.81% with this, the yield of hydroxyacetic acid N-butyl is 92.07%.
Embodiment 8
Used catalyst is D001 type ion exchange resin, and experimental raw is that liquid analysed by n-butyl alcohol alcohol, and other experiment conditions are same as in Example 7, and after reaction terminates, feed liquid total feed is 630mL, wherein quality 165.7g of hydroxyl acetic acid.Tower reactor total load 598.1g(volume 592mL), wherein contain hydroxyacetic acid 0.3600mol/L, hydroxyacetic acid N-butyl 3.283mol/L, can be calculated the conversion ratio of hydroxyacetic acid for 90.23% with this, the yield of hydroxyacetic acid N-butyl is 89.14%.
Claims (5)
1. the present invention relates to the synthetic method of a kind of glycolic acid esters, with alkane chain alcohol and hydroxyacetic acid as raw material, under the catalytic action of the cation exchange resiies such as 732 types, D001 type, the method for continuous synthesis glycolic acid esters ester in board-like (or filler) tower section with the reactive distillation equipment of many stills liquid phase tandem reactor composition.
2. catalyst described in claim 1, the predominantly solid acid catalysts such as cation exchange resin such as 732 types, D001 type, can use continuously in the esterification reaction, life-span is long, it separates easily with reaction raw materials and product, its useful load is 5% ~ 50% that each series connection kettle is long-pending, and preferred amounts is 20% ~ 30%, and tower reactor not loading catalyst.
3. the raw material alkane chain alcohol (referring mainly to methanol, dehydrated alcohol, propanol/isopropanol, butanol etc.) in claim 1 and hydroxyacetic acid, main source is hydroxyacetonitrile sulphuric acid/or other mineral acids (such as phosphoric acid, hydrochloric acid or nitric acid) hydrolysis afterproduct, the alcohol analysis liquid after dehydration, alkane chain alcohol washing removing by-product ammonium sulfate (or ammonium phosphate, ammonium chloride, ammonium nitrate etc.).
4. the continuous reaction rectification equipment in claim 1 is the reactive distillation column of board-like (or filler) tower section and the combination of many stills liquid phase tandem reactor, or the rectifying column of multistage bubble tower composition.
5. operating condition and the technological parameter of the continuous reaction rectification tower in claim 1 is: the ratio of the material amount of alkanol/hydroxyacetic acid is classified as 5:1, the reaction temperature of each tandem reactor is 70 ~ 80 DEG C, bottom temperature 90 ~ 110 DEG C, overhead reflux ratio about 0.1 ~ 1.0, it is preferably 0.3 ~ 0.5, operate with this understanding, reaction conversion ratio in terms of hydroxyacetic acid is up to more than 91%, and the yield of glycolic acid esters is generally up to more than 90%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109843848A (en) * | 2016-10-12 | 2019-06-04 | 巴斯夫欧洲公司 | The method for preparing hydroxy alkyl carboxylic acid's ester |
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| CN101851157A (en) * | 2009-04-03 | 2010-10-06 | 华东理工大学 | Method for preparing and purifying hydroxyacetic acid by using hydroxyacetonitrile as raw material |
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Patent Citations (2)
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| CN101851157A (en) * | 2009-04-03 | 2010-10-06 | 华东理工大学 | Method for preparing and purifying hydroxyacetic acid by using hydroxyacetonitrile as raw material |
| CN101735054A (en) * | 2009-12-17 | 2010-06-16 | 上海化学试剂研究所 | Method for preparing ethyl glycolate |
Non-Patent Citations (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109843848A (en) * | 2016-10-12 | 2019-06-04 | 巴斯夫欧洲公司 | The method for preparing hydroxy alkyl carboxylic acid's ester |
| CN109843848B (en) * | 2016-10-12 | 2023-02-28 | 巴斯夫欧洲公司 | Method for producing hydroxyalkyl carboxylic acid esters |
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Application publication date: 20160810 |