CN101973870B - Preparation of glycollic acid from oxalaldehyde by intramolecular disproportionation method - Google Patents
Preparation of glycollic acid from oxalaldehyde by intramolecular disproportionation method Download PDFInfo
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 28
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 27
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000001556 precipitation Methods 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 19
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- CHRHZFQUDFAQEQ-UHFFFAOYSA-L calcium;2-hydroxyacetate Chemical compound [Ca+2].OCC([O-])=O.OCC([O-])=O CHRHZFQUDFAQEQ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229940015043 glyoxal Drugs 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims abstract description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims abstract 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 77
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 235000011116 calcium hydroxide Nutrition 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229960004275 glycolic acid Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 210000003491 skin Anatomy 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
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- 210000002615 epidermis Anatomy 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- -1 hydrogen ion ion Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- JYVNDCLJHKQUHE-UHFFFAOYSA-N hydroxymethyl acetate Chemical compound CC(=O)OCO JYVNDCLJHKQUHE-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
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Abstract
本发明涉及一种乙二醛分子内歧化法制备羟基乙酸，包括有以下步骤：1）氢氧化钙溶液与乙二醛水溶液进行歧化反应，保温反应，得到悬浮态羟基乙酸钙沉淀混合物；2）硫酸酸析形成羟基乙酸及硫酸钙沉淀，过滤，滤液浓缩至无水分后再过滤；3）步骤2）的滤液加水稀释，加入醋酸钡或氢氧化钡彻底脱除SO4 2-离子，过滤去除硫酸钡沉淀和活性炭，滤液浓缩，即可得到羟基乙酸溶液。本发明的有益效果在于：1）环境污染少；2）在常温常压下进行歧化反应，对设备没有特殊要求，操作简单，副产物能够综合利用，可实现清洁生产；3）反应选择性高，产品杂质少，纯度高，为高纯羟基乙酸晶体的制备创造了便利条件。The invention relates to a glyoxal intramolecular disproportionation method for preparing glycolic acid, comprising the following steps: 1) disproportionation reaction of calcium hydroxide solution and glyoxal aqueous solution, heat preservation reaction, to obtain suspended calcium glycolate precipitation mixture; 2) Sulfuric acid is acidified to form glycolic acid and calcium sulfate precipitates, filtered, and the filtrate is concentrated until there is no water before filtering; 3) The filtrate in step 2) is diluted with water, and barium acetate or barium hydroxide is added to completely remove SO 4 2- ions, and filtered to remove Barium sulfate precipitation and activated carbon, and the filtrate is concentrated to obtain glycolic acid solution. The beneficial effects of the present invention are: 1) less environmental pollution; 2) the disproportionation reaction is carried out at normal temperature and pressure, there is no special requirement for equipment, the operation is simple, by-products can be comprehensively utilized, and clean production can be realized; 3) the reaction selectivity is high , the product has less impurities and high purity, which creates convenient conditions for the preparation of high-purity glycolic acid crystals.
Description
Technical field
The present invention relates to a kind of preparation method of oxyacetic acid, concrete is a kind of preparation method of glycollic acid from oxalaldehyde by intramolecular disproportionation.
Background technology
Oxyacetic acid (hydroxyacetic acid; Glycolic acid), claiming again oxyacetic acid or glycolic acid, is that molecular structure is the simplest
α-alcohol acid.Oxyacetic acid is widely used in the fields such as matting, daily-use chemical industry, biomedical material and sterilant.The hydroxyl and the carboxyl that contain simultaneously high reaction activity in the oxyacetic acid molecule, thereby have unique metal-chelating ability and effectively in and performance, and corrodibility is little, therefore industrial its aqueous solution of 70% commonly used is as the clean-out system of pipeline, boiler etc., to remove the precipitation of calcium, the formation of magnesium plasma; The oxyacetic acid good water solubility has strong perviousness, can pass stratum corneum and be absorbed by the skin, and promotes the metabolism of epidermis, eliminates wrinkle of skin, since the nineties in 20th century,
α-alcohol acid becomes the choosing of the certainty of high-grade special cosmetics additive; Self-polymeric reaction can occur in oxyacetic acid, and the polyglycolic acid that obtains (PGA) has excellent biodegradability and biocompatibility, is to study so far one of the most extensive, that application is maximum Biodegradable material.
At present, the company that produces in the world oxyacetic acid mainly contains du pont company, Union Carbide Corporation, Japanese ball and company and German He Kete company etc., and the domestic enterprise that there is no scale operation.Because oxyacetic acid is of many uses, the market potential demand is large, and the main dependence on import of domestic oxyacetic acid and related products thereof, therefore the national Tenth Five-year plan was once classified oxyacetic acid one of as anxious main foundation Chemicals leaved for development.
The main production method of oxyacetic acid has: (1) cyanide process.Take formaldehyde and prussic acid as raw material, through nucleophilic addition(Adn) synthesis of hydroxy acetonitrile, be hydrolyzed again to get oxyacetic acid, also having device to adopt sodium cyanide instead of hydrogen cyanic acid is raw material.This method Technology is simple, stable operation, and output and quality is better, but owing to use the prussiate of severe toxicity, environmental pollution and safe pressure are larger.(2) formaldehyde carbonylation method.Take formaldehyde, carbon monoxide and water as raw material, reaction obtains oxyacetic acid in the presence of high temperature, high pressure and an acidic catalyst, and yield is about 90%, and wherein an acidic catalyst is sulfuric acid, hydrochloric acid or phosphoric acid.This raw materials technology cost is low, but technical difficulty is large, and one-time investment is large, and equipment need bear the pressure of 30.4-91.2MPa, and this is present external topmost industrial method.(3) Mono Chloro Acetic Acid hydrolysis method.Mono Chloro Acetic Acid and sodium hydroxide react in the presence of methyl alcohol and obtain hydroxy methyl acetate, and then hydrolysis obtains oxyacetic acid.This is domestic traditional production technique, because inefficiency only is suitable for small-scale production, there is heavy corrosion in the simultaneously existence of chlorion to production unit.
Although oxyacetic acid has multiple synthesis technique, no matter the difficult problem that improves of the product purity which kind of technique all exists negative ion impurity difficulty to remove causes.Commercially pure oxyacetic acid product generally is its aqueous solution of 70%, and temperature just can cause oxyacetic acid decomposition dehydration autohemagglutination more than 80 ℃, and the methods such as concentrate drying by routine are difficult to obtain high purity hydroxyl acetic acid crystal like this.Therefore purity and crystal refining technology have consisted of the core link of weighing oxyacetic acid production level height.
Liao Chuanping once reported under the sodium hydroxide katalysis, and through the novel method of Cannizzaro reaction synthesis of hydroxy acetic acid [synthetic chemistry, 2008,16(4): 470-471], but this technique both needed to react at low temperatures from oxalic dialdehyde, and high temperature is concentrated again; Need simultaneously to process metallic cation with strong-acid ion exchange resin, technological process is loaded down with trivial details, and production cost is high, through repeatedly repeated experiments detection discovery by product is many, product purity is low.
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of preparation method of glycollic acid from oxalaldehyde by intramolecular disproportionation for above-mentioned the deficiencies in the prior art, and this technological process is simple, and production cost is low, and by product is few, and product purity is high.
The present invention is that the technical scheme that the problem of the above-mentioned proposition of solution adopts is: preparation method of glycollic acid from oxalaldehyde by intramolecular disproportionation is characterized in that including following steps:
1) adopting calcium hydroxide is disproportionation catalyst, is configured to aqua calcis, then drips mass concentration and is 40% glyoxal water solution and carry out disproportionation reaction, is added dropwise to complete follow-up continuation of insurance temperature and reacts 0.5-1 hour, obtains suspended state Calcium Glycolate precipitation mixture;
2) directly add in the step 1) gained precipitation mixture with the vitriol oil acid out of the mole number such as calcium hydroxide or with precipitation mixture and filter first, it is 50% sulfuric acid acid out that the gained throw out is used the mass concentration with mole numbers such as calcium hydroxides, all form oxyacetic acid and calcium sulfate precipitation, filter, filtrate is elementary oxyacetic acid solution, filtrate is concentrated into without refiltering behind the moisture, to remove a small amount of calcium sulfate of dissolved in filtrate;
3) the filtrate thin up that step 2) obtains behind the filtering calcium sulfate to the mass concentration of oxyacetic acid is 5-15%, adds barium acetate or hydrated barta and thoroughly removes SO
4 2-Ion adds simultaneously that wood activated charcoal decolours and drainage, filters and removes barium sulfate precipitate and gac, and filtrate is concentrated, can obtain oxyacetic acid solution.
Press such scheme, the mass percent concentration of the described aqua calcis of step 1) is 5-40%, and wherein oxalic dialdehyde is 1:0.5-1.2 with the mol ratio of calcium hydroxide.
Press such scheme, the described disproportionation reaction temperature of step 1) is 0～25 ℃.
Press such scheme, step 3) also comprises the crystallization of oxyacetic acid solution deep is obtained high purity hydroxyl acetic acid crystal, described degree of depth crystallization is to be 80-95% with oxyacetic acid solution rotating evaporation concentration to mass percent concentration, 50-65 ℃ of rotary evaporation temperature, vacuum tightness 0.080-0.095MPa, cooling can obtain the oxyacetic acid crystal, is that 60% oxyacetic acid solution is as the detergent washing crystallization with mass percent concentration again, through vacuum-drying, the oxyacetic acid crystal that obtains making with extra care.
Press such scheme, step 3) also comprises the crystallization of oxyacetic acid solution deep is obtained high purity hydroxyl acetic acid crystal, described degree of depth crystallization is to anhydrous fractionating out with oxyacetic acid solution rotating evaporation concentration, enriched material extracts with acetone solvent, behind the extraction liquid precipitation or direct crystallisation by cooling, the oxyacetic acid crystal that obtains making with extra care.
Detect through HPLC, the oxalic dialdehyde transformation efficiency after the degree of depth crystallization is more than 98%, and oxyacetic acid purity is greater than 99.5%, and the oxyacetic acid yield is seen accompanying drawing 1 greater than 90%().
In theory, the alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be as the disproportionation catalyst without the aldehyde of α-H, but the alkalescence of this class alkali is too strong, be easy to cause side reaction, oxyacetic acid is to utilize that simultaneous hydroxyl and carboxyl and calcium, barium plasma form water miscible complex compound or salt in the molecule as the cardinal principle of clean-out system.In the alkaline environment of some strength, oxyacetic acid can form the hydroxyl acetate precipitation with calcium, barium plasma, and acidifying after the precipitate and separate can be obtained oxyacetic acid.Wherein barium belongs to heavy metal ion, should avoid a large amount of uses, therefore selects take calcium hydroxide as Primary Catalysts, and the mass percent concentration of alkali can at 5-40%, be advisable with about 20%; The disproportionation reaction temperature is controlled between 0～25 ℃, considers from cost and reaction efficiency, and temperature of reaction is advisable with 20～25 ℃.Wherein temperature surpasses 25 ℃ and easily causes the side reactions such as oxidation or polymerization, reactant color burn, complicated components.Disproportionation reaction time temperature of reaction when dripping is no more than 25 ℃ as standard, and about 1 hour of general time for adding is added dropwise to complete follow-up continuation of insurance temperature and reacted 0.5-1 hour.
From by-product salt can be easily by precipitate and separate, can fully utilize two factors and consider that the laboratory has been carried out in the alkali with sulfuric acid, phosphoric acid respectively and tested.The vitriol of calcium and barium, phosphoric acid salt all can form precipitation, but consider from cost factor, and experiment selects sulfuric acid as neutralizing acid at last, also available hydrochloric acid neutralization when product is low to the chlorion requirement.
Antacid concentration and consumption: for reducing concentrated amount, with vitriol oil neutralization, or will neutralize with 50% sulfuric acid again after the Calcium Glycolate filtering separation.In and the time should control temperature of reaction and be no more than 25 ℃.The consumption of sulfuric acid is identical with disproportionation alkali consumption mole number.
The removal of sulfate anion: the solubleness of calcium sulfate in water is about 0.2g under the normal temperature, therefore with still having a small amount of SO in the oxyacetic acid solution after the sulfuric acid parsing (forming oxyacetic acid and calcium sulfate precipitation)
4 2-Ion, its content is far longer than SO in the finished product
4 2-Ionic concn needs essence to remove less than the requirement of 30ppm.Normal operation energy and SO
4 2-Ion forms alkali or the salt of the lower sulfate precipitation of solubility product.Here need to seek a kind ofly can make SO
4 2-Ion does not exceed standard, and avoids again the introducing of excess salt and causes oxyacetic acid to reduce product yield because of complexing.Experimental result shows, uses barium acetate or hydrated barta to achieve the goal, and removes SO
4 2-Solution for vacuum concentration behind the ion can obtain the oxyacetic acid solution of mass percent 70%.
Reaction principle of the present invention is: the aldehyde without α-H issues living intramolecular redox in the effect of the alkali of some strength, and a part aldehyde is oxidized to acid as a result, and another molecule aldehyde is reduced into alcohol, i.e. intramolecular disproportionation reaction.At first the carbonyl of hydroxyl radical negative ion and aldehyde carries out nucleophilic addition(Adn), forms the hydroxyl oxygen negative ion; Under catalyst action, strengthened the ortho position carbon atom with the Sauerstoffatom of negative charge in the hydroxyl oxygen negative ion and repelled electronic capability, so that the hydrogen on the carbon is transferred on the carbonylic carbon atom of another molecule aldehyde radical with the negative hydrogen ion form with pair of electrons are.Wherein, the aldehyde that provides negative hydrogen ion is donor (being oxidized to acid); The aldehyde of accepting the negative hydrogen ion ion is acceptor (being reduced into alcohol).For oxalic dialdehyde and say, be intramolecular selfoxidation-reduction reaction, an aldehyde radical is oxidized, and another aldehyde radical is reduced, and oxalic dialdehyde obtains hydroxyl acetate through catalytic disproportionation in the molecule, obtains oxyacetic acid after the acidifying.From the disproportionation reaction principle analysis, in the presence of catalyzer, use the alkali of some strength can finish disproportionation reaction.Oxyacetic acid not only can with the basic metal salify of introducing, but also can form complex compound and consume oxyacetic acid with metal ion.In the acidification step after finishing disproportionation reaction, if the acid of use can form with the alkali of disproportionation the long-pending less salt of content, just can solve simultaneously acidifying and remove the negatively charged ion problem of introducing, therefore can select targetedly disproportionation alkali and neutralizing acid.
Beneficial effect of the present invention is:
1) with calcium hydroxide oxalic dialdehyde being carried out in the molecule disproportionation reaction, to prepare the oxyacetic acid reaction yield high, low in the pollution of the environment, can overcome the deficiency of traditional cyanide process or Mono Chloro Acetic Acid hydrolysis production technique, meets the requirement of Green Chemistry development;
2) carry out at normal temperatures and pressures disproportionation reaction, equipment is not had particular requirement, simple to operate, by product can fully utilize, and can realize cleaner production;
3) reaction preference is high, and product impurity is few, and purity is high, has overcome the difficulty that the high-purity crystal that causes because of impurity is difficult to form, for convenience has been created in the preparation of high purity hydroxyl acetic acid crystal.
Description of drawings
Fig. 1 is the HPLC spectrogram of oxyacetic acid.
Embodiment
The present invention is described in further detail below in conjunction with example.
Embodiment 1:
In three mouthfuls of reaction flasks of 1000ml, add 40g calcium hydroxide and 500ml water (mass percent concentration of aqua calcis is 7.4%), water-bath, mechanical stirring, dropping 145g mass concentration is 40% glyoxal solution from dropping funnel, rate of addition is no more than 25 ℃ with the control temperature of reaction and is advisable, 20-25 ℃ of insulation reaction 1 hour, obtain suspended state Calcium Glycolate precipitation mixture after being added dropwise to complete.Add the 55g vitriol oil (0.54mol) in the suspended state Calcium Glycolate precipitation mixture by dropping funnel while stirring and carry out acidifying, the filtering calcium sulfate precipitation, the filtrate vacuum concentration is to anhydrous timesharing, the a small amount of calcium sulfate that is dissolved in the filtrate is separated out, filtering separation, it is 12% that filtrate is diluted to the oxyacetic acid mass concentration with deionized water, removes micro-SO with the barium acetate solution of mass percent concentration 10%
4 2-Ion is until without new white BaSO
4Till precipitation occurs, add the wood activated charcoal that 1g has decolouring and filtrating aid function, 50-60 ℃ of heating 5 minutes filtered, and filtrate decompression is concentrated, can obtain concentration and be 70% oxyacetic acid solution.HPLC detects, oxyacetic acid purity 〉=98% in the sample, oxyacetic acid yield 〉=92%.
Embodiment 2:
In three mouthfuls of reaction flasks of 1000ml, add 40g calcium hydroxide and 300ml water (mass percent concentration is 11.8%), water-bath, mechanical stirring, dropping 145g mass concentration is 40% glyoxal solution from dropping funnel, rate of addition is no more than 25 ℃ with the control temperature of reaction and is advisable, 20-25 ℃ of insulation reaction 1 hour, obtain suspended state Calcium Glycolate precipitation mixture after being added dropwise to complete.Reaction mixture filters, and the filter cake deionized water wash obtains the precipitation of Calcium Glycolate.Throw out is that 50% sulphuric acid soln carries out acidifying with the 108g mass concentration, the filtering calcium sulfate precipitation, and filtrate removes micro-SO with the barium acetate solution of mass concentration 10%
4 2-Ion is until without new BaSO
4Till precipitation occurs.Add the decolouring of 1g powdery wood activated charcoal and also filter, filtrate decompression is concentrated, can obtain mass concentration and be 70% oxyacetic acid solution.Oxyacetic acid HPLC detects, oxyacetic acid purity 〉=98% in the sample, oxyacetic acid yield 〉=90%.
Embodiment 3:
The oxyacetic acid solution continuation rotary evaporation that embodiment 1 is obtained is concentrated into the oxyacetic acid mass concentration more than 85%, 50-65 ℃ of rotary evaporation temperature, and vacuum tightness 0.080-0.095MPa is cooled to room temperature, namely has thick oxyacetic acid crystal to separate out.Filter, with mass concentration be 60% oxyacetic acid solution as detergent washing crystal secondary, reduced vacuum drying, the oxyacetic acid crystal that obtains making with extra care.HPLC detects, oxyacetic acid content purity 〉=99%, crystal oxyacetic acid yield 〉=75%.
Embodiment 4:
The oxyacetic acid solution continuation rotary evaporation that embodiment 2 is obtained is concentrated into anhydrous fractionating out.The enriched material acetone extract is cooled to room temperature, and filtration drying namely obtains the oxyacetic acid crystal made from extra care; Or with behind the thorough desolvation of acetone extract thing, use deionized water dissolving, and make the oxyacetic acid mass concentration more than 85%, crystallisation by cooling filters drying under reduced pressure, the oxyacetic acid crystal that also can obtain making with extra care.HPLC detects, oxyacetic acid content purity 〉=99.5%, crystal oxyacetic acid yield 〉=70%.
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Non-Patent Citations (4)
| Title |
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| G.D. Yadav et al..Synthesis of glyoxalic acid from glyoxal.《Process Biochemistry》.2000,第36卷第73–78页. |
| Synthesis of glyoxalic acid from glyoxal;G.D. Yadav et al.;《Process Biochemistry》;20001231;第36卷;第73–78页 * |
| 从乙二醛经康尼查罗反应合成羟基乙酸的新方法;廖川平;《合成化学》;20081231;第16卷(第4期);第470-471页 * |
| 廖川平.从乙二醛经康尼查罗反应合成羟基乙酸的新方法.《合成化学》.2008,第16卷(第4期),第470-471页. |
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