CN105669433A - Preparation method of glyoxalic acid monohydrate crystals - Google Patents
Preparation method of glyoxalic acid monohydrate crystals Download PDFInfo
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- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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Abstract
The invention relates to a preparation method of glyoxalic acid monohydrate crystals. The technical scheme is as follows: the method comprises the following steps: heating a glyoxalic acid crude product, adding a precipitant, stirring, cooling, and carrying out vacuum filtration to obtain a filtrate I; adding activated carbon into the filtrate I, cooling, and carrying out vacuum filtration to obtain a filtrate II; concentrating the filtrate II under reduced pressure until the glyoxalic acid concentration is 55-67 wt%, thereby obtaining a crystallizing mother solution; transferring the crystallizing mother solution into a jacket crystallizing kettle, cooling, adding glyoxalic acid monohydrate crystals, keeping the temperature, cooling to -5 to 10 DEG C, and keeping the temperature to obtain a crystalline liquid; filtering the crystalline liquid to obtain a filtrate III and a filter cake; carrying out vacuum drying on the filter cake to obtain the glyoxalic acid monohydrate crystal crystals; treating the filtrate III by the process for treating the filtrate II to obtain a filtrate IV and glyoxalic acid monohydrate crystals; and treating the filtrate IV by the process for treating the filtrate II, thereby obtaining a filtrate V and the glyoxalic acid monohydrate crystals. The method is simple in technique, convenient to operate and suitable for industrial production. The prepared glyoxalic acid monohydrate crystals have the advantages of high purity and high yield.
Description
Technical field
The invention belongs to glyoxalic acid technical field. Be specifically related to a kind of preparation method of glyoxalic acid one crystalline hydrate thing.
Background technology
Glyoxalic acid (glyoxalicacid, CHOCOOH) is the simplest aldehydic acid, has aldehyde and carboxylic acid functional and phase thereof simultaneouslyAnswering chemical property, is a kind of important fine chemical material, be widely used in spices, medical science, paper-making industry, leather, painted, mouldThe fields such as material, agricultural chemicals, coating, food additives, biochemistry, organic and spectroscopy, preparation is as vanillic aldehyde, ethyl chinese cymbidiumElement, heliotropin, allantoin, hydroxyphenylglycine, p-hydroxyphenylaceticacid, acetophenone, 2-Qiang based quinoxaline, mandelic acid andThe chemical products such as hydroxyl phosphine carboxylic acid. Along with the continually developing and expanding production of glyoxalic acid downstream product, the demand of glyoxalic acid is quickIncrease.
Glyoxalic acid in the market mainly exists with the glyoxalic acid solution of 40～50wt%, and glyoxalic acid solution is due in a large numberThe existence of water, is difficult to meet the needs of industry to high-purity crystals type glyoxalic acid product such as medicine, food. Crystal-type acetaldehyde acid groupThere are three kinds of forms according to band crystallization water difference: not being with crystallization water glyoxalic acid (CHOCOOH), is monoclinic crystal body, 98 DEG C of fusing points;Being with half crystallization water glyoxalic acid (CHOCOOHl/2H2O), is colourless column crystallization, and fusing point is 70～75 DEG C; Be with a knotBrilliant water glyoxalic acid (CHOCOOHH20), 50～52 DEG C of fusing points. Crystal-type glyoxalic acid has tedious taste, is a kind ofSevere corrosive acid, easily deliquescence, is exposed in air and can forms pulpous state.
It is assorted that " process for refining and purifying of glyoxalic acid " (CN200510105816.1) provides a kind of employing ion exchange resin to removeThe process for purification of matter, reduced pressure concentration and low temperature crystallization. This method adopts three kinds of ion exchange resin columns to remove impurity, and equipment investment is large,Production cost is higher, and ion exchange resin regeneration step is complicated and be inconvenient to operate.
" a kind of glyoxalic acid process for purification " (CN201210261106.8) provides a kind of employing calcification agent to remove glyoxalic acid crude productIn part oxalic acid, the crystallize out of directly lowering the temperature. After adopting the glyoxylic acid solution placement a period of time after calcification agent precipitation, meeting againProduce precipitation, crystallization and the exterior quality of glyoxylic acid solution after refining are had to adverse effect, and be unfavorable for the product of glyoxalic acid crystalRaw. Directly decrease temperature crystalline is high to glyoxylic acid solution purity requirement, and the impurity such as oxalic acid wherein have a significant impact crystallization. Crystallization obtainsTo the not high and color of glyoxalic acid crystal purity be difficult to reach white, only carry out primary crystallization, glyoxalic acid product yield is not high,Not possessing production application is worth.
Summary of the invention
The present invention is intended to overcome prior art defect, and it is simple, easy to operate and be suitable for suitability for industrialized production that object is to provide a kind of techniqueThe preparation method of glyoxalic acid one crystalline hydrate thing, the glyoxalic acid one crystalline hydrate thing purity prepared by the method is high and yield is high.
For achieving the above object, the technical solution used in the present invention is:
Step 1, glyoxalic acid crude product is heated to 50～70 DEG C, drops into precipitating reagent, the grass in described precipitating reagent and glyoxalic acid crude productThe mol ratio of acid is 1～2: 1, stirs 1～2 hour, is naturally cooled to normal temperature, and suction filtration, obtains filtrate I. At 50～70 DEG C of barsUnder part, in described filtrate I, add active carbon, described active carbon is 1～5wt% of described filtrate I, stir 2～3 hours,Naturally be cooled to normal temperature, suction filtration, obtains filtrate II.
Step 2, under 50～65 DEG C of conditions, it is 55～67wt% that described filtrate II is evaporated to glyoxalic acid concentration, obtains knotBrilliant mother liquor.
Step 3, described crystalline mother solution is proceeded in chuck crystallization kettle, under stirring condition, with the cooling of 2～25 DEG C/hThe crystalline mother solution in described chuck crystallization kettle is down to-1～10 DEG C by speed, then add glyoxalic acid monohydrate crystal as crystal seed,Be incubated 1～2 hour; Then with the rate of temperature fall of 2～25 DEG C/h, the crystalline mother solution that adds crystal seed is cooled to-5～-10 DEG C,Be incubated 1～3 hour, obtain crystal solution.
Step 4, described crystal solution is filtered under dry atmosphere protection, obtain filtrate III and filter cake; Again by described filter cake 20～Vacuum drying 10～20 hours under 35 DEG C of conditions, makes glyoxalic acid one crystalline hydrate thing.
Step 5, according to method described in step 2～step 4, process filtrate III by the method for processing filtrate II, successively filteredLiquid IV and glyoxalic acid one crystalline hydrate thing.
Step 6, according to method described in step 2～step 4, process filtrate IV by the method for processing filtrate II, successively filteredLiquid V and glyoxalic acid one crystalline hydrate thing, filtrate V can be used as the raw material of other products.
Described glyoxalic acid crude product is that concentration is the glyoxalic acid solution of 40～50wt%.
Described precipitating reagent is zirconium dioxide, zirconium carbonate, zinc oxide, zinc carbonate, titanium dioxide, magnesia, magnesium carbonate, hydrogen-oxygenChange the one in magnesium and zinc hydroxide.
The addition of described glyoxalic acid monohydrate crystal is 0.001～1wt% of described crystalline mother solution.
Described dry atmosphere is dry air atmosphere, nitrogen atmosphere, oxygen atmosphere, carbon dioxide atmosphere, argon gas atmosphere, heliumOne in gas atmosphere.
Owing to adopting technique scheme, the present invention compared with prior art has following good effect:
The present invention adopts novel precipitating reagent except oxalic acid, has and better removes oxalic acid effect than the calcification agent generally adopting, and has solved and has used calciumGlyoxylic acid solution after agent precipitation is placed with the difficult problem that precipitation produces again for a long time. Adopt active carbon to carry out to glyoxylic acid solutionDecolouring is processed, and glyoxalic acid solution colourity is obviously reduced, and makes glyoxalic acid crystal color whiter. By reduced pressure concentration, removeThe low boiling impurity existing in glyoxalic acid crude product. By adding decrease temperature crystalline after crystal seed, make glyoxalic acid with a crystalline hydrate thingForm is separated out better, separates with water-solubility impurities such as glyoxals, makes the purity of gained glyoxalic acid one crystalline hydrate thing reach 98%Above, outward appearance is all white in color. Crystalline mother solution is carried out to time use, the recovery rate of glyoxalic acid one crystalline hydrate produce product is reachedMore than 85%. This method technological process is simple, and convenient operation and control is suitable for large-scale industrialization and produces. Prepared glyoxalic acidOne crystalline hydrate produce rate is high and purity is high, has the powerful market competitiveness, meets market to glyoxalic acid one crystalline hydrate thingDemand.
Therefore, to have technique simple, easy to operate and be suitable for the feature of suitability for industrialized production, the acetaldehyde of preparing by the method in the present inventionAcid one crystalline hydrate thing purity is high and yield is high.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described, not the restriction to its protection domain.
Embodiment 1
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Described preparation method's concrete steps are:
Step 1, glyoxalic acid crude product is heated to 50～60 DEG C, drops into precipitating reagent, the grass in described precipitating reagent and glyoxalic acid crude productThe mol ratio of acid is 1～2: 1, stirs 1～2 hour, is naturally cooled to normal temperature, and suction filtration, obtains filtrate I. At 50～60 DEG C of barsUnder part, in described filtrate I, add active carbon, described active carbon is 1～3wt% of described filtrate I, stir 2～3 hours,Naturally be cooled to normal temperature, suction filtration, obtains filtrate II.
Step 2, under 50～55 DEG C of conditions, it is 55～59wt% that described filtrate II is evaporated to glyoxalic acid concentration, obtains knotBrilliant mother liquor.
Step 3, described crystalline mother solution is proceeded in chuck crystallization kettle, under stirring condition, with the cooling of 2～10 DEG C/hThe crystalline mother solution in described chuck crystallization kettle is down to-1～3 DEG C by speed, then add glyoxalic acid monohydrate crystal as crystal seed, addsEnter 0.001～0.01wt% that amount is crystalline mother solution, be incubated 1～2 hour; Then will add with the rate of temperature fall of 2～10 DEG C/hThe crystalline mother solution that enters crystal seed is cooled to-5～-7 DEG C, is incubated 1～3 hour, obtains crystal solution.
Step 4, described crystal solution is filtered under dry atmosphere protection, obtain filtrate III and filter cake; Again by described filter cake 20～Vacuum drying 10～15 hours under 25 DEG C of conditions, makes glyoxalic acid one crystalline hydrate thing.
Step 5, according to method described in step 2～step 4, process filtrate III by the method for processing filtrate II, successively filteredLiquid IV and glyoxalic acid one crystalline hydrate thing.
Step 6, according to method described in step 2～step 4, process filtrate IV by the method for processing filtrate II, successively filteredLiquid V and glyoxalic acid one crystalline hydrate thing, filtrate V can be used as the raw material of other products.
In the present embodiment: described glyoxalic acid crude product is that concentration is the glyoxalic acid solution of 40～45wt%; Described precipitating reagent is dioxyChange zirconium; Described dry atmosphere is dry air atmosphere.
The total recovery of the present embodiment is 87.55～87.61%, purity be 98.15～99.76% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 1;
Table 1
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 52.03～52.11 | 99.39～99.76 | White |
| Secondary crystallization | 53.14～53.20 | 98.92～99.02 | White |
| Three crystallizations | 44.63～44.70 | 98.15～98.44 | White |
Embodiment 2
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Except following parameter, all the other are with embodiment 1:
In the present embodiment: described precipitating reagent is zirconium carbonate; Described dry atmosphere is nitrogen atmosphere.
The total recovery of the present embodiment is 85.81～86.9%, purity be 98.25～99.55% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 2;
Table 2
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 51.73～52.09 | 99.17～99.55 | White |
| Secondary crystallization | 52.88～53.10 | 98.94～99.12 | White |
| Three crystallizations | 45.73～45.82 | 98.25～98.34 | White |
Embodiment 3
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Except following parameter, all the other are with embodiment 1:
In the present embodiment: described precipitating reagent is zinc oxide; Described dry atmosphere is oxygen atmosphere.
The total recovery of the present embodiment is 85.21～87.01%, purity be 98.19～99.65% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 3;
Table 3
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 52.00～52.19 | 99.27～99.65 | White |
| Secondary crystallization | 52.78～53.14 | 98.89～99.11 | White |
| Three crystallizations | 45.65～45.92 | 98.19～98.46 | White |
Embodiment 4
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Described preparation method's concrete steps are:
Step 1, glyoxalic acid crude product is heated to 55～65 DEG C, drops into precipitating reagent, the grass in described precipitating reagent and glyoxalic acid crude productThe mol ratio of acid is 1～2: 1, stirs 1～2 hour, is naturally cooled to normal temperature, and suction filtration, obtains filtrate I. At 55～65 DEG C of barsUnder part, in described filtrate I, add active carbon, described active carbon is 3～5wt% of described filtrate I, stir 2～3 hours,Naturally be cooled to normal temperature, suction filtration, obtains filtrate II.
Step 2, under 55～60 DEG C of conditions, it is 59～63wt% that described filtrate II is evaporated to glyoxalic acid concentration, obtains knotBrilliant mother liquor.
Step 3, described crystalline mother solution is proceeded in chuck crystallization kettle, under stirring condition, with the cooling of 10～18 DEG C/hThe crystalline mother solution in described chuck crystallization kettle is down to 3～6 DEG C by speed, then add glyoxalic acid monohydrate crystal as crystal seed, addsEnter 0.01～0.1wt% that amount is crystalline mother solution, be incubated 1～2 hour; Then will add with the rate of temperature fall of 10～18 DEG C/hThe crystalline mother solution of crystal seed is cooled to-7～-10 DEG C, is incubated 1～3 hour, obtains crystal solution.
Step 4, described crystal solution is filtered under dry atmosphere protection, obtain filtrate III and filter cake; Again by described filter cake 25～Vacuum drying 15～20 hours under 30 DEG C of conditions, makes glyoxalic acid one crystalline hydrate thing.
Step 5, according to method described in step 2～step 4, process filtrate III by the method for processing filtrate II, successively filteredLiquid IV and glyoxalic acid one crystalline hydrate thing.
Step 6, according to method described in step 2～step 4, process filtrate IV by the method for processing filtrate II, successively filteredLiquid V and glyoxalic acid one crystalline hydrate thing, filtrate V can be used as the raw material of other products.
In the present embodiment: described glyoxalic acid crude product is that concentration is the glyoxalic acid solution of 45～50wt%; Described precipitating reagent is carbonic acidZinc; Described dry atmosphere is carbon dioxide atmosphere.
The total recovery of the present embodiment is 86.01～87.20%, purity be 98.08～99.47% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 4;
Table 4
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 52.01～52.08 | 99.27～99.47 | White |
| Secondary crystallization | 51.89～52.56 | 98.98～99.22 | White |
| Three crystallizations | 45.89～46.13 | 98.08～98.44 | White |
Embodiment 5
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Except following parameter, all the other are with embodiment 4:
In the present embodiment: described precipitating reagent is titanium dioxide; Described dry atmosphere is argon gas atmosphere.
The total recovery of the present embodiment is 85.3～86.78%, purity be 98.08～99.46% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 5;
Table 5
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 51.89～52.07 | 99.04～99.46 | White |
| Secondary crystallization | 53.01～53.19 | 98.79～99.07 | White |
| Three crystallizations | 45.88～46.33 | 98.08～98.47 | White |
Embodiment 6
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Except following parameter, all the other are with embodiment 4:
In the present embodiment: described precipitating reagent is magnesia; Described dry atmosphere is helium atmosphere.
The total recovery of the present embodiment is 85.8～86.39%, purity be 98.29～99.37% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 6;
Table 6
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 52.23～52.31 | 99.04～99.37 | White |
| Secondary crystallization | 52.75～53.06 | 98.82～99.05 | White |
| Three crystallizations | 45.24～45.68 | 98.29～98.39 | White |
Embodiment 7
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Described preparation method's concrete steps are:
Step 1, glyoxalic acid crude product is heated to 60～70 DEG C, drops into precipitating reagent, the grass in described precipitating reagent and glyoxalic acid crude productThe mol ratio of acid is 1～2: 1, stirs 1～2 hour, is naturally cooled to normal temperature, and suction filtration, obtains filtrate I. At 60～70 DEG C of barsUnder part, in described filtrate I, add active carbon, described active carbon is 2～4wt% of described filtrate I, stir 2～3 hours,Naturally be cooled to normal temperature, suction filtration, obtains filtrate II.
Step 2, under 60～65 DEG C of conditions, it is 63～67wt% that described filtrate II is evaporated to glyoxalic acid concentration, obtains knotBrilliant mother liquor.
Step 3, described crystalline mother solution is proceeded in chuck crystallization kettle, under stirring condition, with the cooling of 18～25 DEG C/hThe crystalline mother solution in described chuck crystallization kettle is down to 6～10 DEG C by speed, then add glyoxalic acid monohydrate crystal as crystal seed,Addition is 0.1～1wt% of crystalline mother solution, is incubated 1～2 hour; Then will add with the rate of temperature fall of 18～25 DEG C/hThe crystalline mother solution of crystal seed is cooled to-6～-9 DEG C, is incubated 1～3 hour, obtains crystal solution.
Step 4, described crystal solution is filtered under dry atmosphere protection, obtain filtrate III and filter cake; Again by described filter cake 30～Vacuum drying 13～18 hours under 35 DEG C of conditions, makes glyoxalic acid one crystalline hydrate thing.
Step 5, according to method described in step 2～step 4, process filtrate III by the method for processing filtrate II, successively filteredLiquid IV and glyoxalic acid one crystalline hydrate thing.
Step 6, according to method described in step 2～step 4, process filtrate IV by the method for processing filtrate II, successively filteredLiquid V and glyoxalic acid one crystalline hydrate thing, filtrate V can be used as the raw material of other products.
In the present embodiment: described glyoxalic acid crude product is that concentration is the glyoxalic acid solution of 43～48wt%; Described precipitating reagent is hydrogen-oxygenChange magnesium; Described dry atmosphere is nitrogen atmosphere.
The total recovery of the present embodiment is 85.44～87.02%, purity be 98.27～99.72% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 7;
Table 7
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 52.02～52.28 | 99.09～99.72 | White |
| Secondary crystallization | 52.77～53.15 | 98.74～99.03 | White |
| Three crystallizations | 45.69～45.99 | 98.27～98.46 | White |
Embodiment 8
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Except following parameter, all the other are with embodiment 7:
In the present embodiment: described precipitating reagent is magnesium carbonate; Described dry atmosphere is carbon dioxide atmosphere.
The total recovery of the present embodiment is 85.32～86.32%, purity be 98.17～99.49% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 8;
Table 8
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 52.04～52.18 | 99.09～99.49 | White |
| Secondary crystallization | 52.96～53.15 | 98.99～99.17 | White |
| Three crystallizations | 45.39～45.78 | 98.17～98.41 | White |
Embodiment 9
A kind of preparation method of glyoxalic acid one crystalline hydrate thing. Except following parameter, all the other are with embodiment 7:
In the present embodiment: described precipitating reagent is zinc hydroxide; Described dry atmosphere is dry air atmosphere.
The total recovery of the present embodiment is 85.33～87.05%, purity be 98.09～99.75% and outward appearance be all white in color: wherein threeYield, purity and the outward appearance of the glyoxalic acid one crystalline hydrate thing that inferior crystallization obtains are as described in Table 9;
Table 9
| The name of an article | Yield/% | One crystalline hydrate thing purity/% | Outward appearance |
| Primary crystallization | 51.99～52.23 | 99.01～99.75 | White |
| Secondary crystallization | 52.76～53.05 | 98.87～99.22 | White |
| Three crystallizations | 45.89～46.02 | 98.09～98.32 | White |
This detailed description of the invention compared with prior art has following good effect:
This detailed description of the invention adopts novel precipitating reagent except oxalic acid, has and better removes oxalic acid effect than the calcification agent generally adopting, and separatesDetermine and be placed with for a long time and again precipitate the difficult problem producing with the glyoxylic acid solution after calcification agent precipitation. Glyoxylic acid solution is adopted and livedThe processing of decolouring of property charcoal, obviously reduces glyoxalic acid solution colourity, makes glyoxalic acid crystal color whiter. Dense by reducing pressureContracting, has removed the low boiling impurity existing in glyoxalic acid crude product. By adding decrease temperature crystalline after crystal seed, make glyoxalic acid with a hydrationThe form of crystal is separated out better, separates with water-solubility impurities such as glyoxals, makes the purity of gained glyoxalic acid one crystalline hydrate thingReach more than 98%, outward appearance is all white in color. Crystalline mother solution is carried out to time use, make the receipts of glyoxalic acid one crystalline hydrate produce productYield reaches more than 85%. This method technological process is simple, and convenient operation and control is suitable for large-scale industrialization and produces. ObtainedGlyoxalic acid one crystalline hydrate produce rate high and purity is high, there is the powerful market competitiveness, meet market to glyoxalic acid one hydrationThe demand of crystal.
Therefore, it is simple, easy to operate and be suitable for the feature of suitability for industrialized production that this detailed description of the invention has technique, uses the party's legal systemStandby glyoxalic acid one crystalline hydrate thing purity is high and yield is high.
Claims (5)
1. a preparation method for glyoxalic acid one crystalline hydrate thing, is characterized in that described preparation method is:
Step 1, glyoxalic acid crude product is heated to 50～70 DEG C, drops into precipitating reagent, the grass in described precipitating reagent and glyoxalic acid crude productThe mol ratio of acid is 1～2: 1, stirs 1～2 hour, is naturally cooled to normal temperature, and suction filtration, obtains filtrate I; At 50～70 DEG C of barsUnder part, in described filtrate I, add active carbon, described active carbon is 1～5wt% of described filtrate I, stir 2～3 hours,Naturally be cooled to normal temperature, suction filtration, obtains filtrate II;
Step 2, under 50～65 DEG C of conditions, it is 55～67wt% that described filtrate II is evaporated to glyoxalic acid concentration, obtains knotBrilliant mother liquor;
Step 3, described crystalline mother solution is proceeded in chuck crystallization kettle, under stirring condition, with the cooling of 2～25 DEG C/hThe crystalline mother solution in described chuck crystallization kettle is down to-1～10 DEG C by speed, then add glyoxalic acid monohydrate crystal as crystal seed,Be incubated 1～2 hour; Then with the rate of temperature fall of 2～25 DEG C/h, the crystalline mother solution that adds crystal seed is cooled to-5～-10 DEG C,Be incubated 1～3 hour, obtain crystal solution;
Step 4, described crystal solution is filtered under dry atmosphere protection, obtain filtrate III and filter cake; Again by described filter cake 20～Vacuum drying 10～20 hours under 35 DEG C of conditions, makes glyoxalic acid one crystalline hydrate thing;
Step 5, according to method described in step 2～step 4, process filtrate III by the method for processing filtrate II, successively filteredLiquid IV and glyoxalic acid one crystalline hydrate thing;
Step 6, according to method described in step 2～step 4, process filtrate IV by the method for processing filtrate II, successively filteredLiquid V and glyoxalic acid one crystalline hydrate thing, filtrate V can be used as the raw material of other products.
2. the preparation method of glyoxalic acid one crystalline hydrate thing according to claim 1, is characterized in that described glyoxalic acid crude productFor the concentration glyoxalic acid solution that is 40～50wt%.
3. the preparation method of glyoxalic acid one crystalline hydrate thing according to claim 1, is characterized in that described precipitating reagent is twoIn zirconia, zirconium carbonate, zinc oxide, zinc carbonate, titanium dioxide, magnesia, magnesium carbonate, magnesium hydroxide and zinc hydroxideA kind of.
4. the preparation method of glyoxalic acid one crystalline hydrate thing according to claim 1, is characterized in that described glyoxalic acid one waterThe addition of compound crystal is 0.001～1wt% of described crystalline mother solution.
5. the preparation method of glyoxalic acid one crystalline hydrate thing according to claim 1, is characterized in that described dry atmosphere isOne in dry air atmosphere, nitrogen atmosphere, oxygen atmosphere, carbon dioxide atmosphere, argon gas atmosphere, helium atmosphere.
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| JP2003096025A (en) * | 2001-09-21 | 2003-04-03 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing glyoxylic acid monohydrate |
| JP3960025B2 (en) * | 2001-11-29 | 2007-08-15 | 日産自動車株式会社 | Welding method |
| CN101712615A (en) * | 2009-11-27 | 2010-05-26 | 天津市职业大学 | Method for preparing crystal glyoxylic acid |
| CN102786409A (en) * | 2012-07-26 | 2012-11-21 | 湖北省宏源药业有限公司 | Refining method for glyoxalic acid |
-
2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003096025A (en) * | 2001-09-21 | 2003-04-03 | Nippon Synthetic Chem Ind Co Ltd:The | Method for producing glyoxylic acid monohydrate |
| JP3960025B2 (en) * | 2001-11-29 | 2007-08-15 | 日産自動車株式会社 | Welding method |
| CN101712615A (en) * | 2009-11-27 | 2010-05-26 | 天津市职业大学 | Method for preparing crystal glyoxylic acid |
| CN102786409A (en) * | 2012-07-26 | 2012-11-21 | 湖北省宏源药业有限公司 | Refining method for glyoxalic acid |
Non-Patent Citations (1)
| Title |
|---|
| 李建生等: "固体乙醛酸清洁生产新工艺", 《精细与专用化学品》 * |
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