CN102816058A - Method for preparing 2, 2-bis (hydroxymethyl) butyric acid - Google Patents
Method for preparing 2, 2-bis (hydroxymethyl) butyric acid Download PDFInfo
- Publication number
- CN102816058A CN102816058A CN2012103339259A CN201210333925A CN102816058A CN 102816058 A CN102816058 A CN 102816058A CN 2012103339259 A CN2012103339259 A CN 2012103339259A CN 201210333925 A CN201210333925 A CN 201210333925A CN 102816058 A CN102816058 A CN 102816058A
- Authority
- CN
- China
- Prior art keywords
- parts
- add
- preparation
- acid
- butyraldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing 2, 2-bis (hydroxymethyl) butyric acid. The method includes the steps of condensation, neutralization, recycling, oxidation, displacement, concentration, dilution, crystallization, filtering, primary purification, secondary purification and the like. Compared with foreign production methods, the method has the advantages that the selectivity of utilized catalysts is high, the butyraldehyde conversion rate is high, the energy consumption is low, the wastewater output quantity is small, and the solid waste can be effectively utilized.
Description
Technical field
The invention belongs to the chemical preparation field, specifically is a kind of 2, the preparation method of 2-dimethylolpropionic acid.
Background technology
2, the 2-dimethylolpropionic acid is to substitute 2, the new generation of green environmental-protecting chemical article of 2-dimethylol propionic acid.Dimethylolpropionic acid passes through the effect of two one-level hydroxyls, just Urethylaneization or the esterification easily of the 3rd carboxyl that do not need protection, and the unreacted carboxyl of neutralization in ammoniacal liquor makes its water-solubleization then.This product can be widely used in the production of aspects such as aqurous ployurethane, polyester, epoxy resin.Aspect solvability, dimethylolpropionic acid has the unique advantage of oneself, and its fabulous solvability can be increased work efficiency greatly.
But because the difficulty on the technology of preparing; At present about 2; The research of 2-dimethylolpropionic acid synthetic is reported seldom, the report that the whole world once had the Japan company of changing into can carry out scale prodn, but the said firm will have stopped producing the end of the year 2005; Give Bai Situo (Perstorp) company of Sweden with equipment, transfer of technology, the said firm will also stop to produce the end of the year 2009.Even but also there are problems such as catalyst selectivity is poor with reactivity, operational path is complicated, energy consumption is high, environmental pollution is serious in up-to-date in the world synthetic technology, does not meet the mentality of designing that effectively reduces the Green Chemistry of pollution from the source.
?
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of 2, the preparation method of 2-dimethylolpropionic acid.
The principle of technology of the present invention is: under the effect of diluted alkaline; The butyraldehyde-n generation aldol reaction of bimolecular formaldehyde and a part generates 2 of a part, 2-dihydroxymethyl butyraldehyde; 2; 2-dihydroxymethyl butyraldehyde and hydrogen peroxide effect oxidation generate 2, and the 2-dimethylolpropionic acid generates the water of a part simultaneously.
A kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that comprising the steps:
1) in reaction kettle, adds entry, drop into salt of wormwood and Pottasium Hydroxide, add formaldehyde, drip butyraldehyde-n, dropwise the back and keep constant temperature;
2) reaction solution is evacuated to another reaction kettle, adds formic acid and neutralize, concentrating under reduced pressure reclaims unreacted butyraldehyde-n;
3) add methyl alcohol, extract unreacted formaldehyde;
4) intensification and dropping ydrogen peroxide 50 dropwise the back and keep constant temperature;
5) add sulfuric acid, concentrating under reduced pressure then;
6) add ETHYLE ACETATE and make thinner, then crystallisation by cooling;
7) add that MIBK stirs, filters, concentrates, crystallization;
8) add entry, carry out recrystallization, finished product is dried, pulverizes, is sieved, packing.
Described a kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that said step 2) in to add mass percentage concentration be 85% formic acid, add mass percentage concentration in the said step 5) and be 10% sulfuric acid.
Described a kind of 2, the preparation method of 2-dimethylolpropionic acid, the raw material that it is characterized in that adding in each step is according to following parts by weight: 30-50 parts in the water that adds in the step 1), 20-35 parts in formaldehyde; 5-15 parts of butyraldehyde-ns; 0.05-0.5 part in salt of wormwood; 0.2-0.8 part in Pottasium Hydroxide; 0.2-0.6 part in formic acid; 1-7 parts of methyl alcohol; 15-25 parts in ydrogen peroxide 50; 3-15 parts in sulfuric acid; 1-8 parts in ETHYLE ACETATE; 2-15 parts of MIBKs.
Described a kind of 2, the preparation method of 2-dimethylolpropionic acid, the raw material that it is characterized in that adding in each step is according to following parts by weight: 35-45 parts in the water that adds in the step 1), 25-30 parts in formaldehyde; 8-12 parts of butyraldehyde-ns; 0.1-0.3 part in salt of wormwood; 0.4-0.6 part in Pottasium Hydroxide; 0.3-0.5 part in formic acid; 3-5 parts of methyl alcohol; 18-22 parts in ydrogen peroxide 50; 5-10 parts in sulfuric acid; 2-6 parts in ETHYLE ACETATE; 6-10 parts of MIBKs.
Described a kind of 2, the preparation method of 2-dimethylolpropionic acid, the raw material that it is characterized in that adding in each step is according to following parts by weight: 40 parts in the water that adds in the step 1), 26 parts in formaldehyde; 9.6 parts of butyraldehyde-ns; 0.2 part in salt of wormwood; 0.48 part in Pottasium Hydroxide; 0.4 part in formic acid; 4 parts of methyl alcohol; 20 parts in ydrogen peroxide 50; 8 parts in sulfuric acid; 4 parts in ETHYLE ACETATE; 8 parts of MIBKs.
Described a kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that
Keep 10 ℃-30 ℃ of constant temperature in the step 1), preferred 20 ℃, drip ydrogen peroxide 50 after being warmed up to 60 ℃-80 ℃ in the step 4), dropwise the back and keep 60 ℃-80 ℃ of constant temperature, preferred 70 ℃.
Described a kind of 2, the preparation method of 2-dimethylolpropionic acid, the weight ratio that it is characterized in that being evaporated in the step 5) water accounts total amount is below 2%.
Of the present invention a kind of 2, the preparation method of 2-dimethylolpropionic acid, reaction conditions is gentle; Stable operation, the yield of increase product adds sulfuric acid and removes formic acid; Reduce the sour water quantity discharged, reduce discharged waste water and processing cost simultaneously, and useless admittedly vitriolate of tartar can be used as potash fertilizer; Compare with external working method, the catalyst selectivity of use is high, the butyraldehyde transformation efficiency is high, energy consumption is low, the waste water generation is few, Gu useless being utilized effectively.
Description of drawings
Fig. 1 is the process flow sheet of method of the present invention.
?
Embodiment
Embodiment 1
A kind of 2, the preparation method of 2-dimethylolpropionic acid comprises the steps:
1) in the 1500L reaction kettle, adds entry 1000Kg, drop into salt of wormwood 5Kg and Pottasium Hydroxide 12Kg, add formaldehyde 650Kg, drip butyraldehyde-n 240Kg, dropwise 20 ℃ of maintenance constant temperature as alkaline catalysts;
2) reaction solution is evacuated to another reaction kettle, adds formic acid 10Kg neutralization, concentrating under reduced pressure reclaims unreacted butyraldehyde-n;
3) add methyl alcohol 100Kg, extract unreacting acetal;
4) be warmed up to 70 ℃, drip ydrogen peroxide 50 500Kg then, dropwise 70 ℃ of maintenance constant temperature;
5) the adding mass percentage concentration is 10% sulfuric acid 200Kg, and the weight ratio that is evaporated to the water accounts total amount is below 2%;
6) add ETHYLE ACETATE 100Kg and make thinner, crystallisation by cooling;
7) bullion carries out once refining with MIBK 200Kg;
8) add water and carry out secondary refining, finished product is dried, pulverizes, is sieved, packing.
Embodiment 2
A kind of 2, the preparation method of 2-dimethylolpropionic acid comprises the steps:
1) in the 1500L reaction kettle, adds entry 875Kg, drop into salt of wormwood 7.5Kg and Pottasium Hydroxide 10Kg, add formaldehyde 750Kg, drip butyraldehyde-n 200Kg, dropwise 10 ℃ of maintenance constant temperature as alkaline catalysts;
2) reaction solution is evacuated to another reaction kettle, adds formic acid 12.5Kg neutralization, concentrating under reduced pressure reclaims unreacted butyraldehyde-n;
3) add methyl alcohol 125Kg, extract unreacting acetal;
4) be warmed up to 60 ℃, drip ydrogen peroxide 50 450Kg then, dropwise 60 ℃ of maintenance constant temperature;
5) the adding mass percentage concentration is 10% sulfuric acid 250Kg, and the weight ratio that is evaporated to the water accounts total amount is below 2%;
6) add ETHYLE ACETATE 50Kg and make thinner, crystallisation by cooling;
7) bullion carries out once refining with MIBK 150Kg;
8) add water and carry out secondary refining, finished product is dried, pulverizes, is sieved, packing.
Embodiment 3
A kind of 2, the preparation method of 2-dimethylolpropionic acid comprises the steps:
1) in the 1500L reaction kettle, adds entry 1125Kg, drop into salt of wormwood 2.5Kg and Pottasium Hydroxide 15Kg, add formaldehyde 625Kg, drip butyraldehyde-n 300Kg, dropwise 30 ℃ of maintenance constant temperature as alkaline catalysts;
2) reaction solution is evacuated to another reaction kettle, adds formic acid 7.5Kg neutralization, concentrating under reduced pressure reclaims unreacted butyraldehyde-n;
3) add methyl alcohol 75Kg, extract unreacting acetal;
4) be warmed up to 80 ℃, drip ydrogen peroxide 50 550Kg then, dropwise 80 ℃ of maintenance constant temperature;
5) the adding mass percentage concentration is 10% sulfuric acid 125Kg, and the weight ratio that is evaporated to the water accounts total amount is below 2%;
6) add ETHYLE ACETATE 150Kg and make thinner, crystallisation by cooling;
7) bullion carries out once refining with MIBK 250Kg;
8) add water and carry out secondary refining, finished product is dried, pulverizes, is sieved, packing.
Through test, method each item technic index of the present invention is as shown in table 1:
The technic index of table 1 method of the present invention and external traditional technology contrast table
Can find out that from table 1 the present invention compares with external working method, the catalyst selectivity of use is high, the butyraldehyde transformation efficiency is high, energy consumption is low, the waste water generation is few, Gu useless being utilized effectively.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all is included within protection scope of the present invention.
Claims (7)
1. one kind 2, the preparation method of 2-dimethylolpropionic acid is characterized in that comprising the steps:
1) in reaction kettle, adds entry, drop into salt of wormwood and Pottasium Hydroxide, add formaldehyde, drip butyraldehyde-n, dropwise the back and keep constant temperature;
2) reaction solution is evacuated to another reaction kettle, adds formic acid and neutralize, concentrating under reduced pressure reclaims unreacted butyraldehyde-n;
3) add methyl alcohol, extract unreacted formaldehyde;
4) intensification and dropping ydrogen peroxide 50 dropwise the back and keep constant temperature;
5) add sulfuric acid, concentrating under reduced pressure then;
6) add ETHYLE ACETATE and make thinner, then crystallisation by cooling;
7) add that MIBK stirs, filters, concentrates, crystallization;
8) add entry, carry out recrystallization, finished product is dried, pulverizes, is sieved, packing.
2. as claimed in claim 1 a kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that said step 2) in to add mass percentage concentration be 85% formic acid, add mass percentage concentration in the said step 5) and be 10% sulfuric acid.
3. as claimed in claim 2 a kind of 2, the preparation method of 2-dimethylolpropionic acid, the raw material that it is characterized in that adding in each step is according to following parts by weight: 30-50 parts in the water that adds in the step 1), 20-35 parts in formaldehyde; 5-15 parts of butyraldehyde-ns; 0.05-0.5 part in salt of wormwood; 0.2-0.8 part in Pottasium Hydroxide; 0.2-0.6 part in formic acid; 1-7 parts of methyl alcohol; 15-25 parts in ydrogen peroxide 50; 3-15 parts in sulfuric acid; 1-8 parts in ETHYLE ACETATE; 2-15 parts of MIBKs.
4. as claimed in claim 2 a kind of 2, the preparation method of 2-dimethylolpropionic acid, the raw material that it is characterized in that adding in each step is according to following parts by weight: 35-45 parts in the water that adds in the step 1), 25-30 parts in formaldehyde; 8-12 parts of butyraldehyde-ns; 0.1-0.3 part in salt of wormwood; 0.4-0.6 part in Pottasium Hydroxide; 0.3-0.5 part in formic acid; 3-5 parts of methyl alcohol; 18-22 parts in ydrogen peroxide 50; 5-10 parts in sulfuric acid; 2-6 parts in ETHYLE ACETATE; 6-10 parts of MIBKs.
5. as claimed in claim 2 a kind of 2, the preparation method of 2-dimethylolpropionic acid, the raw material that it is characterized in that adding in each step is according to following parts by weight: 40 parts in the water that adds in the step 1), 26 parts in formaldehyde; 9.6 parts of butyraldehyde-ns; 0.2 part in salt of wormwood; 0.48 part in Pottasium Hydroxide; 0.4 part in formic acid; 4 parts of methyl alcohol; 20 parts in ydrogen peroxide 50; 8 parts in sulfuric acid; 4 parts in ETHYLE ACETATE; 8 parts of MIBKs.
6. as claimed in claim 1 a kind of 2, the preparation method of 2-dimethylolpropionic acid is characterized in that
Keep 10 ℃-30 ℃ of constant temperature in the step 1), preferred 20 ℃, drip ydrogen peroxide 50 after being warmed up to 60 ℃-80 ℃ in the step 4), dropwise the back and keep 60 ℃-80 ℃ of constant temperature, preferred 70 ℃.
7. as claimed in claim 1 a kind of 2, the preparation method of 2-dimethylolpropionic acid, the weight ratio that it is characterized in that being evaporated in the step 5) water accounts total amount is below 2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103339259A CN102816058A (en) | 2012-09-11 | 2012-09-11 | Method for preparing 2, 2-bis (hydroxymethyl) butyric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103339259A CN102816058A (en) | 2012-09-11 | 2012-09-11 | Method for preparing 2, 2-bis (hydroxymethyl) butyric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102816058A true CN102816058A (en) | 2012-12-12 |
Family
ID=47300561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103339259A Pending CN102816058A (en) | 2012-09-11 | 2012-09-11 | Method for preparing 2, 2-bis (hydroxymethyl) butyric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102816058A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558652A (en) * | 2018-06-20 | 2018-09-21 | 李先明 | A method of preparing 2,2- dimethylolpropionic acids |
| CN108658754A (en) * | 2018-06-20 | 2018-10-16 | 李先明 | A kind of device and technique of continuous production 2,2- dimethylolpropionic acids |
| CN110483277A (en) * | 2019-09-21 | 2019-11-22 | 河南精众生物科技有限公司 | The preparation method of the exquisite crystallization of dimethylolpropionic acid extraction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130719A (en) * | 1997-10-23 | 1999-05-18 | Mitsubishi Chemical Corp | Purification of dimethylolalkanal |
| JPH11228489A (en) * | 1998-02-17 | 1999-08-24 | Nippon Kasei Chem Co Ltd | Production of 2,2'-bis(hydroxymethyl)alkanoic acid |
| US6072082A (en) * | 1998-02-18 | 2000-06-06 | Nippon Kasei Chemical Company | Process for producing 2,2'-Bis(hydroxymethyl) alkanoic acid |
| CN101279912A (en) * | 2008-05-15 | 2008-10-08 | 江西南城红都化工科技开发有限公司 | Preparation of 2,2-dimethylolbutyric acid |
| CN101381299A (en) * | 2008-10-14 | 2009-03-11 | 山东轻工业学院 | Method for synthesizing 2,2-bis(hydroxymenthyl)butyric acid |
-
2012
- 2012-09-11 CN CN2012103339259A patent/CN102816058A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11130719A (en) * | 1997-10-23 | 1999-05-18 | Mitsubishi Chemical Corp | Purification of dimethylolalkanal |
| JPH11228489A (en) * | 1998-02-17 | 1999-08-24 | Nippon Kasei Chem Co Ltd | Production of 2,2'-bis(hydroxymethyl)alkanoic acid |
| US6072082A (en) * | 1998-02-18 | 2000-06-06 | Nippon Kasei Chemical Company | Process for producing 2,2'-Bis(hydroxymethyl) alkanoic acid |
| CN101279912A (en) * | 2008-05-15 | 2008-10-08 | 江西南城红都化工科技开发有限公司 | Preparation of 2,2-dimethylolbutyric acid |
| CN101381299A (en) * | 2008-10-14 | 2009-03-11 | 山东轻工业学院 | Method for synthesizing 2,2-bis(hydroxymenthyl)butyric acid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558652A (en) * | 2018-06-20 | 2018-09-21 | 李先明 | A method of preparing 2,2- dimethylolpropionic acids |
| CN108658754A (en) * | 2018-06-20 | 2018-10-16 | 李先明 | A kind of device and technique of continuous production 2,2- dimethylolpropionic acids |
| CN110483277A (en) * | 2019-09-21 | 2019-11-22 | 河南精众生物科技有限公司 | The preparation method of the exquisite crystallization of dimethylolpropionic acid extraction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102690423B (en) | Method for producing sodium lignosulphonate by utilizing residues obtained by producing ethanol with crop straws as raw materials | |
| CN106750179B (en) | A kind of preparation method of enzymolysis xylogen base epoxy | |
| CN102816058A (en) | Method for preparing 2, 2-bis (hydroxymethyl) butyric acid | |
| CN101302148B (en) | Method for producing aminic acid by glycerin water thermal reduction of CO2 | |
| CN100486953C (en) | Method for retrieving organic acid, ester from cyclic ethane oxidation liquid | |
| CN103553004A (en) | Method for continuous preparation of sodium azide | |
| CN102389829A (en) | Solid base catalyst for synthetizing aviation fuel intermediates by using furfural and acetone aldol as well as preparation method and purpose | |
| CN105085411A (en) | Preparation method of 6-hydroxy-2,3,5-triamidopyrimidine sulfate | |
| CN204079853U (en) | For the production of the reaction unit of polymethoxy dimethyl ether | |
| CN104876818A (en) | Method for reducing inorganic compound by water as hydrogen source or by molten alkali and use thereof | |
| UA119535C2 (en) | Method for producing ethylene oxide from a thermally integrated ethanol stream | |
| CN102911038A (en) | Preparation method of 2,2-dimethylolpropionic acid | |
| CN111320535A (en) | Preparation method of 3- (benzyloxy) -1-cyclobutanone | |
| CN108707064B (en) | Production method for co-producing dimethyl ether by using blast furnace gas | |
| CN101531574B (en) | Method for preparing 3,4,5-trimethoxy toluene | |
| CN102010291B (en) | Method for producing formic acid and preparing acetone through hydrothermal reduction of CO2 by isopropanol | |
| CN101607879A (en) | A kind of method of producing concentration formic acid and high and polymer phosphate sodium salt with the mixing acid acidifying sodium formate | |
| CN100398206C (en) | Catalyst for producing ethyoxyl quinoline | |
| CN102897962B (en) | Zero-discharge water recycling process used in copper-based catalyst co-precipitation production | |
| CN105669070A (en) | Aliphatic water reducer synthesized from 2-naphthol waste water and preparation method thereof | |
| CN106824996B (en) | Method for degrading biomass waste through photo-thermal coupling | |
| CN105503789A (en) | Method for catalytic conversion of xylose into furfural by use of montmorillonite-supported metal ion solid acid | |
| CN104496773A (en) | Formaldehyde and dimethyl ether co-production technique | |
| CN100355719C (en) | Salicylic acid preparing process | |
| CN202116474U (en) | Device for preparing concrete water reducer by phenolic resin wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20121212 |