CN101967081B - Process for recovering water-containing methanol solution produced in production of antioxygen 1010 - Google Patents
Process for recovering water-containing methanol solution produced in production of antioxygen 1010 Download PDFInfo
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Abstract
The invention relates to a process for receiving water-containing methanol solution produced in the production of antioxygen 1010, which comprises the following steps: 1), neutralizing; 2) dewatering; 3) reacting to obtain alcoholysate; 4) neutralizing and concentrating; 5) crystallizing, filtering, drying and thus obtaining a solid component used as a raw material for producing antioxygen 1010 by a 'one-step' method. The invention has the main advantages that: 1, hydrolysis reaction is avoided; 2, alcoholysis reaction can be performed under an anhydrous condition; and 3, the solid component recovered can be used as the raw material for producing the antioxygen 1010 by the 'one-step' method directly, so the solvent recovery and useful component recovery are completed integrally.
Description
Technical field
The present invention relates to the recovery process of the aqueous methanol solution that produces in single stage method antioxidant 1010 production process, methyl alcohol by this technique in can the efficient recovery aqueous methanol solution also obtains the solid constituent, and this solid constituent can be used as producing the raw material of antioxidant 1010.
Background technology
Antioxidant 1010, its chemical name is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, is particularly polyolefins material a kind of primary antioxidant used of gas chromatography matter.The method of production antioxidant 1010 is " two-step approach " normally: 2, the 6-di-tert-butylphenol reacts with methyl acrylate, obtaining intermediate after the processing such as separating-purifying is (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, intermediate and tetramethylolmethane carry out transesterification reaction, then obtain antioxidant 1010 after the processing such as separating-purifying.The method that " single stage method " produces antioxidant 1010 refers to above-mentioned intermediate, and without processings such as separating-purifying, direct and tetramethylolmethane carries out the method for transesterification reaction.
In " single stage method ", produce in the separating-purifying product sequence in antioxidant 1010 technique, produced the aqueous methanol solution of 3 ~ 4 times of quality producies, wherein desolventize outside water and methyl alcohol, still contain unreacted (3, the 5-di-tert-butyl-hydroxy phenyl) intermediate product three [β-(3 of methyl propionate and tetramethylolmethane, not isolated antioxidant 1010, transesterification reaction, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] composition of the recoverable such as pentaerythritol ester, a large amount of methyl alcohol also must recycling use.
Summary of the invention
Problem to be solved by this invention is the recovery process that proposes the simple antioxidant 1010 aqueous methanol solution of a kind of less energy-consumption, process stabilizing and process, can efficient recovery methyl alcohol in solution, and obtain a kind ofly can directly as the antioxidant 1010 raw materials for production, using the solid constituent
.
The solution that problem adopts that the present invention is the above-mentioned proposition of solution is: a kind of recovery process of producing the aqueous methanol solution of antioxidant 1010 generation is characterized in that including following steps:
1) neutralization: the aqueous methanol solution that will produce the antioxidant 1010 generation joins in reaction vessel, under agitation adds wherein sodium hydroxide, to obtaining neutral aqueous methanol solution;
2) dehydration: under agitation, add a certain amount of hexanaphthene in the aqueous methanol solution of the neutrality of step 1) gained, add thermal distillation, wherein water, methyl alcohol and hexanaphthene ternary azeotrope distillate and flow in water trap after condenser condenses, separate water and carbinol mixture wherein, hexanaphthene refluxes, to obtaining anhydrous solution, continue to be distilled in overhead product without hexanaphthene be in water trap without demixing phenomenon, obtain certain density methanol solution;
3) reaction: under agitation, to step 2) in the certain density methanol solution of gained, add catalyzer KOH, heating reflux reaction 3 ~ 6 hours, obtain the alcoholysis material;
4) neutralization is with concentrated: in the alcoholysis material of step 3) gained, add Glacial acetic acid aobvious neutral to it, then distill out the pending thing that part methyl alcohol obtains normality;
5) crystallization, filtration and dry: under agitation, the pending thing of step 4) gained under agitation is cooled to 35～50 ℃, add a certain amount of water, insulated and stirred 1～2 hour, continue to be cooled to 25 ℃, insulated and stirred 1.5～2 hours, continue to be cooled to 15 ℃, insulated and stirred 2～3 hours, then filter and wash with water filter cake, by filter cake vacuum-drying, obtain the solid constituent that can directly use as " single stage method " antioxidant 1010 raw materials for production.
Press such scheme, component and the component concentration thereof of the described solid constituent of step 5) are by mass percentage: (3,5-di-tert-butyl-hydroxy phenyl) methyl propionate 86%～94%, tetramethylolmethane 6%～14%.
Press such scheme, step 2) consumption of described hexanaphthene is 5% ~ 15% of the aqueous methanol solution quality that produces of the production antioxidant 1010 described in step 1).
Press such scheme, step 2) described certain density methanol solution, refer to the methanol solution that the solute massfraction is 30%～35%.
Press such scheme, 0.3% ~ 0.8% of the aqueous methanol solution quality that the consumption of the described catalyzer of step 3) is the production antioxidant 1010 generation described in step 1).
Press such scheme, the pending thing of the described normality of step 4), refer to the methanol solution that the solute massfraction is 40%～55%.
Press such scheme, 16%～22% of the pending amount that the quality of water that step 5) adds is the described normality of step 4).
Produce the aqueous methanol solution that antioxidant 1010 produces, refer to the aqueous methanol solution produced in " single stage method " antioxidant 1010 production technique, it is aobvious acidity and the aqueous methanol solution of solute massfraction between 5%～10%, and its quality group becomes: solvent is partly water 4% ~ 6%, methyl alcohol 85% ~ 90%; Solute is partly four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2% ~ 3%, (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 3% ~ 4%(is 3, the 5-methyl esters), three [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.5% ~ 1%, acetate and other 0.3% ~ 1%.
Advantage of the present invention is mainly manifested in: 1. at first in the aqueous methanol solution of producing the antioxidant 1010 generation, add a certain amount of sodium hydroxide to carry out neutralization reaction, its objective is the generation that can avoid hydrolysis reaction in subsequent handling under neutrallty condition; 2. add a certain amount of hexanaphthene in neutral antioxidant 1010 aqueous methanol solution, rely on the azeotropic characteristic of water, methyl alcohol and hexanaphthene to carry out distillation dehydration, thereby can obtain certain density absolute methanol solution, before alcoholysis, the moisture in aqueous methanol solution is gone out, purpose is that alcoholysis reaction is suitable to without carrying out under aqueous condition; 3. in certain density absolute methanol solution, add industrial solid potassium hydroxide to make catalyzer, reflux is carried out alcoholysis reaction, then with Glacial acetic acid, neutralized, add a certain amount of water after steaming again a certain amount of methyl alcohol, crystallisation by cooling goes out the solid constituent, after filtration, can obtain the solid constituent after washing, drying, reclaim the raw materials for production that the solid constituent obtained can directly apply to " single stage method " antioxidant 1010, make solvent recuperation and integrated the completing of useful component recovery.
Embodiment
Following instance is to the further illustrating of technique of the present invention, but the present invention is including but not limited to following examples.
Embodiment 1:
The aqueous methanol solution that the production antioxidant 1010 that uses in embodiment 1 produces is the filtrate of filtering of crystallization in process of production and the mixture of the washing lotion after washing leaching cake repeatedly, and its composition through liquid-phase chromatographic analysis is: water 4.5%, methyl alcohol 88.4%; Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2.3%, (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 3.6%, three [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.7%, acetate and other 0.5%.
Taking the aqueous methanol solution 590g that produces the antioxidant 1010 generation puts into agitator, reflux exchanger, in the four-hole boiling flask of thermometer and water trap, add solid sodium hydroxide 2.8g to regulate aqueous methanol solution pH value for neutral, add hexanaphthene 35g, stirring is warming up to backflow, distillation dehydration (water wherein, methyl alcohol and hexanaphthene azeotropic distillate and flow in water trap after condenser condenses, in water trap, after layering, the upper strata hexanaphthene returns to the inflow four-hole boiling flask, lower layer methanol and water are reclaimed), until show wherein anhydrous (collecting altogether aqueous methanol 260.9g) without obvious layering, continuing to steam to distillating without hexanaphthene is without demixing phenomenon (collecting altogether methyl alcohol and hexanaphthene 135.5g) in water trap, obtain the methanol solution that the solute massfraction is 31.8%, add Catalyst potassium hydroxide 3.1g return stirring to carry out alcoholysis reaction 5 hours, add again the 7.7g Glacial acetic acid to be neutralized to neutrality, steam again methyl alcohol 74g, obtain the solute massfraction and be 43.6% pending thing 168.2g.Under agitation slowly cool to 45 ℃, add 36.2g water, insulated and stirred 2 hours, continue to be cooled to 25 ℃, and insulated and stirred 2 hours continues to be cooled to 15 ℃, insulated and stirred 2 hours.Wash filter cake after filtration with water, by the filter cake vacuum-drying after washing, obtain pulverulent solids constituent 73.5g(wherein containing (3,5-di-tert-butyl-hydroxy phenyl) methyl propionate (3,5-methyl esters) 65.3g, the rate of recovery 80.7%; Tetramethylolmethane 6.2g, the rate of recovery 90.3%).
Embodiment 2:
The aqueous methanol solution that the production antioxidant 1010 that uses in embodiment 2 produces is the filtrate of filtering of crystallization in process of production and the mixture of the washing lotion after washing leaching cake repeatedly, and its composition through liquid-phase chromatographic analysis is: water 4.3%, methyl alcohol 87.1%; Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3%, (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 3.8%, three [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.9%, acetate and other 0.9%.
Take the aqueous methanol solution 2000g that produces the antioxidant 1010 generation and put in the four-hole boiling flask with stirring, reflux exchanger, thermometer and water trap, add sodium hydroxide 5.4g to regulate aqueous methanol solution pH value for neutral.Add hexanaphthene 100g, stirring is warming up to backflow, distillation dehydration (water, methyl alcohol and hexanaphthene azeotropic distillate and flow in water trap after condenser condenses, in water trap, after layering, the upper strata hexanaphthene returns to the inflow four-hole boiling flask, lower layer methanol and water are reclaimed), until show wherein anhydrous (collecting altogether aqueous methanol 1408.2g) without obvious layering, continuing to steam to distillating without hexanaphthene is without demixing phenomenon (collecting altogether methyl alcohol and hexanaphthene 284g altogether) in water trap, obtain the methanol solution that the solute massfraction is 34.2%, add Catalyst potassium hydroxide 6.1g return stirring to carry out alcoholysis reaction 5.5 hours, add again the 15g Glacial acetic acid to be neutralized to neutrality, steam again methyl alcohol 157.8g, obtain the solute massfraction and be 51.1% pending thing 276.5g.Under agitation slowly cool to 40 ℃, add 47g water, insulated and stirred 1 hour, continue to be cooled to 25 ℃, and insulated and stirred 2 hours continues to be cooled to 15 ℃, insulated and stirred 3 hours.Wash filter cake after filtration with water, by the filter cake vacuum-drying after washing, obtain pulverulent solids constituent 141.3g(wherein containing 3,5-methyl esters 125g, the rate of recovery 81%; Tetramethylolmethane 11.8g, the rate of recovery 90.2%).
Embodiment 3:
The aqueous methanol solution that the production antioxidant 1010 that uses in embodiment 3 produces is the filtrate of filtering of crystallization in process of production and the mixture of the washing lotion after washing leaching cake repeatedly, and its composition through liquid-phase chromatographic analysis is: water 4.2%, methyl alcohol 87.1%; Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3%, (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 3.8%, three [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.9%, acetate and other 1%.
Taking the aqueous methanol solution 1322g that produces the antioxidant 1010 generation puts into stirring, reflux exchanger, in the four-hole boiling flask of thermometer and water trap, add solid sodium hydroxide 4.6g to regulate aqueous methanol solution pH value for neutral, add hexanaphthene 68g, stirring is warming up to backflow, distillation dehydration (water wherein, methyl alcohol and hexanaphthene azeotropic distillate and flow in water trap after condenser condenses, in water trap, after layering, the upper strata hexanaphthene returns to the inflow four-hole boiling flask, lower layer methanol and water are reclaimed), until show wherein anhydrous (collecting altogether aqueous methanol 762g) without obvious layering, continuing to steam to distillating without hexanaphthene is without demixing phenomenon (collecting altogether methyl alcohol hexanaphthene 273.3g altogether) in water trap, obtain the methanol solution that the solute massfraction is 32.7%.Add Catalyst potassium hydroxide 5.1g return stirring to carry out alcoholysis reaction 4.5 hours, then add the 12.6g Glacial acetic acid to be neutralized to neutrality, then steam methyl alcohol 118g, obtain the solute massfraction and be 44.3% pending thing 259g.Under agitation slowly cool to 45 ℃, add 44g water, insulated and stirred 2 hours, continue to be cooled to 25 ℃, and insulated and stirred 1.5 hours continues to be cooled to 15 ℃, insulated and stirred 2 hours.Wash filter cake after filtration with water, by the filter cake vacuum-drying after washing, obtain pulverulent solids constituent 117.4g(wherein containing 3,5-methyl esters 106.8g, the rate of recovery 80.3%; Tetramethylolmethane 7.4g, the rate of recovery 91.1%).
Embodiment 4:
The aqueous methanol solution that the production antioxidant 1010 that uses in embodiment 4 produces is the filtrate of filtering of crystallization in process of production and the mixture of the washing lotion after washing leaching cake repeatedly, and its composition through liquid-phase chromatographic analysis is: water 4.5%, methyl alcohol 89%; Four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2.6%, (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 3.1%, three [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.7%, acetate and other 0.8%.
Take the aqueous methanol solution 3940g that produces the antioxidant 1010 generation and put in the four-hole boiling flask with stirring, reflux exchanger, thermometer and water trap, add solid sodium hydroxide 7.9g to regulate aqueous methanol solution pH value for neutral.Add hexanaphthene 290g, stirring is warming up to backflow, distillation dehydration (water wherein, methyl alcohol and hexanaphthene azeotropic distillate and flow in water trap after condenser condenses, in water trap, after layering, the upper strata hexanaphthene returns to the inflow four-hole boiling flask, lower layer methanol and water are reclaimed), until show wherein anhydrous (collecting altogether aqueous methanol 3026g) without obvious layering, continuing to steam to distillating without hexanaphthene is without demixing phenomenon (collecting altogether methyl alcohol and hexanaphthene 602g altogether) in water trap, obtain the methanol solution that the solute massfraction is 34.4%, add Catalyst potassium hydroxide 12g return stirring to carry out alcoholysis reaction 4.5 hours, add again the 22.5g Glacial acetic acid to be neutralized to neutrality, steam again methyl alcohol 225g, obtain the solute massfraction and be 50.5% pending thing 419.4g.Under agitation slowly cool to 45 ℃, add 85g water, insulated and stirred 2 hours, continue to be cooled to 25 ℃, and insulated and stirred 2 hours continues to be cooled to 15 ℃, insulated and stirred 2 hours.Wash filter cake after filtration with water, by the filter cake vacuum-drying after washing, obtain pulverulent solids constituent 209.5g(wherein containing 3,5-methyl esters 186g, the rate of recovery 80.8%; Tetramethylolmethane 17.7g, the rate of recovery 90%).
Claims (2)
1. a recovery process of producing the aqueous methanol solution that antioxidant 1010 produces is characterized in that including following steps:
1) neutralization: the aqueous methanol solution that will produce the antioxidant 1010 generation joins in reaction vessel, under agitation adds wherein sodium hydroxide, to obtaining neutral aqueous methanol solution;
2) dehydration: under agitation, add a certain amount of hexanaphthene in the aqueous methanol solution of the neutrality of step 1) gained, 5%～15% of the aqueous methanol solution quality that the consumption of described hexanaphthene is the production antioxidant 1010 generation described in step 1), add thermal distillation, water wherein, methyl alcohol and hexanaphthene ternary azeotrope distillate and flow in water trap after condenser condenses, separate water and carbinol mixture wherein, hexanaphthene refluxes, to obtaining anhydrous solution, continuing to be distilled in overhead product is without demixing phenomenon in water trap without hexanaphthene, obtain certain density methanol solution, described certain density methanol solution, refer to the methanol solution that the solute massfraction is 30%～35%,
3) reaction: under agitation, to step 2) in the certain density methanol solution of gained, add catalyzer KOH, heating reflux reaction 3～6 hours, obtain the alcoholysis material;
4) neutralization is with concentrated: in the alcoholysis material of step 3) gained, add Glacial acetic acid aobvious neutral to it, then distill out the pending thing that part methyl alcohol obtains normality, the pending thing of described normality, refer to the methanol solution that the solute massfraction is 40%～55%;
5) crystallization, filter with dry: under agitation, the pending thing of step 4) gained under agitation is cooled to 35～50 ℃, add a certain amount of water, add 16%～22% of pending amount that the quality of water is the described normality of step 4), insulated and stirred 1～2 hour, continue to be cooled to 25 ℃, insulated and stirred 1.5～2 hours, continue to be cooled to 15 ℃, insulated and stirred 2～3 hours, then filter and wash with water filter cake, by filter cake vacuum-drying, obtain the solid constituent that can directly use as " single stage method " antioxidant 1010 raw materials for production, the component of described solid constituent and component concentration thereof are by mass percentage: (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 86%～94%, tetramethylolmethane 6%～14%.
2. the recovery process of the aqueous methanol solution produced by production antioxidant 1010 claimed in claim 1,0.3%～0.8% of the aqueous methanol solution quality that the consumption that it is characterized in that the described catalyzer of step 3) is the production antioxidant 1010 generation described in step 1).
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| CN103641715A (en) * | 2013-11-21 | 2014-03-19 | 山东省临沂市三丰化工有限公司 | Method for recovering filter residue in antioxidant production process |
| CN108409536B (en) * | 2018-05-11 | 2021-01-15 | 山东省临沂市三丰化工有限公司 | Method for recovering pentaerythritol from alcohol hydrolysis liquid filter residue of antioxidant 1010 mother liquor |
| CN111334300A (en) * | 2020-04-01 | 2020-06-26 | 辽宁石化职业技术学院 | Preparation method of double-effect antioxidant |
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