CN101967081A - Process for receiving water-containing methanol solution produced in production of antioxygen 1010 - Google Patents
Process for receiving water-containing methanol solution produced in production of antioxygen 1010 Download PDFInfo
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- CN101967081A CN101967081A CN2010105078822A CN201010507882A CN101967081A CN 101967081 A CN101967081 A CN 101967081A CN 2010105078822 A CN2010105078822 A CN 2010105078822A CN 201010507882 A CN201010507882 A CN 201010507882A CN 101967081 A CN101967081 A CN 101967081A
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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 technology of the aqueous methanol solution that produces in the single stage method antioxidant 1010 production process, by this technology in can the efficient recovery aqueous methanol solution methyl alcohol and obtain the solid constituent, this solid constituent can be used as the raw material of producing antioxidant 1010.
Background technology
Antioxidant 1010, its chemical name are four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, are the particularly used a kind of primary antioxidants of polyolefins material of multiple organic substance.The method of production antioxidant 1010 is " two-step approach " normally: 2,6-di-tert-butylphenol and methyl acrylate reaction, getting intermediate after the separation purification waits processing is (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, intermediate and tetramethylolmethane carry out transesterification reaction, get antioxidant 1010 through separating after purification waits processing again.The method that " single stage method " produces antioxidant 1010 is meant above-mentioned intermediate, and direct and tetramethylolmethane carries out the method for transesterification reaction without separating processing such as purifications.
In the separation refined product operation in " single stage method " production antioxidant 1010 technology, produced the aqueous methanol solution of 3 ~ 4 times of quality producies, wherein desolventize outside water and the methyl alcohol, still contain unreacted (3, the 5-di-tert-butyl-hydroxy phenyl) the 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 recyclable utilization 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 technology 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 the solution, and obtain a kind ofly can directly using the solid constituent as the antioxidant 1010 raw materials for production
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: a kind of recovery technology 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 the reaction vessel, under agitation to wherein adding sodium hydroxide, to obtaining the neutral aqueous methanol solution;
2) dehydration: under agitation, in the neutral aqueous methanol solution of step 1) gained, add a certain amount of hexanaphthene, add thermal distillation, wherein water, methyl alcohol and hexanaphthene ternary azeotrope distillate and flow in the water trap after condenser condenses, tell wherein water and carbinol mixture, hexanaphthene refluxes, to obtaining anhydrous solution, continue to be distilled to that no hexanaphthene is not have demixing phenomenon in the water trap in the overhead product, obtain certain density methanol solution;
3) reaction: under agitation, to step 2) add catalyzer KOH in the certain density methanol solution of gained, heating reflux reaction 3 ~ 6 hours obtains the alcoholysis material;
4) neutralization is with concentrated: add Glacial acetic acid and show neutral to it in the alcoholysis material of step 3) gained, distill out the pending thing that part methyl alcohol obtains normality then;
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 continues to be cooled to 25 ℃, insulated and stirred 1.5～2 hours, continue to be cooled to 15 ℃, filter cake is filtered and washed with water to insulated and stirred 2～3 hours then, with filter cake vacuum-drying, promptly obtain the solid constituent that can directly use as " single stage method " antioxidant 1010 raw materials for production.
Press such scheme, the component and the component concentration thereof of the described solid constituent of step 5) are by mass percentage: (3, the 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 the step 1).
Press such scheme, step 2) described certain density methanol solution, be meant that the solute massfraction is 30%～35% methanol solution.
Press such scheme, the described catalyst consumption of step 3) is 0.3% ~ 0.8% of the aqueous methanol solution quality that produces of the production antioxidant 1010 described in the step 1).
Press such scheme, the pending thing of the described normality of step 4) is meant that the solute massfraction is 40%～55% methanol solution.
Press such scheme, the quality of entry that step 5) adds be the described normality of step 4) pending amount 16%～22%.
Produce the aqueous methanol solution that antioxidant 1010 produces, be meant the aqueous methanol solution that produces in " single stage method " antioxidant 1010 production technique, it is to show acidity and the aqueous methanol solution of solute massfraction between 5%～10%, and its quality group becomes: solvent partly is water 4% ~ 6%, methyl alcohol 85% ~ 90%; Solute partly is 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.5% ~ 1%, acetate and other 0.3% ~ 1%.
Advantage of the present invention mainly shows: 1. at first add a certain amount of sodium hydroxide and carry out neutralization reaction in the aqueous methanol solution of producing the antioxidant 1010 generation, its objective is the generation that can avoid hydrolysis reaction in subsequent handling under neutrallty condition; 2. in neutral antioxidant 1010 aqueous methanol solution, add a certain amount of hexanaphthene, 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 the aqueous methanol solution is gone out, purpose is that alcoholysis reaction suits to carry out under no aqueous condition; 3. in certain density absolute methanol solution, add industrial solid potassium hydroxide and make catalyzer, reflux is carried out alcoholysis reaction, neutralize with Glacial acetic acid then, add a certain amount of water after steaming a certain amount of methyl alcohol again, crystallisation by cooling goes out the solid constituent, after filtration, can obtain the solid constituent after the washing, drying, reclaim the raw materials for production that the solid constituent that obtains can directly apply to " single stage method " antioxidant 1010, make integrated the finishing of solvent recuperation and useful component recovery.
Embodiment
Following example is to the further specifying of technology of the present invention, but the present invention is including but not limited to following examples.
Embodiment 1:
The aqueous methanol solution that employed production antioxidant 1010 produces among the embodiment 1 is the filtering filtrate of crystallization in process of production and the mixture of the washing lotion behind the washing leaching cake repeatedly, and its composition through liquid-phase chromatographic analysis is: water 4.5%, methyl alcohol 88.4%; 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 3.6%, three [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.7%, acetate and other 0.5%.
The aqueous methanol solution 590g that takes by weighing the generation of production antioxidant 1010 puts into and has agitator, reflux exchanger, in the four-hole boiling flask of thermometer and water trap, it is neutral adding solid sodium hydroxide 2.8g adjusting aqueous methanol solution pH value, add hexanaphthene 35g, stirring is warming up to backflow, distillation dehydration (water wherein, methyl alcohol and hexanaphthene azeotropic distillate and flow in the water trap after condenser condenses, the upper strata hexanaphthene returns the inflow four-hole boiling flask after the layering in water trap, lower layer methanol and water reclaim), show wherein anhydrous (collecting aqueous methanol 260.9g altogether) up to no obvious layering, continue to steam that to distillate to no hexanaphthene be not have demixing phenomenon (collecting methyl alcohol and hexanaphthene 135.5g altogether) in the water trap, obtain the solute massfraction and be 31.8% methanol solution, add catalyzer industrial hydrogen potassium oxide 3.1g backflow stirring and carried out alcoholysis reaction 5 hours, add the 7.7g Glacial acetic acid again and be neutralized to neutrality, steam methyl alcohol 74g again, 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 continues 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 the filtration with water,, obtain pulverulent solids constituent 73.5g(and wherein contain (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate (promptly 3,5-methyl esters) 65.3g, the rate of recovery 80.7% the filter cake vacuum-drying after the washing; Tetramethylolmethane 6.2g, the rate of recovery 90.3%).
Embodiment 2:
The aqueous methanol solution that employed production antioxidant 1010 produces among the embodiment 2 is the filtering filtrate of crystallization in process of production and the mixture of the washing lotion behind the washing leaching cake repeatedly, and its composition through liquid-phase chromatographic analysis is: water 4.3%, methyl alcohol 87.1%; Four [β-(3, the 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.9%, acetate and other 0.9%.
Take by weighing the aqueous methanol solution 2000g that produces the antioxidant 1010 generation and put in the four-hole boiling flask that has stirring, reflux exchanger, thermometer and water trap, it is neutral adding sodium hydroxide 5.4g adjusting aqueous methanol solution pH value.Add hexanaphthene 100g, stirring is warming up to backflow, distillation dehydration (water, methyl alcohol and hexanaphthene azeotropic distillate and flow in the water trap after condenser condenses, the upper strata hexanaphthene returns the inflow four-hole boiling flask after the layering in water trap, lower layer methanol and water reclaim), show wherein anhydrous (collecting aqueous methanol 1408.2g altogether) up to no obvious layering, continue to steam that to distillate to no hexanaphthene be not have demixing phenomenon (collect altogether methyl alcohol and hexanaphthene altogether 284g) in the water trap, obtain the solute massfraction and be 34.2% methanol solution, add catalyzer industrial hydrogen potassium oxide 6.1g backflow stirring and carried out alcoholysis reaction 5.5 hours, add the 15g Glacial acetic acid again and be neutralized to neutrality, steam methyl alcohol 157.8g again, 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 continues 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 the filtration with water, the filter cake vacuum-drying with after the washing obtains pulverulent solids constituent 141.3g(and wherein contains 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 employed production antioxidant 1010 produces among the embodiment 3 is the filtering filtrate of crystallization in process of production and the mixture of the washing lotion behind the washing leaching cake repeatedly, and its composition through liquid-phase chromatographic analysis is: water 4.2%, methyl alcohol 87.1%; Four [β-(3, the 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.9%, acetate and other 1%.
The aqueous methanol solution 1322g that takes by weighing the generation of production antioxidant 1010 puts into and has stirring, reflux exchanger, in the four-hole boiling flask of thermometer and water trap, it is neutral adding solid sodium hydroxide 4.6g adjusting aqueous methanol solution pH value, add hexanaphthene 68g, stirring is warming up to backflow, distillation dehydration (water wherein, methyl alcohol and hexanaphthene azeotropic distillate and flow in the water trap after condenser condenses, the upper strata hexanaphthene returns the inflow four-hole boiling flask after the layering in water trap, lower layer methanol and water reclaim), show wherein anhydrous (collecting aqueous methanol 762g altogether) up to no obvious layering, continue to steam that to distillate to no hexanaphthene be not have demixing phenomenon (collect altogether methyl alcohol hexanaphthene altogether 273.3g) in the water trap, obtain the solute massfraction and be 32.7% methanol solution.Add catalyzer industrial hydrogen potassium oxide 5.1g and reflux to stir and carried out alcoholysis reaction 4.5 hours, add the 12.6g Glacial acetic acid again and be neutralized to neutrality, steam methyl alcohol 118g again, 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 continues 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 the filtration with water, the filter cake vacuum-drying with after the washing obtains pulverulent solids constituent 117.4g(and wherein contains 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 employed production antioxidant 1010 produces among the embodiment 4 is the filtering filtrate of crystallization in process of production and the mixture of the washing lotion behind the washing leaching cake repeatedly, and its composition through liquid-phase chromatographic analysis is: water 4.5%, methyl alcohol 89%; Four [β-(3, the 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, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.7%, acetate and other 0.8%.
Take by weighing the aqueous methanol solution 3940g that produces the antioxidant 1010 generation and put in the four-hole boiling flask that has stirring, reflux exchanger, thermometer and water trap, it is neutral adding solid sodium hydroxide 7.9g adjusting aqueous methanol solution pH value.Add hexanaphthene 290g, stirring is warming up to backflow, distillation dehydration (water wherein, methyl alcohol and hexanaphthene azeotropic distillate and flow in the water trap after condenser condenses, the upper strata hexanaphthene returns the inflow four-hole boiling flask after the layering in water trap, lower layer methanol and water reclaim), show wherein anhydrous (collecting aqueous methanol 3026g altogether) up to no obvious layering, continue to steam that to distillate to no hexanaphthene be not have demixing phenomenon (collect altogether methyl alcohol and hexanaphthene altogether 602g) in the water trap, obtain the solute massfraction and be 34.4% methanol solution, add catalyzer industrial hydrogen potassium oxide 12g backflow stirring and carried out alcoholysis reaction 4.5 hours, add the 22.5g Glacial acetic acid again and be neutralized to neutrality, steam methyl alcohol 225g again, 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 continues 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 the filtration with water, the filter cake vacuum-drying with after the washing obtains pulverulent solids constituent 209.5g(and wherein contains 3,5-methyl esters 186g, the rate of recovery 80.8%; Tetramethylolmethane 17.7g, the rate of recovery 90%).
Claims (7)
1. recovery technology 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 the reaction vessel, under agitation to wherein adding sodium hydroxide, to obtaining the neutral aqueous methanol solution;
2) dehydration: under agitation, in the neutral aqueous methanol solution of step 1) gained, add a certain amount of hexanaphthene, add thermal distillation, wherein water, methyl alcohol and hexanaphthene ternary azeotrope distillate and flow in the water trap after condenser condenses, tell wherein water and carbinol mixture, hexanaphthene refluxes, to obtaining anhydrous solution, continue to be distilled to that no hexanaphthene is not have demixing phenomenon in the water trap in the overhead product, obtain certain density methanol solution;
3) reaction: under agitation, to step 2) add catalyzer KOH in the certain density methanol solution of gained, heating reflux reaction 3～6 hours obtains the alcoholysis material;
4) neutralization is with concentrated: add Glacial acetic acid and show neutral to it in the alcoholysis material of step 3) gained, distill out the pending thing that part methyl alcohol obtains normality then;
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 continues to be cooled to 25 ℃, insulated and stirred 1.5～2 hours, continue to be cooled to 15 ℃, filter cake is filtered and washed with water to insulated and stirred 2～3 hours then, with filter cake vacuum-drying, promptly obtain the solid constituent that can directly use as " single stage method " antioxidant 1010 raw materials for production.
2. press the recovery technology of the aqueous methanol solution of the described production antioxidant 1010 generation of claim 1, the component and the component concentration thereof that it is characterized in that the described solid constituent of step 5) are by mass percentage: (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate 86%～94%, tetramethylolmethane 6%～14%.
3. the recovery technology of the aqueous methanol solution that produces by claim 1 or 2 described production antioxidant 1010s is characterized in that step 2) consumption of described hexanaphthene is 5%～15% of the aqueous methanol solution quality that produces of the production antioxidant 1010 described in the step 1).
4. press the recovery technology of the aqueous methanol solution of claim 1 or 2 described production antioxidant 1010s generations, it is characterized in that step 2) described certain density methanol solution, be meant that the solute massfraction is 30%～35% methanol solution.
5. the recovery technology of the aqueous methanol solution that produces by claim 1 or 2 described production antioxidant 1010s is characterized in that the described catalyst consumption of step 3) is 0.3%～0.8% of the aqueous methanol solution quality that produces of the production antioxidant 1010 described in the step 1).
6. press the recovery technology of the aqueous methanol solution of claim 1 or 2 described production antioxidant 1010s generations, it is characterized in that the pending thing of the described normality of step 4), be meant that the solute massfraction is 40%～55% methanol solution.
7. the recovery technology of the aqueous methanol solution that produces by the described production antioxidant 1010 of claim 6, the quality that it is characterized in that entry that step 5) adds be the described normality of step 4) pending amount 16%～22%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN108409536A (en) * | 2018-05-11 | 2018-08-17 | 山东省临沂市三丰化工有限公司 | A method of recycling pentaerythrite from the alcoholysis 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108409536A (en) * | 2018-05-11 | 2018-08-17 | 山东省临沂市三丰化工有限公司 | A method of recycling pentaerythrite from the alcoholysis liquid filter residue of antioxidant 1010 mother liquor |
| 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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