CN1026104C - Waste oil reproducing process for acrylate ester - Google Patents
Waste oil reproducing process for acrylate ester Download PDFInfo
- Publication number
- CN1026104C CN1026104C CN 92101702 CN92101702A CN1026104C CN 1026104 C CN1026104 C CN 1026104C CN 92101702 CN92101702 CN 92101702 CN 92101702 A CN92101702 A CN 92101702A CN 1026104 C CN1026104 C CN 1026104C
- Authority
- CN
- China
- Prior art keywords
- reactor
- waste oil
- acrylate
- rectifying tower
- rectifying
- 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.)
- Revoked
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a technology for regenerating acrylic ester waste oil. The present invention uses waste oil for producing acrylic ester in great industry as raw materials, the waste oil contains alkoxy-propionic acid-alkyl ester, catalytic reaction is carried out in a third reaction kettle, the temperature of catalytic reaction is above the boiling point of the acrylic acid alkyl ester, the internal pressure of the reaction kettle is from 0.5 to 1 atmospheric pressure, catalysts are added for generating dealcoholization reaction, amd finally, acrylic acid alkyl ester with the purity of 95 to 99.95% is obtained through rectification in a rectifying tower. The present invention has the advantages of high yield of recovered products, high purity of recovered products and simple technology.
Description
The present invention relates to not form in the organic chemistry field, particularly waste oil reproducing process for acrylate ester that contain the reaction of heteroatom functional group.
Contain the 75(weight of having an appointment in the waste oil that in acrylate production, produces) the alkoxypropan acid alkyl ester of %, corresponding alkyl acrylate 5(weight) %, the about 20(weight of other impurity and water) %.These waste oil generally discard need not or be done to burn processing, and many useful matteies are not used, and has polluted environment, and has reduced the big economic performance of industrial enterprises of acrylate.Do not see at present easy processing esters of acrylic acid oil salvage method yet.
The object of the invention is: a kind of waste oil reproducing process for acrylate ester is provided, and this technology can propose corresponding acrylate with simple process from waste oil.
The present invention seeks to reach like this: the component content of the esters of acrylic acid waste oil of the raw material that is used as following (weight) %;
Alkoxypropan acid alkyl ester (ROCH
2CH
2COOR) ... 75
Alkyl acrylate (CH
2=CHCOOR) ... 5
More than the R base of two kinds of compositions identical, R is methyl, ethyl, normal-butyl, iso-octyl or hydroxyethyl;
Other impurity and water ... 20
Above raw material is carried out 3 grades of catalyzed reactions in No. 1 reactor, No. 2 reactors and No. 3 reactors, catalyzed reaction is with sulfuric acid (98%H
2SO
4) as catalyzer, the catalytic amount that is added from No. 1 reactor to 3 reactor is 1: 125 in proper order; 1: 250; 1: the 500(weight ratio), make the generation dealcoholization, in rectifying tower, carry out rectifying at last, catalyzed reaction temperature and rectification temperature are higher than the boiling point of corresponding alkyl acrylate, pressure is 0.5～1 normal atmosphere between reactor and rectifying tower, obtain the alkyl acrylate of 95～99.5% purity at last, its reaction formula is as follows:
R is methyl, ethyl, normal-butyl, iso-octyl or hydroxyethyl in the formula, and by product is an alkyl alcohol.
From accompanying drawing 1 as seen, in No. 1 reactor, add esters of acrylic acid waste oil and as the sulfuric acid (H of catalyzer
2SO
4) its part by weight is 125: 1, generate the esters of acrylic acid of 50～60% purity after the catalyzed reaction, enter reactor No. 2, add above-mentioned catalyzer, its part by weight is 250: 1, in No. 2 stills, generate the esters of acrylic acid of 65～70% purity after the catalyzed reaction, enter No. 3 reactor reactions, all the other unreacteds or not reactant return still No. 1, in No. 3 stills, add with the feed weight ratio be that 500: 1 above-mentioned catalyzer carries out catalyzed reaction, No. 3 still also can have 2, and accompanying drawing 1 is exactly the example that is equipped with 2 No. 3 reactors, generates the esters of acrylic acid of 75～80% purity behind No. 3 still internal reactions, all the other unreacteds or not reactant return still No. 1, enter rectifying tower rectifying then, rectifying tower can have 2, and accompanying drawing 1 is exactly the example that is equipped with 2 rectifying tower.The Heating temperature of reactor and rectifying tower is on the boiling point of this acrylate respectively, reactor and rectifying tower internal pressure are 0.5～1 normal atmosphere, produce 95～99.5% pure useless alkyl acrylates at last, the byproduct alkyl alcohol that produces concentrates in together or makes and enters still No. 3, and press molecular weight with vinylformic acid and calculate mixed continuation reaction, generate corresponding alkyl acrylate.
According to the difference of the alkyl R in the alkyl acrylate, its catalytic temperature is also slightly variant, has nothing in common with each other at the boiling point for them.Catalytic temperature is seen the literary composition back as table 1:(table 1)
Esters of acrylic acid waste oil recovery process of the present invention has many advantages:
1) employing repeatedly adds catalyzed reaction, improves yield, and final purity reaches 95～99.5%;
2) technology is simple, is convenient to operation;
3) make waste oil regeneration, increase economic efficiency, reduce environmental pollution.
Embodiment 1:
With art breading n-butyl acrylate waste oil of the present invention, use 2 of No. 1 reactor and No. 2 each one, No. 3 reactors of reactor, all be 2 tons of capacity, 2 on rectifying tower, high 12 meters, n-butyl acrylate waste oil and vitriol oil part by weight are 125: 1 at the 1st reactor, the 2nd reactor, the 3rd reactor in proper order; 250: 1; 500: 1.N-butyl acrylate waste oil is 2012 kilograms, and the vitriol oil is successively used totally 28.7 kilograms of 16.5+8.2+4 kilograms in three reactors.In 3 reactors, the catalyzed reaction temperature sequence is 210 ℃, and 190 ℃, 158 ℃, temperature is 158 ℃ at the bottom of the rectifying tower, 149 ℃ of top temperature.Reactor and rectifying tower internal pressure are 0.8 kg/cm.Obtain 206 kilograms of 1100 kilograms of n-butyl acrylates (purity 97.5%) and propyl carbinols.Reaction formula is as follows:
Embodiment 2:
Handle methyl acrylate waste oil with waste oil recovery process of the present invention.Use each one of No. 1 reactor and No. 2 reactor, 2 of No. 3 reactors all are 2 tons of capacity, and 2 on rectifying tower is high 12 meters.Methyl acrylate waste oil and vitriol oil part by weight are 125: 1 at the 1st reactor, the 2nd reactor the 3rd reactor in proper order; 250: 1; 500: 1.Methyl acrylate waste oil is 2010 kilograms, and the vitriol oil is used totally 28.5 kilograms of 16.4+8+4.5 kilograms in proper order in three reactors.In 3 reactors, the catalyzed reaction temperature sequence is: 170 ℃; 145 ℃; 100 ℃, at the bottom of the rectifying Tata 100 ℃, 85 ℃ of cats head.Reactor and rectifying tower internal pressure are 0.6 kg/cm, obtain 1103 kilograms of methyl acrylates (purity 98.4%), 204 kilograms of methyl alcohol.Its reaction formula is as follows:
Embodiment 3:
Handle ethyl propenoate waste oil with waste oil recovery process of the present invention.Equipment and catalyzer vitriol oil consumption are identical with embodiment 1 and 2.2006 kilograms in vinylformic acid acetate waste oil, the vitriol oil successively add 16 kilograms+8 kilograms+4 kilograms totally 28 kilograms, and in three reactors, the catalyzed reaction temperature sequence is 180 ℃; 160 ℃; 118 ℃, at the bottom of the rectifying Tata 120 ℃, 102 ℃ of cats head.Reactor and rectifying tower internal pressure are 0.7 kg/cm, obtain 1099 kilograms of ethyl propenoates (purity 98.9%), 200 kilograms of ethanol, and its reaction formula is as follows:
Embodiment 4:
Identical with embodiment 1 and 2 with waste oil recovery process processing Isooctyl acrylate monomer waste oil equipment of the present invention and waste oil to vitriol oil ratio.Isooctyl acrylate monomer waste oil is 2024 kilograms, and the vitriol oil successively adds 16.5 kilograms+8 kilograms+4.5 kilograms totally 29 kilograms, and in three reactors, the catalyzed reaction temperature sequence is 270 ℃; 240 ℃; 225 ℃, at the bottom of the rectifying Tata 225 ℃, 219 ℃ of cats head.Reactor and rectifying tower internal pressure are 0.8 kg/cm, obtain 1108 kilograms of Isooctyl acrylate monomers (purity 98.7%), 210 kilograms of isooctyl alcohol, and its reaction formula is as follows:
Embodiment 5:
Handle Hydroxyethyl acrylate waste oil with waste oil recovery process of the present invention.Equipment is identical with embodiment 1 to vitriol oil ratio with waste oil.Reactor and rectifying tower internal pressure are 0.8 kg/cm, and 2020 kilograms in vinylformic acid 2-hydroxyl ethyl ester waste oil, the vitriol oil successively add 16.5 kilograms+8 kilograms+4.5 kilograms totally 29 kilograms.In three reactors, the catalyzed reaction temperature sequence is 160 ℃; 140 ℃; 90 ℃, at the bottom of the rectifying Tata 90 ℃, 77 ℃ of cats head.Obtain 205 kilograms of vinylformic acid 2-hydroxyl ethyl ester 1102 kilograms (purity 98%) and hydroxyl ethanol, its reaction formula is as follows:
＊CH
2OCHOCH
2CH
2COOCHOCH
2CH
2＝CHCOOCHOCH
2+CH
2OCHOH
Claims (6)
1, acrylate oil salvage technology is characterized in that: as the component content following (weight %) of the acrylate of raw material:
Alkoxypropan acid alkyl ester (ROCH
2CH
2COOR) ... 75
Alkyl acrylate (CH
2=CHCOOR) ... 5
More than the R base of two kinds of compositions identical, R is methyl, ethyl, normal-butyl, iso-octyl or hydroxyethyl;
Other impurity and water ... 20
Above raw material is carried out 3 grades of catalyzed reactions in No. 1 reactor, No. 2 reactors and No. 3 reactors, catalyzed reaction is with sulfuric acid (98%H
2SO
4) as catalyzer, be 1: 125 in proper order from No. 1 reactor and catalytic amount that No. 3 reactor added; 1: 250; 1: 500 (weight ratio), make the generation dealcoholization, in rectifying tower, carry out rectifying at last, catalyzed reaction temperature and rectification temperature are higher than the boiling point of corresponding alkyl acrylate, pressure is 0.5～1 normal atmosphere between reactor and rectifying tower, obtain the alkyl acrylate of 95～99.5% purity at last, its reaction formula is as follows:
R is methyl, ethyl, normal-butyl, iso-octyl or hydroxyethyl in the formula.
2, according to the said technology of claim 1, it is characterized in that: when handling n-butyl acrylate waste oil, from the catalyzed reaction temperature sequence of No. 1 reactor to 3 reactor be: 210 ℃; 190 ℃ and 158 ℃, 149 ℃ of rectifying tower cats head, at the bottom of the tower 158 ℃, reactor and rectifying tower internal pressure are 0.8 kg/cm, obtain n-butyl acrylate and propyl carbinol.
3, according to the said technology of claim 1, it is characterized in that: when handling methyl acrylate waste oil, from the catalyzed reaction temperature sequence of No. 1 reactor to 3 reactor be: 170 ℃; 145 ℃; 100 ℃, at the bottom of the rectifying Tata 100 ℃, 85 ℃ of cats head, reactor and rectifying tower internal pressure are 0.6 kg/cm, obtain vinylformic acid formic acid and methyl alcohol.
4, according to the said technology of claim 1, it is characterized in that: when handling ethyl propenoate waste oil, from the catalyzed reaction temperature sequence of No. 1 reactor to 3 reactor be: 180 ℃; 160 ℃; 118 ℃, at the bottom of the rectifying Tata 120 ℃, 102 ℃ of cats head, reactor and rectifying tower internal pressure are 0.7 kg/cm, obtain ethyl propenoate and ethanol.
5, according to the said technology of claim 1, it is characterized in that: when handling Isooctyl acrylate monomer waste oil, from the catalyzed reaction temperature sequence of No. 1 reactor to 3 reactor be: 270 ℃; 240 ℃; 225 ℃, at the bottom of the rectifying Tata 225 ℃, 219 ℃ of cats head, reactor and rectifying tower internal pressure are 0.8 kg/cm, obtain Isooctyl acrylate monomer and isooctyl alcohol.
6, according to the said technology of claim 1, it is characterized in that: when handling Hydroxyethyl acrylate waste oil, from the catalyzed reaction temperature sequence of No. 1 reactor to 3 reactor be: 160 ℃; 140 ℃; 90 ℃, at the bottom of the rectifying Tata 90 ℃, 77 ℃ of cats head, reactor and rectifying tower internal pressure are 0.9 kg/cm, obtain vinylformic acid 2-hydroxyl ethyl ester and hydroxyl ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101702 CN1026104C (en) | 1992-03-17 | 1992-03-17 | Waste oil reproducing process for acrylate ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101702 CN1026104C (en) | 1992-03-17 | 1992-03-17 | Waste oil reproducing process for acrylate ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063678A CN1063678A (en) | 1992-08-19 |
| CN1026104C true CN1026104C (en) | 1994-10-05 |
Family
ID=4939261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92101702 Revoked CN1026104C (en) | 1992-03-17 | 1992-03-17 | Waste oil reproducing process for acrylate ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1026104C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19536184A1 (en) | 1995-09-28 | 1997-04-03 | Basf Ag | Process for the esterification of (meth) acrylic acid with an alkanol |
| DE19536191A1 (en) * | 1995-09-28 | 1997-04-03 | Basf Ag | Process for the esterification of (meth) acrylic acid with an alkanol |
| DE19536183A1 (en) * | 1995-09-28 | 1997-04-03 | Basf Ag | Process for the preparation of alkyl esters of (meth) acrylic acid |
| DE19547485A1 (en) | 1995-12-19 | 1996-05-09 | Basf Ag | Methacrylic] acid esterification with alkanol for alkyl methacrylate] |
| DE19547459A1 (en) | 1995-12-19 | 1996-07-25 | Basf Ag | Esterifying (meth)acrylic acid with alkanol in presence of esterification catalyst |
| DE10127941A1 (en) | 2001-06-08 | 2002-05-29 | Basf Ag | Production of (meth)acrylate esters by transesterification comprises recycling by-product alcohol to the production of the starting (meth)acrylate |
| CN100398505C (en) * | 2006-07-28 | 2008-07-02 | 沈福昌 | Treatment method of acrylic acid and esters waste oil resource |
| EP4015498B1 (en) | 2020-12-18 | 2024-04-24 | Basf Se | Method for the continuous production of acrylic acid n-butylester |
| FR3126416B1 (en) | 2021-08-25 | 2023-07-14 | Arkema France | IMPROVED PROCESS FOR MANUFACTURING HIGH PURITY BUTYL ACRYLATE |
| FR3128459B1 (en) | 2021-10-25 | 2023-09-22 | Arkema France | HIGH PURITY BUTYL ACRYLATE |
| FR3141174B1 (en) | 2022-10-19 | 2024-09-06 | Arkema France | IMPROVED PROCESS FOR THE MANUFACTURE OF HIGH PURITY BUTYL ACRYLATE |
-
1992
- 1992-03-17 CN CN 92101702 patent/CN1026104C/en not_active Revoked
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063678A (en) | 1992-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1026104C (en) | Waste oil reproducing process for acrylate ester | |
| CN1041410C (en) | High yield process for the production of methacylic acid esters | |
| CN1280119A (en) | Method for producing carboxylic acid and alcohol | |
| CN1696082A (en) | Method for treating water reacted from Fischer-Tropsch synthesis | |
| DE102007031473A1 (en) | Process for the preparation of ethylene glycol dimethacrylate | |
| EP2162423A1 (en) | Method for producing (meth)acrylates | |
| CN101056841A (en) | Method for preparing asymmetric linear carbonate | |
| CN104053642B (en) | The method of vinylformic acid 2-octyl group ester is prepared by transesterify | |
| CN1058390A (en) | The treatment process of waste liquid containing alkoxyl propionic ester | |
| US20230183163A1 (en) | Method for preparing alkyl carboxylic acid ester and apparatus for preparing alkyl carboxylic acid ester | |
| CN1305833C (en) | Method for producing a hydroxyacid esters | |
| CN1054117C (en) | Method for producing alkyl acrylate or alkyl methacrylate | |
| CN1325840A (en) | Process for preparing ethyl acetate | |
| CN1468835A (en) | Ester exchange process of methyl acetate to prepare fatty alcohol acetate | |
| CN1089333C (en) | Synthetic method of isotridecyl fatty acid ester | |
| CN1283615C (en) | Synthesis method of asymmetric carbonate ester | |
| CN1194958C (en) | Method of using methyl acetate and aliphatic alcohol as raw material to prepare corresponding acetic alcohol acetate | |
| CN1125810C (en) | Process for producing formamide | |
| JPH09235244A (en) | Transesterification | |
| CN1280129A (en) | Directly synthesizing technology for rare earth organic compounds | |
| JPH0713050B2 (en) | Method for producing dimethylaminoethyl acrylate | |
| CN1660767A (en) | Method for preparing 3-methoxy methyl propionate | |
| US10954182B2 (en) | Reactive distillation process/equipment for fatty acid ester hydrolysis to produce carboxylic acid and alcohol | |
| CN117263802B (en) | Recycling recovery method of methyl methacrylate production waste liquid | |
| CN104053643A (en) | Method For The Production Of 2-octyl Acrylate By Means Of Transesterification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C28 | Revocation of patent right or utility model | ||
| RW01 | Full revocation of patent right |