CN1063678A - Waste oil reproducing process for acrylate ester - Google Patents
Waste oil reproducing process for acrylate ester Download PDFInfo
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- CN1063678A CN1063678A CN 92101702 CN92101702A CN1063678A CN 1063678 A CN1063678 A CN 1063678A CN 92101702 CN92101702 CN 92101702 CN 92101702 A CN92101702 A CN 92101702A CN 1063678 A CN1063678 A CN 1063678A
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- reactor
- acrylate
- waste oil
- rectifying
- catalyzed reaction
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Abstract
The present invention relates to waste oil reproducing process for acrylate ester.The present invention uses the waste oil of big industrial production acrylate as raw material, this waste oil contains the alkoxypropan acid alkyl ester, in the third order reaction still, carry out catalyzed reaction, the catalyzed reaction temperature is higher than the respectively boiling point of this alkyl acrylate, reacting kettle inner pressure is 0.5～1 normal atmosphere, add catalyzer and make the generation dealcoholization, last again in rectifying tower rectifying obtain the alkyl acrylate of 95～99.5% purity.The present invention reclaims the yield and the purity height of product, and technology is simple.
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.Like this, from the waste oil of above any alkyl acrylate with regard to recyclable corresponding alkyl acrylate, thereby the object of the invention has just reached fully.
The present invention is described in detail below in conjunction with accompanying drawing and embodiment.
Accompanying drawing 1 is a process flow sheet of the present invention.
The used esters of acrylic acid waste oil of the present invention raw material is that the big industrial production of acrylate factory discards the waste oil that maybe will burn, this waste oil is according to the original esters of acrylic acid of producing and the ingredient difference, the waste oil of for example producing methyl acrylate and being produced only contains methoxypropionic acid methyl esters and a small amount of methyl acrylate, can only the acrylic acid methyl esters with this waste oil.Used waste oil composition of the present invention and content (weight) % are as follows:
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
With above esters of acrylic acid waste oil No. 1 reactor, No. 2 reactors and and No. 3 reactors in carry out 3 grades of catalyzed reactions, as catalyzer, the catalytic amount that is added from No. 1 reactor to 3 reactor is 1: 125 to catalyzed reaction in proper order with sulfuric acid (98%H SO); 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, entering No. 3 reactors reacts, 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, accompanying drawing 1 is exactly the example that is equipped with 2 No. 3 reactors, behind No. 3 still internal reactions, generate the esters of acrylic acid of 75～80% purity, 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, because their boiling point has nothing in common with each other.Catalytic temperature such as table 1:
Table 1
| No. 1 still | No. 2 stills | No. 3 stills | Rectifying tower | ||
| The top temperature | End temperature | ||||
| Methyl acrylate | 115～175℃ | 90～155℃ | 85～135℃ | <82℃ | 85～135℃ |
| Ethyl propenoate | 135～195℃ | 110～175℃ | 105～155℃ | <103℃ | 105～175℃ |
| N-butyl acrylate | 180～220℃ | 153～200℃ | 148～180℃ | <150℃ | 148～180℃ |
| Isooctyl acrylate monomer | 248～288℃ | 220～268℃ | 216～265℃ | <215℃ | 216～265℃ |
| Propylene 2-hydroxyl ethyl ester | 110～170℃ | 85～150℃ | 80～130℃ | <78℃ | 80～130℃ |
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 ℃, 190 ℃, and 158 ℃, 158 ℃ of rectifying tower top temperature, 149 ℃ of end 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 ethyl propenoate 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:
Handle Isooctyl acrylate monomer waste oil with waste oil recovery process of the present invention.Equipment and waste oil are identical with embodiment 1 and 2 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-hydroxyethanoic acid 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:
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=CHOOR) ... 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 the catalytic amount that is added to reactor to 3 reactor for No. 1; 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 ℃, at the bottom of the rectifying Tata 149 ℃, 158 ℃ of cats head.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 methyl acrylate 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 ℃, 97 ℃ 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 true CN1063678A (en) | 1992-08-19 |
| CN1026104C 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) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0765860A1 (en) | 1995-09-28 | 1997-04-02 | Basf Aktiengesellschaft | Process for esterifying (meth)acrylic acid with an alcanol |
| EP0780360A1 (en) | 1995-12-19 | 1997-06-25 | Basf Aktiengesellschaft | Esterification process of (meth)acrylic acid with an alcanol |
| EP0780359A1 (en) | 1995-12-19 | 1997-06-25 | Basf Aktiengesellschaft | Esterification process of (meth)acrylic acid with an alcanol |
| US5763643A (en) * | 1995-09-28 | 1998-06-09 | Basf Aktiengesellschaft | Preparation of alkyl esters of (meth)acrylic acid |
| US5910603A (en) * | 1995-09-28 | 1999-06-08 | Basf Aktiengesellschaft | Esterification of (meth)acrylic acid with an alkanol |
| US7026503B2 (en) | 2001-06-08 | 2006-04-11 | Basf Aktiengesellschaft | Method for producing (meth)acrylic acid esters |
| CN100398505C (en) * | 2006-07-28 | 2008-07-02 | 沈福昌 | Treatment method of acrylic acid and esters waste oil resource |
| EP4015498A1 (en) | 2020-12-18 | 2022-06-22 | Basf Se | Method for the continuous production of acrylic acid n-butylester |
| WO2023025999A1 (en) | 2021-08-25 | 2023-03-02 | Arkema France | Improved method for producing high-purity butyl acrylate |
| FR3128459A1 (en) | 2021-10-25 | 2023-04-28 | Arkema France | HIGH PURITY BUTYL ACRYLATE |
-
1992
- 1992-03-17 CN CN 92101702 patent/CN1026104C/en not_active Revoked
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0765860A1 (en) | 1995-09-28 | 1997-04-02 | Basf Aktiengesellschaft | Process for esterifying (meth)acrylic acid with an alcanol |
| US5763643A (en) * | 1995-09-28 | 1998-06-09 | Basf Aktiengesellschaft | Preparation of alkyl esters of (meth)acrylic acid |
| US5767306A (en) * | 1995-09-28 | 1998-06-16 | Basf Aktiengesellschaft | Esterification of (meth)acrylic acid with an alkanol |
| US5910603A (en) * | 1995-09-28 | 1999-06-08 | Basf Aktiengesellschaft | Esterification of (meth)acrylic acid with an alkanol |
| EP0780360A1 (en) | 1995-12-19 | 1997-06-25 | Basf Aktiengesellschaft | Esterification process of (meth)acrylic acid with an alcanol |
| EP0780359A1 (en) | 1995-12-19 | 1997-06-25 | Basf Aktiengesellschaft | Esterification process of (meth)acrylic acid with an alcanol |
| US7026503B2 (en) | 2001-06-08 | 2006-04-11 | Basf Aktiengesellschaft | Method for producing (meth)acrylic acid esters |
| CN100398505C (en) * | 2006-07-28 | 2008-07-02 | 沈福昌 | Treatment method of acrylic acid and esters waste oil resource |
| EP4015498A1 (en) | 2020-12-18 | 2022-06-22 | Basf Se | Method for the continuous production of acrylic acid n-butylester |
| WO2023025999A1 (en) | 2021-08-25 | 2023-03-02 | Arkema France | Improved method for producing high-purity butyl acrylate |
| FR3126416A1 (en) | 2021-08-25 | 2023-03-03 | Arkema France | IMPROVED PROCESS FOR MANUFACTURING HIGH PURITY BUTYL ACRYLATE |
| FR3128459A1 (en) | 2021-10-25 | 2023-04-28 | Arkema France | HIGH PURITY BUTYL ACRYLATE |
| WO2023073303A1 (en) | 2021-10-25 | 2023-05-04 | Arkema France | Improved method for producing high-purity butyl acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1026104C (en) | 1994-10-05 |
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