CN108530295A - A kind of technique of the acrylic acid N-butyl from waste oil - Google Patents
A kind of technique of the acrylic acid N-butyl from waste oil Download PDFInfo
- Publication number
- CN108530295A CN108530295A CN201810399002.0A CN201810399002A CN108530295A CN 108530295 A CN108530295 A CN 108530295A CN 201810399002 A CN201810399002 A CN 201810399002A CN 108530295 A CN108530295 A CN 108530295A
- Authority
- CN
- China
- Prior art keywords
- butyl
- acrylic acid
- waste oil
- reaction
- acid
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 56
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 230000032050 esterification Effects 0.000 claims abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 74
- 239000003112 inhibitor Substances 0.000 claims description 69
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 238000006116 polymerization reaction Methods 0.000 claims description 46
- 238000010025 steaming Methods 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000006096 absorbing agent Substances 0.000 claims description 16
- 239000003377 acid catalyst Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229940120693 copper naphthenate Drugs 0.000 claims description 3
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- NGWKGSCSHDHHAJ-YPFQVHCOSA-N Liquoric acid Chemical compound C1C[C@H](O)C(C)(C)C2CC[C@@]3(C)[C@]4(C)C[C@H]5O[C@@H]([C@](C6)(C)C(O)=O)C[C@@]5(C)[C@@H]6C4=CC(=O)C3[C@]21C NGWKGSCSHDHHAJ-YPFQVHCOSA-N 0.000 claims 1
- NGWKGSCSHDHHAJ-UHFFFAOYSA-N Liquoric acid Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CC5OC(C(C6)(C)C(O)=O)CC5(C)C6C4=CC(=O)C3C21C NGWKGSCSHDHHAJ-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims 1
- 229940092714 benzenesulfonic acid Drugs 0.000 claims 1
- 238000001256 steam distillation Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 33
- 238000012545 processing Methods 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 36
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229940048053 acrylate Drugs 0.000 description 6
- -1 butoxy n-butyl Chemical group 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical group CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 201000008197 Laryngitis Diseases 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 210000001508 eye Anatomy 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 208000013220 shortness of breath Diseases 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The technique for acrylic acid N-butyl that the invention discloses a kind of from waste oil, including depolymerization, esterification, it is thick steam, neutralize, de- light, de- weight and it is de- it is light after light component de- ether step.The present invention optimizes the process conditions of depolymehzation step, improves the conversion ratio of acrylic acid in waste oil；The sodium hydroxide for being replaced the prior art using sodium carbonate in neutralization procedure, is reduced the post processing cost of waste liquid, improves the safety of operation；The light component obtained in rapid to de- fox trot carries out in de- ether processing and recovery to esterif iotacation step, while removing the moisture in light component, avoids causing product purity to decline because applying mechanically n-butyl ether too high levels in light component.
Description
Technical field
The present invention relates to acrylate waste oil recycling fields, and in particular to a kind of acrylic acid N-butyl from waste oil
Technique.
Background technology
N-butyl acrylate is colourless liquid, not soluble in water, is miscible in ethyl alcohol, ether.N-butyl acrylate is mainly used
Make organic synthesis intermediate, adhesive, emulsifier.N-butyl acrylate is harmful to health, by sucking, eating, percutaneous absorbtion.
Its steam or mist have a stimulation to eyes, mucous membrane and respiratory tract, poisoning manifestations have burn feeling, cough, pant, laryngitis, shortness of breath,
Headache, nausea and vomiting.N-butyl acrylate waste oil group is divided into n-butyl acrylate, acrylic acid, n-butanol, water and butoxy third
The ingredient of olefin(e) acid N-butyl, acrylic acid waste oil is acrylic acid dimer, water, acrylic acid.Therefore, the recycling one of industrial acrylate
As include depolymerization, esterification, de- light, de- weight four steps, in de- light light component obtained by treated main component be n-butanol,
Water, in order to realize making full use of for n-butanol material, in the prior art using the processing means for being applied to esterification.In industry
Acrylic acid dimer and n-butyl acrylate depolymerization are corresponding monomer, depolymerization by depolymehzation step in the removal process of acrylate
Step determines the rate of recovery of n-butyl acrylate, therefore in order to which the rate of recovery for improving industrial acrylate is needed to depolymehzation step
In technological parameter optimize.Two molecule n-butanols are dehydrated generate n-butyl ether in acid condition in depolymehzation step simultaneously,
If not generating light component to de- light industry sequence during continuous production carries out de- ether processing, but directly set is used in esterification step
Suddenly, the n-butyl ether in product n-butyl acrylate can be caused constantly to accumulate with increasing for number is applied mechanically, influences the positive fourth of acrylic acid
The purity of ester.
Invention content
It is an object of the present invention to overcome defect existing in the prior art, propylene acid recovering rate in a kind of waste oil is provided
Height, the high n-butyl acrylate recovery process of product purity.
To achieve the above object, the technical scheme is that a kind of technique of the acrylic acid N-butyl from waste oil,
Include the following steps：
S1:Depolymerization, n-butyl acrylate waste oil, acrylic acid waste oil, esterified acid catalyst, polymerization inhibitor, water absorbing agent and positive fourth
Alcohol is warming up to insulation reaction after de-polymerization temperature, after reaction by n-butyl acrylate, n-butanol, acrylic acid and water in depolymerization kettle
Mixed vapour distills, and mixed vapour is condensed, stratification, obtains organic phase depolymerization mixed liquor, the esterified acid catalyst is
P-methyl benzenesulfonic acid, pyrovinic acid and phosphotungstic acid it is catalyst compounded, the polymerization inhibitor is phenthazine, copper naphthenate, nitrobenzene, right
One or more of benzenediol is used in compounding, a concentration of 800~1500ppm of polymerization inhibitor.Polypropylene is solved in depolymehzation step
Acid dimer, n-butyl acrylate dimer, because acrylic acid dimer is unstable, therefore addition polymerization inhibitor prevents acrylic acid list
Body is polymerized to acrylic acid dimer.Occur inevitably to will produce side reaction while esterification in depolymehzation process.
S2:Esterification, organic phase depolymerization mixed liquor, n-butanol, esterified acid catalyst, polymerization inhibitor are pumped into esterifying kettle, are risen
Temperature to esterification temperature carries out esterification, obtains esterification reaction solution, the mixed vapour of n-butanol and water is condensed, quiet in esterifying kettle
Layering is set, n-butanol is recycled；
S3:Thick to steam, esterification reaction solution keeps the temperature thick steaming after heating up at reduced pressure conditions, thick to steam the gained condensed pipe of mixed vapour
Condensing recovery obtains slightly steaming n-butyl acrylate mixed liquor and thick steaming raffinate；
S4:It neutralizes, lye is carried out neutralization reaction under normal pressure with thick steaming n-butyl acrylate mixed liquor removes thick steaming third
Esterified acid catalyst and acrylic acid in olefin(e) acid N-butyl mixed liquor, stratification, obtains organic phase and water phase after reaction；
S5:De- light, by the organic phase obtained after neutralization, rectifying removes the light component of three-phase azeotropic under the reduced pressure that heats up
N-butanol, water and n-butyl ether obtain the mixed liquor after taking off gently；
S6:Weight is taken off, the mixed liquor after taking off gently is taken off into weight through the rectification under vacuum that heats up, the steam distillated is condensed, flows back, and obtains
N-butyl acrylate finished product and de- weight raffinate.
Preferred technical solution is that the n-butanol recovery of the S2 recycling is in esterif iotacation step；The thick steaming raffinate and
De- weight raffinate recovery is in depolymehzation step；Light component during the de- fox trot is rapid is condensed, layering, organic phase recovery in
Esterif iotacation step.Thick steam in raffinate and de- weight raffinate also contains part propylene acid dimer, in order to realize the further recycling of material
It applies mechanically, realizes the maximum rate of recovery, while reducing content of organics in the raffinate burned via incinerator to the greatest extent, will slightly steam raffinate
With de- heavy raffinate recovery in depolymehzation step.
Preferred technical solution, the S1 depolymehzation steps, temperature programming keep 30min, are risen in 10~25min to 80 DEG C
Temperature is to 145 DEG C~180 DEG C, 10~15h of depolymerization time；The S2 esterification process reaction temperature be 80~95 DEG C, reaction temperature by
The steam of 0.8~1.0MPa provides in reactor jacket, and reaction pressure is -0.10~-0.08MPa, 13~15h of reaction time.
Preferred technical solution, it is 140~146 DEG C that step condition is slightly steamed in the S3, reaction pressure is -0.1~-
0.095MPa；The neutralization procedure of the S4, reaction condition are 20~38 DEG C；The de- fox trot of S5 is rapid, and reaction temperature is 90~118
DEG C, reaction pressure is -0.06~-0.05MPa；The de- heavy step of S6, reaction temperature be 130~140 DEG C, reaction pressure be-
0.06~-0.05MPa.
The mass percent of preferred technical solution, the esterified acid catalyst is p-methyl benzenesulfonic acid 40~50%, methyl
Sulfonic acid 40~50% and phosphotungstic acid 0~10%, the pyrovinic acid are 70% pyrovinic acid.Phosphotungstic acid is a kind of multi-functional new
Type catalyst has very high catalytic activity, and stability is good, environmentally safe, is green catalyst, is dissolved in alcohol and water.
Preferred technical solution, the polymerization inhibitor are that phenthazine is used in compounding with hydroquinone, phenthazine and hydroquinone
Mass ratio be 1~5:1.The phenthazine has synergistic effect with hydroquinone.
Preferred technical solution, the water absorbing agent be high temperature resistant water-absorbing resin, high temperature resistant Bibulous Silica Gel, the water absorbing agent
Granular size is 0.1~1mm, and the additive amount of water absorbing agent is the 1~5% of waste oil total amount, and water absorbing agent is added into depolymerization kettle in three batches
In.Water absorbing agent is added in depolymerization kettle, water absorbing agent large specific surface area can absorb in the water and waste oil generated in esterification
Water ensures that the reversible esterification of n-butanol and acrylic acid is carried out to n-butyl acrylate direction is generated, and n-butyl acrylate is logical
It crosses distillation to separate from waste oil, the rate of recovery of acrylic acid in waste oil can be improved.Used high temperature water-absorbing resin and silicon
Glue has good biological degradability.
The N-process of preferred technical solution, the N-process of S4, S4 is configured to using natrium carbonicum calcinatum and n-butanol
The mass percent of lye, natrium carbonicum calcinatum is 15~25%, and the pH value of mixed liquor is controlled 7~8 after neutralization, and N-process is anti-
It is 3~4h between seasonable.Lye is prepared using natrium carbonicum calcinatum and substitutes traditional sodium hydroxide for n-butyl acrylate production
Neutralization reaction avoids the problems such as traditional handicraft is strong, waste water salt content is high using liquid caustic soda corrosivity, reduces the place of production waste water
Manage cost.The advantages such as, danger classes low, energy conservation and environmental protection low with production cost.
Preferred technical solution, the de- light industry skill of S5 take off n-butyl ether process using a kind of work in benzene, toluene or hexamethylene
For water entrainer, mixed to light component and ethyl alcohol and polymerization inhibitor be added in liquid, be heated to 78~82 DEG C, distilled under normal pressure ethyl alcohol, benzene, water and
N-butyl ether azeotropic mixture removes by-product n-butyl ether.
Preferred technical solution, the depolymerization thick steam, de- light, de- are all made of condenser condensation again；It is being solved in depolymehzation step
The depolymerization inhibitor solution that organic phase depolymerization batch mixing is mixed with polymerization inhibitor is added in poly- condenser top；Thick steam slightly is being steamed in step
The thick thick steaming inhibitor solution for steaming n-butyl acrylate mixed liquor and being mixed with polymerization inhibitor is added in condenser top；During de- fox trot is rapid
The de- light inhibitor solution that de- light rear batch mixing is mixed with polymerization inhibitor is added on de- condenser light top；In de- weight in de- weight step
The de- heavy inhibitor solution that n-butyl acrylate finished product is mixed with polymerization inhibitor is added in condenser top, and the thick steaming polymerization inhibitor is molten
Liquid, the polymerization inhibitor taken off in light inhibitor solution, de- weight inhibitor solution are 600~800ppm.Acrylic monomers easily occurs poly-
Reaction is closed, and polymerisation is exothermic reaction, if polymerisation occurs in distillation process easily causes the accidents such as explosion, in order to
It reduces acrylic acid in distillation process to polymerize, polymerization inhibitor is added while condensation using condenser.
The advantages of the present invention are：A kind of technique of the acrylic acid N-butyl from waste oil of the present invention,
The high temperature resistant water absorbing agent that large specific surface area is added in depolymehzation step, contributes to the reversible reaction of n-butanol and acrylic acid to generation
The direction of n-butyl acrylate carries out, and under 145~180 DEG C of de-polymerization temperature, acrylic acid, n-butanol and catalyst are all with gas
State form is present in depolymerization kettle, is conducive to accelerate the reaction time, improves reaction efficiency；By to de- fox trot it is rapid in obtain it is light
Component carries out in de- ether processing and recovery to esterification step, while removing the moisture in light component, avoids because applying mechanically light group
Divide the too high levels of middle n-butyl ether and is not readily separated the decline of final products purity；In neutralization procedure, by by the prior art
Middle replaced with using highly basic sodium hydroxide preparation lye prepares lye using sodium carbonate, reduces the processing cost of production waste water, drop
The danger classes of low operation, production technology are more energy-saving and environmentally friendly.
Specific implementation mode
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical scheme of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
The raw material of a kind of technique of the acrylic acid N-butyl from waste oil, n-butyl acrylate waste oil recovery process is third
The group of olefin(e) acid N-butyl waste oil, n-butyl acrylate waste oil is divided into n-butyl acrylate 51.4%, acrylic acid 5.5%, n-butanol
1.1%, water 1.1% and butoxy n-butyl acrylate 40.5%, also containing 0.4% 3- butoxy n-butyl propionates.
S1：Depolymerization kettle is added in n-butyl acrylate waste oil, esterification catalyst, polymerization inhibitor, n-butanol and water absorbing agent by depolymerization
In, using 1.5 DEG C/min temperature programmings to 80 DEG C, 30min is kept the temperature, is sufficiently stirred through the blender in depolymerization kettle, it is big with particle
The small high temperature resistant water-absorbing resin for 0.1mm absorbs the moisture generated in moisture and esterification in waste oil, water-absorbing resin point three
Secondary addition, the additive amount of water-absorbing resin are the 2% of waste oil total amount.Using 5 DEG C/min of temperature programming, 175~180 DEG C are warming up to,
Depolymerization time 10h.Keep the temperature depolymerization acrylic acid dimer, esterification and inevitable side reaction, the acrylic acid in depolymerization kettle
N-butyl, n-butanol, acrylic acid and water mixed vapour distillate, mixed vapour is condensed, stratification, obtains organic phase depolymerization
Batch mixing, raffinate concentration is transferred to waste collection kettle in depolymerization kettle, and kettle internal jacket lead to steam insulation, then is kept the temperature and sent to burning with jacketed pipe
Stove burns.
It is two molecule acrylic acid that the main reaction of depolymehzation step, which is a molecule acrylic acid dimer depolymerization, a molecule acrylic acid and
One molecule n-butanol esterification generate n-butyl acrylate, 3- butoxy n-butyl propionate ether bond ruptures generate n-butyl acrylate and
N-butanol, side reaction are that the dehydration of two molecule n-butanols generates a molecule n-butyl ether.
S2：Esterification, organic phase depolymerization mixed liquor, n-butanol, esterified acid catalyst, polymerization inhibitor is pumped into esterifying kettle, ester
It is 80~95 DEG C to change reaction temperature, and reaction pressure is -0.10~-0.08MPa, and the reaction time, 13~15h obtained esterification reaction solution,
The mixed vapour of n-butanol and water is condensed in esterifying kettle, stratification, and recycling n-butanol is applied in esterif iotacation step.
It for mass percent is p-methyl benzenesulfonic acid to use esterified acid catalyst: 70% pyrovinic acid=50: 50%.Esterification is anti-
The main reaction answered is n-butanol and acroleic acid esterification generates n-butyl acrylate, and side reaction is that n-butyl acrylate and water addition are anti-
2 hydroxy propanoic acid N-butyl should be generated.
S3：Thick to steam, esterification reaction solution is warming up to 140 DEG C under -0.1~-0.095MPa reduced pressures, keeps the temperature thick steaming, slightly
It steams the gained condensed device condensing recovery of mixed vapour to obtain slightly steaming n-butyl acrylate mixed liquor and thick steaming raffinate, the thick raffinate that steams returns
Receipts are applied in depolymehzation step.
S4：It neutralizes, under the carbonic acid soda lye and thick steaming n-butyl acrylate mixed liquor normal pressure for being 25% by mass percent
Neutralization reaction is carried out, reaction temperature is 20~25 DEG C, and neutralization reaction removes remaining right in thick steaming n-butyl acrylate mixed liquor
Toluenesulfonic acid, pyrovinic acid and acrylic acid, 7~8, the N-process reaction time is 3h, reaction knot for the pH value control of neutralizer
Stratification after beam, obtains water layer and organic layer.
Described 25% carbonic acid soda lye using natrium carbonicum calcinatum and by esterif iotacation step recycling butanol solution prepare and
At, improve the utilization ratio of raw materials for production, using carbonic acid soda lye neutralized crude steam n-butyl acrylate mixed liquor can be formed it is bright
Aobvious water oil layer avoids the formation of floating ash.
Neutralization reaction institute product is sodium acrylate, paratoluenesulfonic acid sodium salt and sodium methanesulfonate, is dissolved in water layer and detaches.
S5：It is de- light, the organic phase obtained in S4 under -0.06~-0.05MPa reduced pressures, reaction temperature is 110~
Light component n-butanol, water and the n-butyl ether of 118 DEG C of rectifying removing three-phase azeotropic obtain de- light rear mixed liquor；Light component is condensed,
Layering, organic phase recovery to esterif iotacation step.
Contain unreacted n-butanol and by-product n-butyl ether in esterifying liquid；It is total that n-butanol, water, n-butyl ether can form ternary
Boiling, azeotropic point are 90.6 DEG C；N-butanol and water can form two-spot azeotropic, and azeotropic point is 93 DEG C；N-butyl ether and water can form two-spot
Azeotropic mixture, azeotropic point are 94.1 DEG C；N-butanol and n-butyl ether can form two-spot azeotropic mixture, and azeotropic point is 117.6 DEG C.
S6：De- heavy, reaction temperature is 130~140 DEG C, and reaction pressure is -0.06~-0.05MPa, takes off light rear mixed liquor warp
The de- weight of the rectification under vacuum that heats up distillates condensed gas, reflux n-butyl acrylate finished product and de- weight raffinate, takes off weight raffinate recycling
It is applied in depolymehzation step.
S7:De- ether, finished product ethyl alcohol, benzene (water entrainer), polymerization inhibitor and n-butyl acrylate light component are pumped into de- ether kettle.
Jacket steam heating makes to be stepped up to 80 DEG C only in de- ether kettle, steam early period (mainly ethyl alcohol, benzene, water, n-butyl ether) by
Rectifying after first de- ether condenser condensation, later stage steam (mainly butyl acrylate, n-butanol, n-butyl ether and water) are taken off by second
Ether condenser is collected, is layered, recovery after upper oil phase rectifying cooling.
Depolymerization thick steam, de- light, de- is all made of condenser condensation again；On depolymerization condenser top, addition is organic in depolymehzation step
The solubility of the depolymerization inhibitor solution that phase depolymerization batch mixing is mixed with polymerization inhibitor, depolymerization inhibitor solution is 800ppm, used
Polymerization inhibitor is phenthazine and hydroquinone, and the weight of phenthazine accounts for the 80% of polymerization inhibitor total weight；It is thick steam in step slightly steam it is cold
The thick thick steaming inhibitor solution for steaming n-butyl acrylate mixed liquor and being mixed with polymerization inhibitor is added in condenser top, and it is molten slightly to steam polymerization inhibitor
The solubility of liquid is 600ppm；During de- fox trot is rapid de- condenser light top be added it is de- it is light after batch mixing mix with polymerization inhibitor it is de- light
Inhibitor solution, the solubility for taking off light inhibitor solution are 600ppm；Acrylic acid is being added just on de- weight condenser top in de- weight step
The de- heavy inhibitor solution that butyl ester finished product is mixed with polymerization inhibitor, the solubility for taking off light inhibitor solution are 600ppm.Polymerization inhibitor
Concentration according in condensed steam acrylic acid content determine.
Production technology described in the present embodiment makes the conversion ratio of acrylic acid in n-butyl acrylate waste oil be 98%, final finished
Purity be 99.52%.
Embodiment 2
The raw material of a kind of technique of the acrylic acid N-butyl from waste oil, n-butyl acrylate waste oil recovery process is third
Olefin(e) acid waste oil, the group in acrylic acid waste oil are divided into acrylic acid dimer 38.5%, water 5.8% and acrylic acid 55.7%.
Embodiment 2 with implement 1 difference lies in：The technique of de- n-butyl ether, it is 78 DEG C to take off ether temperature；S1 depolymehzation steps it is anti-
It answers temperature from 80 DEG C, using 3.5 DEG C/min of temperature programming, is warming up to 145~150 DEG C, depolymerization time 14h；S2 esterif iotacation steps
85~90 DEG C of reaction temperature, reaction time 14h；S3 slightly steams 140 DEG C of the reaction temperature of step, and reaction pressure is -0.1~-
0.095MPa；The reaction temperature of S4 neutralization procedures is 25~30 DEG C；It is 90~118 DEG C that S5, which takes off the rapid reaction temperature of fox trot, reaction
Pressure is -0.06~-0.05MPa；It is 130~140 DEG C that the reaction temperature that S6 takes off weight step, which is reaction temperature, reaction pressure is-
0.06~-0.05MPa.
The ingredient of esterified acid catalyst in depolymehzation step and esterif iotacation step is：P-methyl benzenesulfonic acid 50%, pyrovinic acid
40% and phosphotungstic acid 10%.Water absorbing agent is high temperature resistant silica gel in depolymehzation step, and the granular size of silica gel is 0.5mm, and silica gel adds
Dosage is the 5% of waste oil gross weight.Polymerization inhibitor in n-butyl acrylate recovery process is copper naphthenate 40% and phenthazine 60%.
Organic phase depolymerization batch mixing is added on depolymerization condenser top in depolymehzation step to inhibit with the depolymerization that polymerization inhibitor mixes
The solubility of agent solution, depolymerization inhibitor solution is 1200ppm；Thick steaming acrylic acid is being added just on thick evaporation condenser top in thick steam in step
The thick steaming inhibitor solution that butyl ester mixed liquor is mixed with polymerization inhibitor, the thick solubility for steaming inhibitor solution are 800ppm；It is de- light
The de- light inhibitor solution that de- light rear batch mixing is mixed with polymerization inhibitor is added on de- condenser light top in step, takes off light polymerization inhibitor
The solubility of solution is 800ppm；In de- weight step de- weight condenser top be added n-butyl acrylate finished product mixed with polymerization inhibitor and
At de- heavy inhibitor solution, take off light inhibitor solution solubility be 800ppm.
Production technology described in the present embodiment make acrylic acid in acrylic acid waste oil conversion ratio be 98.7%, final products it is pure
Degree is 99.26%
Embodiment 3
Difference lies in the technique for taking off n-butyl ether, it is 78 DEG C to take off ether temperature to embodiment 3 with embodiment 1；S1 depolymehzation steps
Reaction temperature, using 5 DEG C/min of temperature programming, is warming up to 150~180 DEG C, depolymerization time 13h from 80 DEG C；S2 esterif iotacation steps
90~95 DEG C of reaction temperature, reaction time 13h；S3 slightly steams 142~146 DEG C of the reaction temperature of step, and reaction pressure is -0.1~-
0.095MPa；The reaction temperature of S4 neutralization procedures is 30~38 DEG C, neutralizes time 1.5h；It is 90 that S5, which takes off the rapid reaction temperature of fox trot,
~115 DEG C, reaction pressure is -0.06~-0.05MPa；It is 135~140 DEG C that the reaction temperature that S6 takes off weight step, which is reaction temperature,
Reaction pressure is -0.06~-0.05MPa.
The ingredient of esterified acid catalyst in depolymehzation step and esterif iotacation step is：P-methyl benzenesulfonic acid 45%, pyrovinic acid
45% and phosphotungstic acid 10%.Water absorbing agent is fire resistant resin in depolymehzation step, and the granular size of silica gel is 1mm, the addition of silica gel
Amount is the 1% of waste oil gross weight.Polymerization inhibitor in n-butyl acrylate recovery process is nitrobenzene 20% and phenthazine 80%.
Production technology described in the present embodiment make acrylic acid in n-butyl acrylate waste oil conversion ratio be 97.5%, finally at
The purity of product is 99.42%.
Reference examples：
The raw material of n-butyl acrylate waste oil recovery process is n-butyl acrylate waste oil, the group of n-butyl acrylate waste oil
It is divided into n-butyl acrylate 51.4%, acrylic acid 5.5%, n-butanol 1.1%, water 1.1% and butoxy n-butyl acrylate
40.5%, also containing 0.4% 3- butoxy n-butyl propionates.
Reference examples and embodiment 1 difference lies in：Water absorbing agent is not added in S1 depolymehzation steps, reaction temperature is by room temperature program
175~180 DEG C are warming up to, depolymerization time 12h；Reaction temperature is 80~95 DEG C in S2 esterif iotacation steps, and reaction pressure is -0.10
~-0.08MPa, the reaction time, 13~15h obtained esterification reaction solution；S3 slightly steams step, 140 DEG C of reaction temperature, reaction pressure-
0.1~-0.095MPa is thick to steam in raffinate recovery to depolymehzation step；S4 neutralization procedures, synthesis under normal pressure, reaction temperature 20~
25℃；The de- fox trots of S5 are rapid, 110~118 DEG C of reaction temperature, reaction pressure -0.06~-0.05MPa；The de- weight steps of S6, reaction temperature
130~140 DEG C of degree, reaction pressure are -0.06~-0.05MPa.
The ingredient of esterified acid catalyst in depolymehzation step and esterif iotacation step is：The concentrated sulfuric acid.N-butyl acrylate recycles work
Polymerization inhibitor in skill is phenthazine.Lye is sodium hydroxide solution in neutralization procedure.
Production technology described in this reference examples makes the conversion ratio of acrylic acid in n-butyl acrylate waste oil be 85%, final finished
Purity be 97.49%.
Contain n-butyl acrylate, micro n-butanol, polymerization inhibitor and other impurities in 1 gained finished product of embodiment.Reference examples
Not using the n-butyl acrylate recovery process for taking off ether processing, after 5 times or more recoveries, final finished purity is less than
95%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made.
Claims (10)
1. a kind of technique of the acrylic acid N-butyl from waste oil, which is characterized in that include the following steps：
S1:Depolymerization, n-butyl acrylate waste oil, acrylic acid waste oil, esterified acid catalyst, polymerization inhibitor, water absorbing agent and n-butanol liter
Insulation reaction after temperature to de-polymerization temperature after reaction mixes n-butyl acrylate, n-butanol, acrylic acid and water in depolymerization kettle
Steam distillation, mixed vapour is condensed, stratification, obtains organic phase depolymerization mixed liquor, and the esterified acid catalyst is to first
Benzene sulfonic acid, pyrovinic acid and phosphotungstic acid it is catalyst compounded, the polymerization inhibitor be phenthazine, copper naphthenate, nitrobenzene, to benzene two
One or more of phenol is used in compounding, a concentration of 800~1500ppm of polymerization inhibitor；
S2:Esterification, organic phase depolymerization mixed liquor, n-butanol, esterified acid catalyst, polymerization inhibitor are pumped into esterifying kettle, are warming up to
Esterification temperature carries out esterification, obtains esterification reaction solution, and the mixed vapour of n-butanol and water is condensed in esterifying kettle, stands point
Layer recycles n-butanol；
S3:Thick to steam, esterification reaction solution keeps the temperature thick steaming after heating up at reduced pressure conditions, thick to steam the gained condensed pipework condensation of mixed vapour
Recycling obtains slightly steaming n-butyl acrylate mixed liquor and thick steaming raffinate；
S4:It neutralizes, lye and the thick n-butyl acrylate mixed liquor that steams is subjected to the thick steaming acrylic acid of neutralization reaction removing under normal pressure
Esterified acid catalyst in N-butyl mixed liquor and acrylic acid, stratification, obtains organic phase and water phase after reaction；
S5:De- light, by the organic phase obtained after neutralization, rectifying removes the positive fourth of light component of three-phase azeotropic under the reduced pressure that heats up
Alcohol, water and n-butyl ether obtain the mixed liquor after taking off gently；
S6:Weight is taken off, the mixed liquor after taking off gently is taken off into weight through the rectification under vacuum that heats up, the steam that rectifying goes out is condensed, flows back, and obtains third
Olefin(e) acid N-butyl finished product and de- weight raffinate.
2. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that the S2
The n-butanol recovery of recycling is in esterif iotacation step；The thick steaming raffinate and de- weight raffinate recovery are in depolymehzation step；It is described
Light component during de- fox trot is rapid is condensed, layering, and organic phase recovery is in esterif iotacation step.
3. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that the S1
Depolymehzation step, temperature programming keep 30min to 80 DEG C, are warming up to 145 DEG C~180 DEG C in 10~25min, and the depolymerization time 10~
15h；The S2 esterification process reaction temperature be 80~95 DEG C, reaction temperature by 0.8~1.0MPa in reactor jacket steam
It provides, reaction pressure is -0.10~-0.08MPa, 13~15h of reaction time.
4. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that the S3
In slightly steam step condition be 140~146 DEG C, reaction pressure be -0.1~-0.095MPa；The neutralization procedure of the S4 reacts item
Part is 20~38 DEG C；The de- fox trot of S5 is rapid, and reaction temperature is 90~118 DEG C, and reaction pressure is -0.06~-0.05MPa；S6's
De- weight step, reaction temperature are 130~140 DEG C, and reaction pressure is -0.06~-0.05MPa.
5. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that the ester
The mass percent for changing acid catalyst is p-methyl benzenesulfonic acid 40~50%, pyrovinic acid 40~50% and phosphotungstic acid 0~10%.
6. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that the resistance
Poly- agent is that phenthazine is used in compounding with hydroquinone, and the mass ratio of phenthazine and hydroquinone is 1~5:1.
7. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that the suction
Aqua is high temperature resistant water-absorbing resin, and the granular size of high temperature resistant Bibulous Silica Gel, the water absorbing agent is 0.1~1mm, and water absorbing agent adds
Dosage is the 1~5% of waste oil total amount, and water absorbing agent is added into three batches in depolymerization kettle.
8. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that in S4
Lye is configured to using natrium carbonicum calcinatum and n-butanol with process, the mass percent of natrium carbonicum calcinatum is 15~25%, is neutralized
7~8, the N-process reaction time is 3~4h for the pH value control of mixed liquor afterwards.
9. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that S5's is de-
Light industry skill takes off n-butyl ether process and being used as water entrainer using a kind of in benzene, toluene or hexamethylene, mixed to light component and second is added in liquid
Alcohol and polymerization inhibitor are heated to 78~82 DEG C, and ethyl alcohol, benzene, water and n-butyl ether azeotropic mixture are distilled under normal pressure, remove the positive fourth of by-product
Ether.
10. a kind of technique of acrylic acid N-butyl from waste oil according to claim 1, which is characterized in that described
Depolymerization thick steam, de- light, de- is all made of condenser condensation again；Organic phase depolymerization is added on depolymerization condenser top in depolymehzation step to mix
The depolymerization inhibitor solution that material is mixed with polymerization inhibitor；The thick steaming positive fourth of acrylic acid is added on thick evaporation condenser top in thick steam in step
The thick steaming inhibitor solution that ester mixed liquor is mixed with polymerization inhibitor；It is mixed after de- condenser light top is added and takes off gently during de- fox trot is rapid
The de- light inhibitor solution that material is mixed with polymerization inhibitor；In de- weight step de- weight condenser top be added n-butyl acrylate at
The de- heavy inhibitor solution that product and polymerization inhibitor mix, thick the steamings inhibitor solution take off light inhibitor solution, take off and inhibit again
Polymerization inhibitor in agent solution is 600~800ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810399002.0A CN108530295A (en) | 2018-04-28 | 2018-04-28 | A kind of technique of the acrylic acid N-butyl from waste oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810399002.0A CN108530295A (en) | 2018-04-28 | 2018-04-28 | A kind of technique of the acrylic acid N-butyl from waste oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108530295A true CN108530295A (en) | 2018-09-14 |
Family
ID=63476187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810399002.0A Pending CN108530295A (en) | 2018-04-28 | 2018-04-28 | A kind of technique of the acrylic acid N-butyl from waste oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108530295A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452116A (en) * | 2019-07-17 | 2019-11-15 | 江苏新东风化工科技有限公司 | A kind of n-butyl acrylate esterification device and its reaction process |
| CN113121340A (en) * | 2021-03-15 | 2021-07-16 | 江苏新东风化工科技有限公司 | Butyl acrylate waste oil recovery process |
| CN113121348A (en) * | 2021-03-15 | 2021-07-16 | 江苏新东风化工科技有限公司 | Deetherizing process for producing n-butyl acrylate |
| CN113511973A (en) * | 2021-03-16 | 2021-10-19 | 南京福昌环保有限公司 | Method for recycling acrylic acid and ester waste oil by utilizing series catalytic esterification reaction device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201807368U (en) * | 2010-10-11 | 2011-04-27 | 安徽师范大学 | Propyl p-hydroxybenzoate production equipment |
| CN102633639A (en) * | 2012-04-06 | 2012-08-15 | 华远医药研究院有限公司 | Synthesis process for trifluoroacetic acid ethyl ester |
| CN104844456A (en) * | 2015-04-17 | 2015-08-19 | 江苏新东风化工科技有限公司 | n-butylacrylate waste oil recovery process and n-butylacrylate waste oil recovery apparatus |
| CN104892410A (en) * | 2015-04-28 | 2015-09-09 | 江苏新东风化工科技有限公司 | Methyl acrylate waste oil recovery technology |
-
2018
- 2018-04-28 CN CN201810399002.0A patent/CN108530295A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201807368U (en) * | 2010-10-11 | 2011-04-27 | 安徽师范大学 | Propyl p-hydroxybenzoate production equipment |
| CN102633639A (en) * | 2012-04-06 | 2012-08-15 | 华远医药研究院有限公司 | Synthesis process for trifluoroacetic acid ethyl ester |
| CN104844456A (en) * | 2015-04-17 | 2015-08-19 | 江苏新东风化工科技有限公司 | n-butylacrylate waste oil recovery process and n-butylacrylate waste oil recovery apparatus |
| CN104892410A (en) * | 2015-04-28 | 2015-09-09 | 江苏新东风化工科技有限公司 | Methyl acrylate waste oil recovery technology |
Non-Patent Citations (2)
| Title |
|---|
| 吕苗苗: "塞来昔布的合成" * |
| 李静等: "超声波作用下乙酸异戊酯的合成" * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452116A (en) * | 2019-07-17 | 2019-11-15 | 江苏新东风化工科技有限公司 | A kind of n-butyl acrylate esterification device and its reaction process |
| CN113121340A (en) * | 2021-03-15 | 2021-07-16 | 江苏新东风化工科技有限公司 | Butyl acrylate waste oil recovery process |
| CN113121348A (en) * | 2021-03-15 | 2021-07-16 | 江苏新东风化工科技有限公司 | Deetherizing process for producing n-butyl acrylate |
| CN113121340B (en) * | 2021-03-15 | 2024-04-19 | 江苏新东风化工科技有限公司 | Butyl acrylate waste oil recovery process |
| CN113511973A (en) * | 2021-03-16 | 2021-10-19 | 南京福昌环保有限公司 | Method for recycling acrylic acid and ester waste oil by utilizing series catalytic esterification reaction device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108530295A (en) | A kind of technique of the acrylic acid N-butyl from waste oil | |
| CN104844456B (en) | A kind of n-butyl acrylate waste oil recovery process and device | |
| CN108124444A (en) | The extraction process of MMA- carbinol mixtures containing sodium salt | |
| NZ543299A (en) | Transesterification method of preparing biodiesel from vegetable oil and meat fat | |
| CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
| CN102936198B (en) | Produce the method for vinyl acetate | |
| CN106220532B (en) | A kind of method of separation of extractive distillation acetonitrile and triethylamine | |
| CN106008157B (en) | A kind of preparation method of 2,2,4- trimethyl -1,3- pentanediol diisobutyrate | |
| EP2821384B1 (en) | Production process for preparing cyclohexanol and cyclohexanone by cyclohexane oxidation | |
| CN104768908B (en) | Combine the preparation method of the high-purity anhydrous sugar alcohol utilizing membrane distillation and short-path distillation successively | |
| CN101602770B (en) | Method for preparing herbicide | |
| CN107814778B (en) | α -acetyl-gamma-butyrolactone continuous flow microchannel reaction production process | |
| CN110372509A (en) | A kind of cracking recovery process of n-butyl acrylate heavy constituent | |
| CN108484406A (en) | A kind of Isooctyl acrylate monomer waste oil recovery process | |
| CN106478415B (en) | A kind of ethyl acetate energy-saving processing technique | |
| CN106518620B (en) | A kind of method and device preparing sec-butyl alcohol | |
| CN105315168B (en) | N (4 carboethoxyphenyl) N ' methyl Ns ' phenyl formamidine intermediate green preparation process | |
| CN104892410B (en) | A kind of methyl acrylate waste oil recovery process | |
| CN204644234U (en) | A kind of n-butyl acrylate drain oil recovery equipment | |
| CN110437034A (en) | A kind of acrylate waste oil recovery processing technique | |
| CN104892416A (en) | 2-Ethylhexyl acrylate waste oil recovery technology | |
| CN114181040B (en) | Preparation method of dichloropropanol | |
| CN108752200A (en) | A method of being used for acrylic acid methyl esters waste oil | |
| CN105419952B (en) | A kind of method of biodiesel synthesis in eutectic system | |
| CN104262320A (en) | Method for converting safrole into iso-safrole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180914 |
|
| RJ01 | Rejection of invention patent application after publication |