CN101274890A - Continuous preparation of alkyl esters of (meth) acrylic acid - Google Patents
Continuous preparation of alkyl esters of (meth) acrylic acid Download PDFInfo
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- CN101274890A CN101274890A CNA2007100897182A CN200710089718A CN101274890A CN 101274890 A CN101274890 A CN 101274890A CN A2007100897182 A CNA2007100897182 A CN A2007100897182A CN 200710089718 A CN200710089718 A CN 200710089718A CN 101274890 A CN101274890 A CN 101274890A
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title description 2
- 125000005907 alkyl ester group Chemical group 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 (methyl) methyl Chemical group 0.000 claims abstract description 31
- 238000009835 boiling Methods 0.000 claims abstract description 26
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims description 50
- 150000002148 esters Chemical class 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 241000282326 Felis catus Species 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000006200 vaporizer Substances 0.000 claims description 9
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000008676 import Effects 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 238000003672 processing method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 241001550224 Apha Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 1
- VTDOEFXTVHCAAM-UHFFFAOYSA-N 4-methylpent-3-ene-1,2,3-triol Chemical compound CC(C)=C(O)C(O)CO VTDOEFXTVHCAAM-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- OKKJLVBELUTLKV-MICDWDOJSA-N deuteriomethanol Chemical compound [2H]CO OKKJLVBELUTLKV-MICDWDOJSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 229910021514 lead(II) hydroxide Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical group 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical group 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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Abstract
The invention relates to a method for continuously producing (methyl) methacrylate alkyl ester by reaction between (methyl) methyl acrylate and alcohol with boiling point higher than that of methanol. The method obtains the quality standard of products by a special processing technique, which is not reached up to now; besides, extremely high space-time-yield and overall yield can be reached.
Description
Invention scope
The present invention relates to be reflected to generate by (methyl) methyl acrylate (A) and alcohols (B) make (methyl) alkyl acrylate (C) successive method more under free methanol (D) situation by following reaction formula.
R
1＝H，CH
3
R wherein
2For straight chain, branching or the cyclic alkyl or aryl that contains 2 to 12 C atoms, as pure R
2OH, for example can be ethanol, propyl alcohol or Virahol, butanols or isopropylcarbinol, amylalcohol, hexalin or hexanol, enanthol, octanol or isooctyl alcohol and 2-Ethylhexyl Alcohol, other also can use iso-borneol, phenylcarbinol, tetrahydrofurfuryl alcohol, vinyl carbinol, ethylene glycol, 3 as alcohol, 3,4-cyclonol, phenylethyl alcohol, butylidene glycol ether, uncle-Ding monoethanolamine, diethylaminoethanol, ethylidene triglycol, methylene tri glycol, butyldiglycol or isopropylidene two glycerine (isopropylidenglycerin).
The state of the art
(methyl) alkyl acrylate can be with different processing method manufacturings:
In acetone cyanohydrin in the presence of the sulfuric acid and alcohol reaction or (methyl) methyl acrylate and alcohol reaction in the presence of a catalyzer, in reaction process, can use the also available heterogenetic catalyzer of homogeneous, reaction is often carried out in the presence of a tetralkyl titanate (four titan-alkoxides), can get rid of from reaction mixture by the separation column methyl alcohol that will dissociate in order to help influencing molecular balance in reaction.
Described multiple combining in the literature and be interrupted the method (batch ester exchange reaction method) of carrying out transesterification reaction with different catalysts.
Continuous interpolation material composition and continuous continuous ester interchange reaction method of deriving product in exploring more economical method, have been found, continuous reaction method has been compared following advantage with the interruption reaction method: regulate-and regulate expenditure is lower, personnel need less, quality product is better few with fluctuation, owing to saved the time variable control work of each production stage (reinforced, reaction, low-boiling-point substance separation, product separation, emptying), plant capacity be improved.
The continuous ester interchange method is known
EP0960877 (Elf Atochem S.A.) has described and has a kind ofly made the method for methacrylic ester continuously by dialkylamino alcohol, uses dialkylamino alcohol and common (methyl) methyl acrylate to react as follows and obtains (methyl) vinylformic acid dialkylaminoalkyl ester:
Raw mix ((methyl) methyl acrylate and dialkylamino alcohol) with as the tetralkyl titanate of transesterification catalyst, (metatitanic acid-four butyl ester for example,-tetra-ethyl ester or four (2-ethylhexyl)) and at least a stopper (phenothiazine for example, tert-butyl catechol, hydroquinone monomethyl ether or Resorcinol) continuously join in the stirred reactor together, in the time of 90-120 ℃, generate (methyl) vinylformic acid dialkylaminoalkyl ester through transesterify, steam simultaneously azeotropic (methyl) methyl acrylate/methyl alcohol-mixture continuously, rough reaction mixture (thick ester) is added in first distillation tower, under reduced pressure distill cat head and steam a liquid stream that does not contain catalyzer substantially, in base product liquid, then discharge catalyzer and a spot of (methyl) vinylformic acid dialkylaminoalkyl ester.Liquid of top of the tower with first distillation tower is added in the second column then, under reduced pressure steam the low-boiling-point substance that contains a small amount of (methyl) vinylformic acid dialkylaminoalkyl ester in top of tower, and in liquid at the bottom of the tower, extract the liquid that mainly constitutes out and flow and stopper by (methyl) vinylformic acid dialkylaminoalkyl ester, the latter is added to rectifying under reduced pressure in the 3rd distillation tower, can obtain desired (methyl) vinylformic acid dialkylaminoalkyl ester at cat head, and extraction is essentially stopper in liquid at the bottom of the tower.Liquid can be sent back in the reactor as the liquid of top of the tower of second column by the further refining back of thin-film evaporator at the bottom of the tower of first distillation tower.
This method has been saved pure dehydration before reinforced, and water can make the tetralkyl titanate hydrolysis of interpolation generate undesirable solid sediment, thereby cause may increasing of catalyst deactivation, the shortcoming that exists of this processing method also has catalyzer at the bottom of the first distillation Tata to be in to be heated under the relatively-high temperature to make catalyst decomposes easily in addition.
Comprise that in the method twice totally of the material composition that reacts and product-are refining through cat head, this need consume very high energy and and have four rectifying tower, and the size that has must be very big, so this process need bears very high investment and running cost.
EP0968995 (Mitsui aerochemistry company) has described the processing method of application response tower and has made (methyl) alkyl acrylate continuously, and transesterification reaction is directly to finish (be reactor and what steam (methyl) methyl acrylate/methanol azeotrope be an equipment) in distillation tower.Raw material ((methyl) methyl acrylate and alcohol) successively adds, and necessary catalyzer is preferably titanium compound herein equally, then is present in the distillation tower.And catalyzer need be added in the distillation tower continuously and quantitatively under the situation of homogeneous catalyst.The flushing effect that refluxes in distillation tower owing to liquid when using homogeneous catalyst in distillation tower can improve catalyst consumption and produce the device that the catalyst solid throw out stains tower; Catalyzer is arranged in reaction tower under with the situation of heterogeneous catalyst, but the catalyzer maintenance is defective in distillation tower, can produce a bigger pressure-losses and be the high process costs of routine cleaning distillation tower needs in distillation tower, heterogeneous catalyst also may be because of producing disadvantageous polyreaction inactivation in addition.
Task
Task of the present invention provides a kind of (methyl) methyl acrylate and carries out the continuous processing method of transesterification reaction with the alcohol that is higher than the methyl alcohol boiling point, and the defective that can avoid above-mentioned two kinds of methods to exist.Following ester class and the derivative that is meant vinylformic acid and methacrylic acid about (methyl) acrylate or (methyl) alkyl acrylate, and the product that new process provides is being better than the product that exists so far qualitatively on market, uses new processing method to produce (methyl) alkyl acrylate with alapization expense and energy expenditure (promptly helping cost) in addition.
This task and other do not describe in detail in detail; but mention some tasks that to extend out undoubtedly the explanation of the state of the art from the front; achieve a solution by the processing method with claim 1 characteristics, the change that has a superiority by method of the present invention is all listed in the claim that claim 1 is associated and is protected.
The processing method explanation
Synoptic diagram among Fig. 1 has been represented this processing method
Explanation to mark of correlation among Fig. 1
1, conversion unit
2, azeotrope distillation tower
3, low-boiling-point substance distillation tower
4, high boiling material distillation tower
5, thin-film evaporator
6, thin-film evaporator
11, (methyl) methyl acrylate-and catalyzer-charging
12, alcohol-charging
13, methyl alcohol/(methyl) methyl acrylate-azeotrope
14, low-boiling-point substance recycle stream
15, thick ester
16, pure ester
17, high boiling material and catalyzer
With material composition (methyl) methyl acrylate (MMA, 11) and alcohol (12) continuously not Disconnected joining in the consersion unit (1) that suits is available single reaction vessel herein, also can Adopt the reaction vessel of a plurality of series connection as the multistage cascade, preferably all reaction vessels all are equipped with Evaporated liquor discharge system to azeotropic mixture destilling tower (2) to remove the first of in course of reaction, dissociating Alcohol.
As the required tetralkyl titanate of the catalyst (MMA of four alkoxytitanium content to adding Be preferably the 0.2-0.5 % by weight) and polymerization inhibitor preferably also should quantitatively be added to continuously consersion unit (1) in. Can use the at present known ester exchange catalysis of all technology maturations as ester exchange catalyst Agent for example can be used as having of catalyst: 1 of acetylacetone,2,4-pentanedione zirconium and other zirconium, and the 3-dione compounds, In addition, the mixing that is consisted of by alkali metal cyanate or alkali metal thiocyanate and alkali halide Thing also can adopt, and also has zinc compound, alkaline earth oxide or alkaline earth metal hydroxide, Such as CaO, Ca (OH)2、MgO、Mg(OH)
2, or the mixture of above-claimed cpd and alkali gold Belong to hydroxide, alkali metal oxide and lithium halide and lithium hydroxide, also can use above-mentionedization The mixture that compound and aforesaid alkaline earth metal compound and lithium salts form, dialkyltin, Alkali carbonate, alkali carbonate and quaternary ammonium salt, for example TBAH or 16 Alkyl trimethyl ammonium bromide one is reinstated, and other also has two organic group tin oxide and the halogenation of organic group tin The mixed catalyst that thing forms, acid-exchange resin, assorted many phosphomolybdic acids, Ti alkoxides, Huge legendary turtle compound, lead compound that Titanium, zirconium, iron or zinc and 1,3-dicarbonyl compound form, as The carboxylate of the alcoholates of lead oxide, lead hydroxide, lead, ceruse or lead etc.
Can be that for example the hydroquinones methyl ether combines with oxygen as polymerization inhibitor.
The alcohol of using can be moisture, water content in the used alcohol in the n-butanol situation is being (0.05-0.005 % by weight) between 50 to 500ppm, preferably before entering consersion unit, passes through earlier by alcohol azeotropic mixture tower (2) distillation dehydration, at this moment contained water steams by cat head in the alcohol, pollute the alcohol that adds for fear of methyl alcohol/MMA azeotropic mixture (13), preferably make pure charging be selected in the bottom of destilling tower (2), the alcohol of application also can dewater by alternate manner and method:
-through one dewater in advance distillation tower or
-handle with a dewatering agent, for example molecular sieve or
-by a kind of membrane separation process method, for example pervaporation.
The significance of dehydration is because contained water can make the catalyzer (for example alkyl ester of metatitanic acid) in the reactor be subjected to irreversible infringement in the alcohol, through having avoided the hydrolysis of catalyzer after the dehydration, otherwise catalytic amount need increase and handle the problem of precipitated solid thing, all can cause cost to increase.The scope of the temperature of in conversion unit, reacting between 80 to 160 ℃, the preferable reaction temperature interval is between 110 to 135 ℃, dissociate in the reaction process methyl alcohol that and MMA steams from distillation tower (2) as azeotrope (13) molecular balance had the active influence effect, most of by (methyl) alkyl acrylate, unreacted MMA and alcohol and small amount of methanol, catalyzer, the reaction mixture that stopper and very a spot of by product constitute at 0.5-3 hour reaction time of process (the preferred residence time is 0.75-1.5 hour) afterwards, be sent to continuously in the low-boiling-point substance distillation tower (3) that has moved, under decompression state, preferably at 20-200mbar, telling with respect to product ester is lower boiling constituent, be mainly methyl alcohol, MMA and unreacted raw alcohol composition, they steam and send back to reaction zone (14) through the distillation tower cat head.Can guarantee that by this recycle stream the material MMA that added and alcohol are for whole process, in fact all react, be mixed with catalyzer, stopper and the high boiling point by-products produced thick ester (15) that exist in liquid at the bottom of the tower of distillation tower (3) are preferably the product ester that contains 98 weight %, it can be imported other underpressure distillation operation (4 continuously, 5) reprocessing in, its working pressure is isolated the high purity product ester as overhead product (16) herein continuously between 20 to 200mbar.
For from thick ester (15) if isolate catalyzer and stopper and high boiling point by-products produced implementing with a routine as at present technical known vacuum still, then the high heat load that can not bear because of existence in liquid at the bottom of the tower can cause catalyst decomposes, and meanwhile dissociate raw alcohol and part material alcohol generate ethers again.
Two kinds of compounds (raw alcohol of adding and this pure ether) are low boiling component to product ester, and become the impurity of product ester, thereby quality product is obviously descended.The thin film evaporation equipment (5) that the solution of this problem can be adopted the harmless effect of a pair of material is with catalyzer and stopper and high boiling point by-products producedly separate from product ester, known in this respect suitable equipment have falling liquid film-, thin layer-and short-path evaporator.
In order to reach the purity (product ester＞99.9 weight %) of the highest product ester, alcohol＜120ppm, MMA＜10ppm, ether＜5ppm, colour (Apha)＜1) the high boiling product distilling period (4) of can connecting in the back, because this moment, the shortcoming with the individual equipment existence of thin film evaporation was the purification efficiency deficiency, make the high boiling product by product be blended in the straight product ester (16), the way that addresses this problem is isolated high boiling product exactly from the straight product ester, add a decompression treating tower (4) in the thin film evaporation its upper side.
From thick ester, isolate catalyzer, stopper and high boiling point by-products produced after, in liquid product at the bottom of the tower, also retain portioned product ester composition, liquid has good flowing and transportation performance at the bottom of the tower of emitting, for in catalyzer and high boiling point by-products produced (17) liquid effluent, reducing product loss as far as possible, should add a reduction vaporization section (6) at the rear portion again, its working pressure is 20-200mbar, still adopts thin film evaporation equipment to finish this task herein.As the equipment that is suitable for know still with falling liquid film-, thin layer-and short-path evaporator, the product ester that derives from the evaporator section top is difficult to guarantee that the high boiling product component concentration can satisfy the specification requirement of pure ester, it is also because catalyzer pyrolysated reason contains the ether of raw alcohol composition and the formation of part material alcohol composition herein, directly it is not sent to high boiling product distillation tower (4) for from distillate stream, extracting contained product ester for these reasons, but must return conversion unit (1) or preferably send into low boilers distillation tower (3), so that low boilers is separated earlier before at first evaporator section (5).
By following example the inventive method is further illustrated, but be not to be confined to this.
The example of being implemented be the formation of (hour inlet amount is that 6-8kg raw material (MMA and alcohol) is the 5-6kg product ester) experimental installation of in the experimental installation of pilot scale, carrying out as shown in Figure 1, promptly in process explanation, done description.
As reactor (1) is that water is steam-heated, the stainless steel cauldron that on-mechanical stirs, and maximum packed space is 151, reactor links to each other with azeotrope distillation tower (2) on being installed in it by an evaporated liquor pipeline.Azeotrope distillation tower (roof pressure=1bar absolute pressure) is-the glass tower that amplifies in laboratory that the Sulzer CY wire mesh packing of H=2m is filled, and diameter is D=0.1m, and the opening for feed of a raw alcohol composition is arranged at tower middle part (H=1m).The reactor distillate is sent to low boilers distillation tower (3) continuously, this distillation tower is decompression glass tower (roof pressure=120mbar absolute pressure) the diameter D=0.1m that amplify in the laboratory of the Sulzer CY wire mesh packing filling of a usefulness H=3.8m, opening for feed is positioned at the H=2m place, liquid at the bottom of the water steam heating tower.Reactor is sent in the top discharge of condensation (circulating fluid) (14) continuously back to, being different from falling-film evaporator (5) liquid discharging at the bottom of the tower of low boilers distillation tower (15) of representing among Fig. 1, to add man-hour continuously be to adopt heated oil heated glass thin layer evaporator, its evaporation area A=0.1m
2The evaporated liquor of this flass vaporizer is sent to the high boiling product distillation tower of installing on top (4) continuously, it is the laboratory amplification decompression glass tower (roof pressure=120mbar absolute pressure) of the Sulzer CY wire mesh packing filling of a usefulness H=0.5m, diameter D=0.05m.The liquid discharging imports one second smaller same heated oil heated glass thin layer evaporator (6) (roof pressure=120mbar absolute pressure), evaporation area A=0.02m of using continuously at the bottom of the tower
2, the evaporated liquor of the second flass vaporizer condenses and goes out materials flow with reactor and merge and to be sent to low boilers one distillation tower continuously, and liquid goes out materials flow (17) and discharges continuously from process at the bottom of the tower.
The continuous and quantitative charging of material composition (MMA and alcohol) can apply by the piston-type pump of constant delivery type, catalyzer (tetralkyl titanate) is dissolved in the MMA charging (to meet anhydrous specification) at this moment, the MMA/ catalyst charge is directly sent into reactor, and pure charging then needs preheating (temperature to the tower) to be added to the middle part of azeotropic point thing distillation tower.
By tubing sucker-rod pump the continuously feeding of stabiliser solution (being dissolved in the hydroquinone monomethyl ether of 0.2 weight % in MMA or the product ester) with 50-100g/h is added in the phegma of distillation tower.The continuous conveying of streams is available piston pump of constant delivery type between the device each several part, and also available decompression inhalation realizes that process tank (surge volume) as far as possible need not.
The available gas chromatography determination of the composition of material liquid stream (MMA-, alcohol-, MeoH-and product ester-content).
Example 1 (preparing n-BMA continuously)
In reactor, quantitatively add 4kg/h MMA/ catalyst charge for preparing n-BMA (n BuMA) continuously, wherein tetra-n-butyl titanate (Ti (n-OBu)
4) content be 0.45 weight % and the charging of 2.7kg/h propyl carbinol.In addition, loop back flow liquid in addition from low boilers distillation tower cat head and continuously flow into reactor (2.8kg/h, it consists of: 1.0 weight %n-BuMA, 38.3 weight %n-BuOH, 57.3 weight %MMA and 3.4 weight %MeOH), mol ratio at the inlet MMA:n-BuOH of reactor is 1.1: 1, the residence time in reactor is that 1 hour and MMA/MeOH azeotrope discharging speed are 1.5kg/h, temperature of reaction is controlled at 115 ℃, the MMA/MeOH-azeotrope consist of 82 weight %MeOH, 18 weight %MMA and＜5ppm n-BuOH; The outflow logistics total from reactor is 8kg/h, and it consists of: 64.6 weight %n-BuMA, and 13.5 weight %n-BuOH, 20.3 weight %MMA, 1.3 weight %MeOH and 0.3 weight % by product, therefore, reactor Space-Time-yield of n-BuMA is 570kg/h/m
3Based on being that lower boiling component almost can be told fully with respect to n-BuMA, the thick ester (5.8kg/h) that obtains in liquid at the bottom of the low-boiling-point substance fractionation Tata contains＞99.5 weight %n-BuMA and whole catalyzer and stablizers, and therefore whole process almost reaches 100% to the yield of BuOH meter; Whole process causes MMA loss because of formation MMA/MeOH azeotrope counts to the yield of MMA meter before the deduction, also is almost 100%.Evaporite ratio in first bigger thin layer evaporator (evaporated liquor is to the ratio of material logistics) is about the pure n-BuMA that obtained 5.1kg/h at 90% o'clock at the high boiling product distillation tower, it consists of＞99.92 weight %n-BuMA,＜120ppmn-BuOH,＜10ppm MMA,＜5ppm di-n-butyl ether, colour (Apha)＜0.2; Total discharging (catalyzer, stablizer, high boiling point by-products produced, n-BuMA) that evaporite ratio in second less thin layer evaporator is about 90% o'clock process is 0.1kg/h, and the yield losses of n-BuMA is pure for producing-n BuMA, is＜0.5 weight %.
Example 2 (preparing Propenoic acid, 2-methyl, isobutyl ester continuously)
In the reaction response still, quantitatively add 3.4kg/h MMA/ catalyst charge, wherein contained metatitanic acid four isobutyl esters (Ti (i-OBu) for preparing Propenoic acid, 2-methyl, isobutyl ester (i-BuMA) continuously
4) be 0.56 weight % and 2.36kg/h i-BuOH charging.In addition, loop back flow liquid in addition from low-boiling-point substance distillation tower cat head and continuously flow into reactor (2.4kg/h, it consists of: 6.2 weight %i-BuMA, 35.3 weight %i-BuOH, 56.3 weight %MMA and 2.2 weight %MeOH), mol ratio at the inlet MMA:i-BuOH of reactor is 1.1: 1, the residence time in reactor is that the discharging speed of 1.2 hours and MMA/MeOH-azeotrope is 1.26kg/h, temperature of reaction is controlled at 115 ℃, the MMA/MeOH-azeotrope consist of 82 weight %MeOH, 18 weight %MMA and＜5ppm i-BuOH; The outflow logistics total from reactor is 6.9kg/h, and it consists of: 67.3 weight %i-BuMA, and 12.0 weight %i-BuOH, 19.4 weight %MMA, 0.8 weight %MeOH and 0.5 weight % by product, therefore, reactor Space-Time-yield of i-BuMA is 516kg/h/m
3Almost can isolate fully based on the component that with respect to i-BuMA is low boilers, the thick ester (5.0kg/h) that obtains in liquid discharging at the bottom of the low-boiling-point substance fractionation Tata contains i-BuMA and has reached 99.5 weight % and whole catalyzer and stablizer, and therefore whole process almost reaches 100% to the yield of i-BuOH meter; Whole process is to the yield of MMA, counts and causes the MMA loss because of forming the MMA/MeOH-azeotrope before the deduction, also almost 100%.Evaporite ratio in first bigger vaporizer (evaporated liquor is to the material logistics ratio) is about at 90% o'clock, obtain the pure i-BuMA of 4.5kg/h at high boiling material distillation cat head, it consists of:＞99.9 weight %i-BuMA,＜150ppm i-BuOH,＜10ppm MMA, 0ppm Di-Isobutyl ether, colour (Apha)＜0.2.Evaporite ratio in second less thin layer evaporator is about at 90% o'clock, and total discharging of process (catalyzer, stablizer, high boiling point by-products produced, i-BuMA) is 0.05kg/h, the i-BuMA yield losses, and the pure-i-BuMA for producing is＜0.5 weight %.
Claims (17)
1. the method for formula (C) (methyl) alkyl acrylate is made in operate continuously
R wherein
1For-H or CH
3-Ji and R
2Be one to contain straight chain or the branching or the cyclic alkyl or aryl of 2 to 12 C atoms, a compound of through type (B)
R
2OH(B)
R herein
2Be the above-mentioned definition that provides, with (methyl) methyl acrylate (A) reaction,
R wherein
1For-H-or CH
3-Ji, in the presence of a transesterification catalyst and at least one stopper, in an equipment, carry out the continuous ester interchange reaction, it is characterized in that, reactant joins in the suitable conversion unit (1) continuously, steam continuously by a distillation tower (2) as azeotropic methyl alcohol/(methyl) methyl acrylate-mixture (13) with the methyl alcohol that when reacting, generates, in addition
-reaction mixture imports the distillation tower (3) from conversion unit continuously, through cat head volatile components (A, B, methyl alcohol) and very micro-product ester (C) are steamed and send back to conversion unit by underpressure distillation at this, at the bottom of the tower the liquid with product ester (C) with catalyzer and stopper and high boiling point by-products produced discharge;
Liquid stream (15) imports a vaporizer (5) continuously at the bottom of the tower of-distillation tower (3), this through underpressure distillation with product ester (C) and catalyzer and stopper and high boiling point by-products produced the separation.
2. press the method for claim 1, it is characterized in that, the evaporated liquor stream of vaporizer (5) is sent in the distillation tower (4) continuously, through underpressure distillation, steam high purity product ester (C) (16) and by discharging catalyzer and stopper and high boiling point by-products produced and carry a spot of product ester (C) secretly at the bottom of the tower at this by cat head.
3. press the method for claim 1, it is characterized in that, the liquid logistics imports an other thin-film evaporator (6) continuously at the bottom of the tower of distillation tower (4) or vaporizer (5), at the bottom of tower, discharge catalyzer and stopper and high boiling by product and steam remaining product ester (C) by underpressure distillation at this, and send distillation tower (3) or conversion unit (1) back to through cat head.
4. by the method for claim 1, it is characterized in that, through alcohol (B) the importing conversion unit of distillation tower (2) dehydration.
5. by the method for claim 1, it is characterized in that, between 1 and 2, be preferably 1.05-1.15 in inlet (methyl) methyl acrylate of reactor and pure mol ratio.
6. by the method for claim 1, it is characterized in that, adopt tetralkyl titanate as transesterification catalyst.
7. by the method for claim 1, it is characterized in that the amount of applications catalyst is counted 0.1-2 weight % with the MMA that adds.
8. by the method for claim 7, it is characterized in that the amount of applications catalyst is counted 0.2-1 weight % with the MMA that adds.
9. by the method for claim 1, it is characterized in that both can adopt phenothiazine, tert-butyl catechol, Resorcinol mono-methyl, also available its mixture of Resorcinol as stopper, the amount of stopper is counted between 100 to 5000ppm with reaction mixture.
10. by the method for claim 1, it is characterized in that, as the also additional oxygen of using of stopper.
11. by the method for claim 1, it is characterized in that, as alcohol preferably propyl carbinol or isopropylcarbinol.
12. the method by claim 1 is characterized in that the pressure in first distillation tower (3) is between 20 to 200mbar.
13. the method by claim 1 is characterized in that the pressure in second column (4) and the thin-film evaporator (5) (6) is between 20 to 200mbar.
14. the method by claim 1 is characterized in that the residence time is between 0.5 and 1.5 hour in conversion unit.
15. the method by claim 1 is characterized in that vaporizer (5) is a thin-film evaporator.
16. the method by claim 3 is characterized in that vaporizer (5) and vaporizer (6) are thin-film evaporators.
17. the method by claim 1 is characterized in that, is to use 2-Ethylhexyl Alcohol as alcohol.
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| CNA2007100897182A CN101274890A (en) | 2007-03-27 | 2007-03-27 | Continuous preparation of alkyl esters of (meth) acrylic acid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102557849A (en) * | 2011-12-13 | 2012-07-11 | 浙江新和成股份有限公司 | Continuous reaction method |
| CN104918911A (en) * | 2012-12-17 | 2015-09-16 | 阿肯马法国公司 | Process for preparing alkyl acrylate |
| CN105050997A (en) * | 2013-03-01 | 2015-11-11 | 阿肯马法国公司 | Process for producing 2-propylheptyl acrylate by transesterification |
| CN105481688A (en) * | 2015-11-27 | 2016-04-13 | 江门谦信化工发展有限公司 | Efficient environmentally-friendly butyl methacrylate production process |
| CN110935188A (en) * | 2019-12-18 | 2020-03-31 | 万华化学集团股份有限公司 | Continuous rectification separation method and device for hydroxyethyl (meth) acrylate crude product |
| CN116143619A (en) * | 2022-12-14 | 2023-05-23 | 湖北三里枫香科技有限公司 | A production process and device for preparing n-isobutyl (octyl) (meth)acrylate by transesterification |
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2007
- 2007-03-27 CN CNA2007100897182A patent/CN101274890A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557849A (en) * | 2011-12-13 | 2012-07-11 | 浙江新和成股份有限公司 | Continuous reaction method |
| CN102557849B (en) * | 2011-12-13 | 2014-09-24 | 浙江新和成股份有限公司 | Continuous reaction method |
| CN104918911A (en) * | 2012-12-17 | 2015-09-16 | 阿肯马法国公司 | Process for preparing alkyl acrylate |
| CN104918911B (en) * | 2012-12-17 | 2018-02-23 | 阿肯马法国公司 | Process for preparing alkyl acrylate |
| CN105050997A (en) * | 2013-03-01 | 2015-11-11 | 阿肯马法国公司 | Process for producing 2-propylheptyl acrylate by transesterification |
| CN105050997B (en) * | 2013-03-01 | 2017-05-31 | 阿肯马法国公司 | The method that the Propylheptyl of acrylic acid 2 is manufactured by ester exchange |
| CN105481688A (en) * | 2015-11-27 | 2016-04-13 | 江门谦信化工发展有限公司 | Efficient environmentally-friendly butyl methacrylate production process |
| CN105481688B (en) * | 2015-11-27 | 2017-12-29 | 江门谦信化工发展有限公司 | A kind of butyl methacrylate production technology of high-efficiency environment friendly |
| CN110935188A (en) * | 2019-12-18 | 2020-03-31 | 万华化学集团股份有限公司 | Continuous rectification separation method and device for hydroxyethyl (meth) acrylate crude product |
| CN116143619A (en) * | 2022-12-14 | 2023-05-23 | 湖北三里枫香科技有限公司 | A production process and device for preparing n-isobutyl (octyl) (meth)acrylate by transesterification |
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