CN108373409A - The preparation method of methacrylic acid and methacrylate - Google Patents
The preparation method of methacrylic acid and methacrylate Download PDFInfo
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- CN108373409A CN108373409A CN201810206739.6A CN201810206739A CN108373409A CN 108373409 A CN108373409 A CN 108373409A CN 201810206739 A CN201810206739 A CN 201810206739A CN 108373409 A CN108373409 A CN 108373409A
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 159
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 287
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims description 368
- 239000012071 phase Substances 0.000 claims description 310
- 238000000926 separation method Methods 0.000 claims description 123
- 238000000605 extraction Methods 0.000 claims description 95
- 238000009835 boiling Methods 0.000 claims description 80
- 150000002148 esters Chemical class 0.000 claims description 70
- 238000002425 crystallisation Methods 0.000 claims description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 60
- 238000007254 oxidation reaction Methods 0.000 claims description 60
- 230000003647 oxidation Effects 0.000 claims description 59
- 230000032050 esterification Effects 0.000 claims description 49
- 238000005886 esterification reaction Methods 0.000 claims description 49
- 239000012074 organic phase Substances 0.000 claims description 49
- 239000012452 mother liquor Substances 0.000 claims description 48
- 230000008025 crystallization Effects 0.000 claims description 47
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000003960 organic solvent Substances 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 20
- 238000010791 quenching Methods 0.000 claims description 20
- 230000000171 quenching effect Effects 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 17
- 239000000284 extract Substances 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 15
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 238000003672 processing method Methods 0.000 abstract description 3
- 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 abstract description 2
- 239000013078 crystal Substances 0.000 description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 38
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 32
- 238000000746 purification Methods 0.000 description 32
- 238000005406 washing Methods 0.000 description 28
- 239000003054 catalyst Substances 0.000 description 24
- -1 by isobutene Chemical compound 0.000 description 22
- 238000004821 distillation Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 17
- 239000012535 impurity Substances 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 14
- 238000005191 phase separation Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000005201 scrubbing Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 229920001427 mPEG Polymers 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000009834 vaporization Methods 0.000 description 10
- 230000008016 vaporization Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 238000005194 fractionation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000000638 solvent extraction Methods 0.000 description 6
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000010533 azeotropic distillation Methods 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000374 eutectic mixture Substances 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 125000005395 methacrylic acid group Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- FZXRXKLUIMKDEL-UHFFFAOYSA-N 2-Methylpropyl propanoate Chemical compound CCC(=O)OCC(C)C FZXRXKLUIMKDEL-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 238000006471 dimerization reaction Methods 0.000 description 2
- 208000018459 dissociative disease Diseases 0.000 description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- XFOYMWPSASGDSQ-UHFFFAOYSA-N 1-[2-(2-hydroxyethoxy)ethoxy]butan-2-ol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCC(O)COCCOCCO XFOYMWPSASGDSQ-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical class CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- ACWQBUSCFPJUPN-UHFFFAOYSA-N 2-methylbut-2-enal Chemical compound CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 1
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- AXPZIVKEZRHGAS-UHFFFAOYSA-N 3-benzyl-5-[(2-nitrophenoxy)methyl]oxolan-2-one Chemical compound [O-][N+](=O)C1=CC=CC=C1OCC1OC(=O)C(CC=2C=CC=CC=2)C1 AXPZIVKEZRHGAS-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- WODYQWZKXZFPME-UHFFFAOYSA-N CC(=CC(=O)O)C.NC(=O)OCC Chemical class CC(=CC(=O)O)C.NC(=O)OCC WODYQWZKXZFPME-UHFFFAOYSA-N 0.000 description 1
- AKSFWDNJWGSQMY-UHFFFAOYSA-N CC(=CC(=O)OCCCCO)C Chemical compound CC(=CC(=O)OCCCCO)C AKSFWDNJWGSQMY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000242583 Scyphozoa Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- YTAHJIFKAKIKAV-XNMGPUDCSA-N [(1R)-3-morpholin-4-yl-1-phenylpropyl] N-[(3S)-2-oxo-5-phenyl-1,3-dihydro-1,4-benzodiazepin-3-yl]carbamate Chemical compound O=C1[C@H](N=C(C2=C(N1)C=CC=C2)C1=CC=CC=C1)NC(O[C@H](CCN1CCOCC1)C1=CC=CC=C1)=O YTAHJIFKAKIKAV-XNMGPUDCSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- VPSLGSSVPWVZFG-UHFFFAOYSA-N butan-2-yl propanoate Chemical compound CCC(C)OC(=O)CC VPSLGSSVPWVZFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- KTIGDTYUEDDRFL-UHFFFAOYSA-N chloromethane prop-1-ene Chemical group [H]CCl.[H]C=C([H])C KTIGDTYUEDDRFL-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XPJRQAIZZQMSCM-UHFFFAOYSA-N heptaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCO XPJRQAIZZQMSCM-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 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 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229940113165 trimethylolpropane Drugs 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0004—Crystallisation cooling by heat exchange
- B01D9/0013—Crystallisation cooling by heat exchange by indirect heat exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0036—Crystallisation on to a bed of product crystals; Seeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/004—Fractional crystallisation; Fractionating or rectifying columns
- B01D9/0045—Washing of crystals, e.g. in wash columns
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Abstract
The present invention relates to the preparation methods of methacrylic acid and methacrylate.More particularly it relates to the preparation method of at least one of methacrylic acid and methacrylate；The invention further relates to the processing methods of the water phase comprising at least one organic compound, and the equipment for being used to prepare at least one of methacrylic acid and metha crylic ester.
Description
The application be September in 2011 16 application No. is the 201180073459.9, applying date, entitled " methyl
The divisional application of the Chinese patent application of the preparation method of acrylic acid and methacrylate ".
Technical field
The present invention relates to the preparation method of methacrylic acid, the preparation method of methacrylate and have comprising at least one
The processing method of the water phase of machine compound.
Background technology
Methacrylic acid (MAA) and methacrylate, such as methyl methacrylate (MMA) and methacrylic acid fourth
Ester is used for various applications.The industrial production of methacrylic acid particularly by isobutene, the tert-butyl alcohol, methacrolein or
The gaseous oxidation of the heterogeneous catalysis of isobutylaldehyde carries out.By cooling and condensation, by the vapor reaction phase transition obtained in this way at
Metering system aqueous acid optionally divides with low-boiling substance such as acetaldehyde, acetone, acetic acid, methacrylaldehyde and methacrolein
From, solvent extraction tower is then introduced, with the extractant that utilization is suitable, such as short hydrocarbon, extraction and separation methacrylic acid.By institute
The methacrylic acid of separation is further purified, such as by distillation, to detach high boiling impurity, such as benzoic acid, maleic acid
And terephthalic acid (TPA), to obtain pure methacrylic acid.Such known method is for example described in EP 0 710 643, US
4,618,709, in US 4,956,493, EP 386 117 and US 5,248,819.
Such known method generates a large amount of waste water in each operation stage, and maximum is in mutually to extract from quenching in them
Take remaining water phase form after methacrylic acid.Water essentially from enter gaseous oxidation step addition steam or water, and
Use from water as the quenchant in cooling and condensing steps, and carry out automatic oxidation reaction itself.This waste water contains phase
When a large amount of organic compound and in the case where not being further processed to remove these organic compounds at least partly
It cannot reuse or safely throw aside.Such organic compound generally includes desirable product such as methacrylic acid and (returns
Because being extracted into organic extractant in not exclusively) and oxidation step other by-products such as acrylic acid, acetic acid and propionic acid,
They are also commercially valuable.Content of organics in this waste water it is generally too high without at water treatment technology such as biology
Reason, such as activated-sludge method are compatible without requiring significantly dilution, considerable time and very big treatment facility, so that
In the production of business methacrylic acid, the waste water is often made to burn, for example, US 4, described in 618,709 like that.However, waste water
Burning is all in the environment and economically unfavorable, it is desirable that high-energy inputs, and causes to may require before it can be discharged into environment
The emission being further processed also results in the loss for being present in the potential valuable organic compound in waste water in addition, and
The loss of water itself.
The organic compound being present in waste water can be recycled at least partly therefore can be advantageous.Also it will be advantageous that
Recycle-water itself it is at least some, or with for it undergo biological treatment and/or for being discharged into environment it is sufficiently low
Content of organics, or be enough to reuse in the water, be used for example as industrial process waters or be used for methacrylic acid/metering system
Purity in sour methyl esters preparation process itself.CN 1903738 propose using membrane separator then rectifying column with purify come from third
The waste water and acrylic acid, toluene and acetic acid of olefin(e) acid production.In general the shortcomings that membrane filtration is, it is desirable that a large amount of water (warp
It is often used waste water itself) rinse out the not component by filter.This washings with increased organic compound concentrations
Then it itself have to be further processed or burn.
In addition, various method and steps, especially the methacrylic acid methacrylic acid after being extracted in aqueous quenching phase
It detaches, is resulted in as the methacrylic acid phase of distillate and as residue (sometimes referred to as with the general distillation of extractant
Bottom phase, distillation leftover or waste oil) higher-boiling compound phase, still contain a large amount of methacrylic acids.It can be from height boiling
Point compound, which mutually recycles at least some of this methacrylic acid, to be advantageous.For the place of such higher-boiling compound phase
Reason is it has been proposed that various methods.
EP 1 043 302 is proposed handles the waste oil produced from acrylic or methacrylic acid with solvent, to prevent from giving up
Generation of the polymerization and/or sediment of oil in waste oil.US 2005/0054874 is disclosed to be closed in acrylic or methacrylic acid
The higher boiling heavy ingredient being discharged from each step is classified by their acrylic or methacrylic acid content at middle, and
Them are handled by mutually merging them with the higher boiling from other industrial process, so that they can be heavy in no solid
It is stored in the case of shallow lake.However, all recycling methacrylic acid from waste oil without introduction in any piece in those references.
Invention content
The purpose of the present invention is usually the shortcomings that overcoming art methods as far as possible.
Another purpose is to increase methacrylic acid and/or methyl by mutually recycling methacrylic acid from higher-boiling compound
The gross production rate of methyl acrylate preparation method.
Another purpose is by recycling the totality that organic compound increases methacrylic acid preparation method from technique waste water
Efficiency and/or yield.
Another object of the present invention is by reducing technique waste water as far as possible by orgnic compound pollution from this waste water
Recycle-water undergoes biologically pure process, or be discharged into environment so that this water can reuse, optionally in biology or other
It is discharged into environment after the purification process of type, rather than is incinerated together with organic compound.
Another purpose is by recycling the totality that organic compound increases methacrylic acid preparation method from technique waste water
Efficiency and/or yield.
For solving the contribution of above-mentioned purpose by the preparation method of at least one of methacrylic acid and methacrylate
It makes, this method includes following methods step：
A1) at least one C4The gaseous oxidation of compound includes the reaction phase of methacrylic acid to obtain；
A2) quenching of the reaction phase is to obtain the thick water phase for including methacrylic acid；
A3) at least part of the methacrylic acid is extracted into organic molten from the thick water phase comprising methacrylic acid
In agent, to obtain the thick organic phase and the first water phase that include methacrylic acid, wherein first water phase includes following components
I. at least 65 weight %, preferably 65 weight %-99.9 weight %, more preferable 70 weight %-99.8 weight % water, then
More preferable 75 weight %-99 weight %, more preferable 76 weight %-98.5 weight %, more preferable 77 weight %-98 weight %, very
To more preferable 78 weight %-97.5 weight %, even more preferably 79 weight %-95 weight %, even more preferably 80 weight %-90 are heavy
% water is measured, based on the total weight of first water phase, and
Ii. it is no more than 35 weight %, preferably 0.1 weight %-35 weight %, preferably 0.2 weight %-30 weight %, it is more excellent
1 weight %-25 weight % are selected, even more preferably 1.5 weight %-24 weight %, more preferable 2 weight %-23 weight %, even more excellent
2.5 weight %-22 weight %, even more preferably 5 weight %-21 weight % are selected, even more preferably 10 weight %-20 weight % are extremely
A kind of few organic compound, based on the total weight of first water phase,
The sum of the weight amount of wherein i. and ii. is 100 weight %；
A4) the separation of at least part of the methacrylic acid and the thick organic phase comprising methacrylic acid and optionally
Purifying；
A5) optionally, step a4) in obtain the methacrylic acid at least part of esterification；
B) be included in step a3) obtained in the first water phase in water at least part and at least one component ii.
At least part of separation, to obtain the second water phase and organic phase, wherein the organic phase includes at least one component ii.,
The wherein described second water phase at least one component ii. of dilution compared with the first water phase；
C) optionally, at least part of at least one organic compound and the second water phase of acquisition in method and step b)
Separation is to obtain third water phase；
D) optionally, the separation of at least part of at least one component ii. and the organic phase obtained in method and step b).
Contribution for solving above-mentioned purpose is also made by the processing method of the water phase comprising at least one organic compound,
This method includes following methods step：
A) the first water phase for including following components is provided
I. at least 65 weight %, preferably 65 weight %-99.9 weight %, more preferable 70 weight %-99.8 weight % water, then
More preferable 75 weight %-99 weight %, more preferable 76 weight %-98.5 weight %, more preferable 77 weight %-98 weight %, very
To more preferable 78 weight %-97.5 weight %, even more preferably 79 weight %-95 weight %, even more preferably 80 weight %-90 are heavy
% water is measured, based on the total weight of first water phase, and
Ii. it is no more than 35 weight %, preferably 0.1 weight %-35 weight %, preferably 0.2 weight %-30 weight %, it is more excellent
1 weight %-25 weight % are selected, even more preferably 1.5 weight %-24 weight %, more preferable 2 weight %-23 weight %, even more excellent
2.5 weight %-22 weight %, even more preferably 5 weight %-21 weight % are selected, even more preferably 10 weight %-20 weight % are extremely
A kind of few organic compound, the total weight based on first water phase；
The sum of the weight amount of wherein i. and ii. is 100 weight %；
B) at least part of the water in the first water phase provided in method and step a) and at least one component are included in
Ii. at least part of separation is to obtain the second water phase and organic phase, wherein the organic phase includes at least one component
And the wherein described second water phase at least one component ii. of dilution compared with the first water phase ii.,；
C) optionally, at least part of at least one organic compound and the second water phase of acquisition in method and step b)
Separation is to obtain third water phase；
D) optionally, the separation of at least part of at least one component ii. and the organic phase obtained in method and step b).
In one embodiment of the invention, the preparation side of at least one of methacrylic acid and methacrylate
Method, including following methods step：A1) gaseous oxidation of at least one C4 compounds is to obtain the reaction for including methacrylic acid
Phase；A2) quenching of the reaction phase is to obtain the thick water phase for including methacrylic acid；A3) at least the one of the methacrylic acid
Part is extracted into from the thick water phase comprising methacrylic acid in organic solvent, thick organic comprising methacrylic acid to obtain
Phase and the first water phase, wherein first water phase includes following components：I. at least 65 weight %, preferably 65 weight %-99.9 weights
Measure %, more preferable 70 weight %-99.8 weight % water, even more preferably 75 weight %-99 weight %, more preferable 76 weight %-
98.5 weight %, more preferable 77 weight %-98 weight %, even more preferably 78 weight %-97.5 weight %, even more preferably 79
Weight %-95 weight %, even more preferably 80 weight %-90 weight % water, total weight and ii. based on first water phase are not
More than 35 weight %, preferably 0.1 weight %-35 weight %, preferably 0.2 weight %-30 weight %, more preferable 1 weight %-25 weights
% is measured, even more preferably 1.5 weight %-24 weight %, more preferable 2 weight %-23 weight %, even more preferably 2.5 weight %-22
Weight %, even more preferably 5 weight %-21 weight %, even more preferably at least one organic compound of 10 weight %-20 weight %
Object, based on the total weight of first water phase, the sum of the weight amount of wherein i. and ii. are 100 weight %；A4) the methyl
It the separation of at least part of acrylic acid and the thick organic phase comprising methacrylic acid and optionally purifies；A5) optionally, step
A4 at least part of esterification of the methacrylic acid obtained in)；B) be included in step a3) obtained in the first water phase
In at least part of water detached at least one at least part of of component ii., to obtain the second water phase and organic phase,
The wherein described organic phase includes at least one component ii., and dilution is at least compared with the first water phase for wherein described second water phase
A kind of component ii.；C) optionally, at least part of at least one organic compound and the second water obtained in method and step b)
The separation of phase, to obtain third water phase；D) optionally, at least part of at least one component ii. is obtained with method and step b)
The separation of the organic phase obtained.
In step a1 according to the method for the present invention) in experience gaseous oxidation C4Compound be preferably selected from isobutene,
The C of the tert-butyl alcohol, isobutylaldehyde and methacrolein4The mixture of compound or two or more in them.The one of the present invention
In a preferred aspect, C4Compound is derived from the division of methyl tertiary butyl ether(MTBE) (MTBE) or ethyl tert-butyl ether (ETBE) (ETBE).
Step a1 according to the method for the present invention) in gaseous oxidation preferably in the presence of at least one oxidation catalyst into
Row.If C4Compound is isobutene or the tert-butyl alcohol, and the gaseous oxidation to obtain the gas phase containing methacrylic acid can be one
It is carried out in a step, one of step is considered herein as referring to initial oxidation into methacrolein and be further oxidized to
The process of methacrylic acid substantially carries out in the same reaction zone in the presence of at least one catalyst.Optionally, step a1)
In gaseous oxidation can in more than one step, preferably in two steps, preferably be separated from each other two or more
It is carried out in reaction zone, wherein it is preferred that there are two or more catalyst, each catalyst is preferably in and another catalyst
In the reaction zone being separated from each other.In two step gaseous oxidations, first step is preferably C4Compound is at least partly oxidized to methyl
Methacrylaldehyde, then methacrolein be at least partly oxidized to methacrylic acid.Thus, for example, in the first reaction step, preferably
In the presence of being suitable at least one C4Compound oxidation at methacrolein at least one catalyst, and in second reaction step
In, there is at least one catalyst for being suitable for that methacrolein is oxidized to methacrylic acid.
The suitable reaction condition of catalytic gas phase oxidation is, for example, about 250 DEG C-about 450 DEG C, preferably approximately 250
DEG C-about 390 DEG C of temperature, and about 5 atmospheric pressure of about 1 atmospheric pressure-pressure.Space velocity can be about 100-
About 6000/ hour (NTP), preferably approximately 500- about 3000/ hour.C4Raw material such as isobutene to methacrolein and/
Or the oxidation of methacrylic acid, such as catalytic gas phase oxidation and catalyst used are well known in the literature, such as from US
5,248,819、US 5,231,226、US 5,276,178、US 6,596,901、US 4,652,673、US 6,498,270、US
5,198,579, well known to US 5,583,084.
It is suitable for the especially preferred catalysis at methacrolein and/or methacrylic acid by isobutene or Oxidation of t-Butanol
Agent and method description are suitable for methacrolein being oxidized to the especially preferred of methacrylic acid urging in EP 0 267 556
Agent and method description are in EP 0 376 117.These documents are incorporated by reference as and are formed as the disclosure of invention accordingly
A part.
According to the method for the present invention gaseous oxidation from middle methacrolein to methacrylic acid preferably about 250- about
350 DEG C and temperature below, under the pressure of about 3 atmospheric pressure of about 1-, and about 800- about 1800Nl/l/h's
It is carried out under volume load.
As oxidant, usually using oxygen, for example, be in air form, or in pure oxygen or at least one in reaction item
The diluted oxygen form of inert gas (such as at least one of nitrogen, carbon monoxide and carbon dioxide), wherein air under part
Preferably as oxidant and nitrogen and/or carbon dioxide are preferably as diluent gas.If carbon dioxide is used as diluent gas,
It is preferably the carbon dioxide of the burning from reaction gas and/or by-product, preferred catalytic or hot burns recirculated.Undergo basis
The step a1 of the method for the present invention) in gaseous oxidation gas preferably also include water, usually be in vapor form exist.It can be with
Before or during gas phase reaction, or before and during gas phase reaction, oxygen, one or more inert gases and water are introduced
Reaction phase or and C4Compound combines.
In a preferred embodiment according to the method for the present invention, walked being supplied comprising the mixture of following substance
Rapid a1)：At least one C4Gas is discharged in compound, air or oxygen and the oxidation reactor of recycling, preferably in recycling
The preceding oxidation reactor discharge gas to have burnt.The reactor discharge gas preferably comprises at least a kind of unreacted C4Change
Object, at least one oxycarbide, nitrogen and oxygen are closed, Yi Jishui, this depends on presence and the work of separation condition and combustion step
With.
In two steps gaseous oxidation according to the present invention, C in the first step4Compound:O2:H2O:Inert gas
Preferred volume ratio is usually 1:0.5-5:1-20:3-30, preferably 1:1-3:2-10:7-20.Metering system in second step
Aldehyde:O2:H2O:The volume ratio of inert gas is preferably 1:1-5:2-20:3-30, preferably 1:1-4:3-10:7-18.
In step a2 according to the method for the present invention) in, keep the gas phase comprising methacrylic acid cooling and condensation (is commonly referred to as
Quenching) and obtain the condensate in the thick aqueous solution form comprising methacrylic acid.Condensation can pass through those skilled in the art
It is known and seem that suitable any means carry out, such as by the way that the gas phase for containing methacrylic acid is cool below its group
Point at least one of dew point, the especially temperature of the dew point of at least one of water and methacrylic acid.Suitable cooling means
It is known to the skilled in the art, for example, cooled down using at least one heat exchanger, or by quenching, such as by with liquid,
Such as with water, water-based composition or organic solvent, for example, organic solvent selected from aromatics or aliphatic hydrocarbon or they at least two
The mixture of kind, sprays the gas phase, wherein preferred organic solvent has under quenching conditions compared with low-vapor pressure, such as heptan
Alkane, toluene or dimethylbenzene, wherein water form cold preferably as quenching liquid according to the present invention, and in being quenched step itself
At least part of condensate is even more preferably.Suitable method of quenching is known to the skilled in the art, such as from DE 21
36 396、EP 297 445、EP 297 788、JP 01193240、JP 01242547、JP 01006233、US 2001/
0007043,6 US, 596,901, US 4,956,493, US 4,618,709, US 5,248,819 know that they are related to third
Olefin(e) acid and the disclosure of methacrylic acid quenching introduce and are formed as a part for present disclosure accordingly.It is excellent according to the present invention
Choosing is that gas phase is cooled to 40-80 DEG C of temperature and is included with being washed derived from the water and/or condensate for being quenched step
The aqueous solution of methacrylic acid, the aqueous solution can also include different amounts of impurity such as acetic acid, maleic acid, fumaric acid, lemon health
Acid, acrylic acid and formic acid and aldehyde for example formaldehyde, acetaldehyde, propionic aldehyde, methacrylaldehyde, methacrolein, ketone and it is unreacted a kind of or
A variety of C4Compound.These impurity and water are detached with methacrylic acid to obtain high-purity with needing the degree of maximum possible
Methacrylic acid.
At least part of the methacrylic acid is from the extraction of the thick aqueous solution containing methacrylic acid in method and step a3)
It is middle to utilize organic extractant, for example, at least one organic solvent, preferably at least a kind of organic solvent substantially unmixing with water
It carries out, so that water phase and organic phase can be formed.Method and step a3) further include being separated from each other the water phase and organic phase.It can
For step c) according to the method for the present invention preferred organic solvent have it is different from the boiling point of methacrylic acid, preferably compare
Its lower boiling point.It is preferred that in the method according to the invention, method and step a3) in the organic extractant that uses have big
What is measured under air pressure is less than 161 DEG C of boiling point.The organic extractant then can be in principle in step according to the method for the present invention
Rapid a4) in detached with methacrylic acid, such as by distillation, preferably at least partly, preferably to detach to a large extent,
In it preferably at least partly be used as low-boiling-point substance in distiller position more higher than pure methacrylic acid remove.Can by institute
Organic extractant or the part of it guiding of separation return to method and step a3), optionally at least one cooling and/or purifying step
After rapid.The step for preferred organic solvent be especially selected from alkane and aromatics, the hydrocarbon of optimizing alkyl aromatics, wherein being selected from
C6-C8At least one organic solvent of hydrocarbon is preferred, and wherein heptane, toluene and dimethylbenzene are especially preferred, most preferably heptan
Alkane, preferably normal heptane.Method and step a3) can by it is known to those skilled in the art just look at suitable any means into
Row, tower, rotating extractor, scrubbing tower, phase are packed or filled with preferably as counter-current extraction, such as using solvent extraction tower, pulse
Separator is suitable for carrying out with organic solvent aqueous phase extracted and by organic phase miscellaneous equipment separated from the water.According to the present invention
Preferably, by least part of the methacrylic acid included in metering system aqueous acid, preferably at least 50 weight %,
Preferably at least about 70 weight %, preferably at least about 80 weight %, more preferably at least about 90 weight % are extracted into organic phase
In.
Therefore in step a3 according to the method for the present invention) two phases of middle acquisition：Include the thick organic phase of methacrylic acid,
It is led to step a4 according to the method for the present invention), and (water and at least one have by amount i. containing component described above and ii.
Machine compound) the first water phase.Can be anti-in gaseous oxidation as the component ii. organic compounds being included in the first water phase
Any organic compound formed during answering, for example, it is associated with the thick water phase obtained in being quenched step above mentioned by that
A bit and unreacted C4Compound and remain in any methacrylic acid in water phase.Although the first water phase includes a small amount of uses
In method and step a2) in the organic solvent of extraction be possible, such as be attributed to organic phase and the first water phase not exclusively point
From, but this solvent is not intended as component ii..
In step a4 according to the method for the present invention) in, allow step a3) in obtain it is thick organic comprising methacrylic acid
Mutually experience separation, preferred thermal separation process, by least part of the methacrylic acid wherein included with as method
Step a3) in extractant organic solvent separation.If using thermal release, this is preferably distilled, wherein method and step a3)
In for extraction top product of the organic solvent preferably as destilling tower or the upper position in destilling tower, preferably in destilling tower
The first half in position, removed preferably at the position in upper one third, and methacrylic acid or rich methacrylic acid
Mutually removed in the lower position of the ratio extractant of destilling tower.Bottom product in tower, wherein term " bottom product " also include
Any phase of the low position collection in one or more positions of one or more methacrylic acid phases, quilt are collected in the ratio of destilling tower
It is considered higher-boiling compound phase according to the present invention.This bottom product generally comprises the boiling point group higher than methacrylic acid
Point and polymer material, together with the methacrylic acid of variable quantity, the wherein amount of methacrylic acid can reach higher boiling chemical combination
Most about 95 weight % or even more of the total weight of object phase.It can also use, for example, fractionation or rectifying column, so that boiling
Point is retained in bottom product higher than the impurity of methacrylic acid and can be in tower position more higher than the bottom product
Remove the methacrylic acid of higher purity.In this case, the methacrylic acid of bottom product (higher-boiling compound phase) contains
The case where amount can be less than with when simple destilling tower.If the organic solvent for extraction has the boiling point than methacrylic acid
Higher boiling point can also then remove at the top of tower and/or position more higher than one or more positions of removing extractant
Demethyl acrylic acid phase.The methacrylic acid or rich being further purified for methacrylic acid phase obtained in this way can pass through ability
Means known to field technique personnel, for example, it is for example logical using further thermal process, such as distillation or rectifying, or by other means
Crystallization is crossed to carry out.Intermediate steps can also include within according to the method for the present invention, in method and step a4) before or during, example
If stripped or distilling to detach low-boiling compound or higher-boiling compound, filter to remove solid impurity, crystallization, in washing etc.
Any one or more.The number of purifying and other separating steps depends on the required pure of contaminant capacity and methacrylic acid final product
Degree.If methacrylic acid will use as it is, such as single as the monomer or copolymerization for being used to prepare methacrylate polymer
Body uses, then higher purity may be preferred, and this particularly depends on final applications.If methacrylic acid will be esterified,
Then the lower purity of methacrylic acid can be acceptable, for example, if ester final product can be simpler than methacrylic acid
It is single, if more effective or more efficient purifying.As using any thermal process for being related to methacrylic acid or methacrylate, divided
From and/or purifying preferably carried out in the presence of one or more polymerization inhibitors.
In a preferred embodiment according to the method for the present invention, method and step a4) include method and step aa4) high
The separation of boiling-point compound phase and thick organic phase.
In this embodiment according to the method for the present invention, the higher-boiling compound mutually distillation as above-mentioned thick organic phase
In bottom product separation.Term " bottom product " is in this article referred in the bottom of distillation, rectifying or fractionating column or in lower part
Position, the preferably product in the extraction of the position of about lower part one third.Higher-boiling compound can include mutually up to about 95
Weight %, preferably approximately 60 weight %- about 90 weight % of about 95 weight %, more preferably from about 65 weight %- are more preferably big
About 85 weight % methacrylic acids of about 70 weight %-, based on the total weight of higher-boiling compound phase, the higher-boiling compound
Remaining weight of phase is made of the boiling point component higher than methacrylic acid (" higher-boiling compound "), such as higher boiling acid such as lemon
Health acid, maleic acid, terephthalic acid (TPA), trimellitic acid and analog, aldehyde such as p-tolualdehyde and benzaldehyde, polymer material,
Especially the polymer of methacrylic acid and polymerization inhibitor are for example, quinhydrones, hydroquinone monomethyl ether, phenthazine, benzo phenthazine.
, it is preferred according to the present invention that by method and step aa4) in detach higher-boiling compound phase at least part,
Preferably at least 50 weight %, more preferably at least 60 weight %, more preferably at least 70 weight %, even more preferably at least 80 weight %,
Even more desirably at least 90 weight %, more preferably at least 95 weight %, are even more preferably fully incorporated method and step a3) in obtain
Or the first water phase provided in method and step a).In this way, higher-boiling compound phase can be handled together with the first water phase, and
At least part of the methacrylic acid included in the higher-boiling compound phase can be recycled.When by the first water phase with
When mutually merging a small amount of precipitation may occur for higher-boiling compound, so that if necessary, for example, if the amount of sediment
It is enough to adversely affect one or more further method and steps, or the conveying of interference liquid phase, especially via pipeline,
It, can be into the solid- liquid separation of line option then before liquid phase is directed to further method and step.According to the method for the present invention
This embodiment quotes the first water phase and is also intended to refer to comprising the higher-boiling compound phase in the description of the method for the present invention
At least part of first water phase.(they are regarded as " giving up " before this mutually and general higher-boiling compound phase with the first water phase
Be incinerated) this processing also have the advantage that, i.e. their processing and methacrylic acid/methacrylate preparation side
Method is parallel.This is avoided any possible negative effect to methacrylic acid/methacrylate preparation method, this may pass through
One or both of these phases are directly recycled at least partly in methacrylic acid/methacrylate preparation method
Come carry out.
At least part of the methacrylic acid obtained in this way is in method and step a5) in esterification can be by this field skill
Suitable any mode is just looked at known to art personnel to carry out, and is optionally carried out in the presence of polymerization inhibitor, to prevent metering system
The polymerization of acid and/or methyl methacrylate.Step a5) in the means that are esterified do not limited especially.Esterification can example
Such as, such as US 6,469,202, JP 1249743, EP 1 254 887, US 4,748,268, US 4,474,981, US 4,956,
493 or US 4 is carried out like that described in 464,229, the disclosure of their esterification for being related to acrylic acid and methacrylic acid
A part for present disclosure is introduced and is formed as accordingly.Liquid phase esterification is preferred.If esterification using methacrylic acid and
Directly reaction between alcohol carries out, then preferably the reaction passes through suitable catalyst.Esterification catalyst is art technology
Personnel are known and include, for example, multiphase or homogeneous catalyst such as solid catalyst or liquid catalyst.Esterification catalyst is excellent
Choosing be acid-exchange resin such as US 6,469,292, JP 1249743, described in EP 1 254 887 or can be with quotient
The name of an article(Rohm and Haas Corp.)、(Dow Corp.) or
Those of commercially available from (Lanxess AG), or it is capable of the acid of catalytic esterification, such as sulfuric acid H2SO4。
According to the present invention in method and step a5) in prepare methacrylate preferably have formula [CH2=C (CH3) C (=O)
O]n- R, and can be by with formula R (OH)mAlcohol methacrylated is formed, wherein
N and m represents 1-10, preferably 1-6, more preferable 1-5, more preferable 1-4, the integer of more preferable 1-3
R is selected from linear chain or branched chain, saturation or unsaturation, the hydrocarbon of the ring of aliphatic series or aromatics or straight chain and linear chain or branched chain, satisfies
And/or the ring or straight chain of unsaturated, aliphatic series or aromatics contains heteroatomic hydrocarbon, such as alkyl, hydroxyalkyl, aminoalkyl, Qi Tahan
The residue of nitrogen and/or oxygen, glycol, glycol, triol, bis-phenol, fatty acid residue, wherein R preferably represent methyl, ethyl, and propyl is different
Propyl, butyl, especially normal-butyl, isobutyl group, ethoxy, preferably 2- ethoxys and hydroxypropyl, preferably 2- hydroxypropyls or 3- hydroxyls
Propyl, 2- ethylhexyls, isodecyl, cyclohexyl, isobornyl, benzyl, 3,3,5- trimethylcyclohexyls, stearyl, diformazan ammonia
Base ethyl, dimethylaminopropyl, 2- tertiary butyl aminoethyls, ethyl triethylene glycol, tetrahydrofurfuryl, butyldiglycol, methoxyl group are poly-
Ethylene glycol -350, methoxy poly (ethylene glycol) 500, methoxy poly (ethylene glycol) 750, methoxy poly (ethylene glycol) 1000, the poly- second of methoxyl group
Glycol 2000, methoxy poly (ethylene glycol) 5000, allyl, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, poly- second
Glycol 400,1,3-BDO, 1,4-butanediol, 1,6- hexylene glycol, glycerine, two urethanes, Ethoxylated bisphenol A, containing 10 oxidations
The Ethoxylated bisphenol A of ethylene unit；Trimethylolpropane, ethoxylation C16-C18Aliphatic alcohols are as contained 25 ethylene oxide lists
Those of member, 2- trimethylammoniumethyls.
Methacrylate can also by other methods well known by persons skilled in the art, such as by transesterification, by
It is prepared by methyl methacrylate.In another possible preparation of hydroxyester derivative, methacrylic acid according to the present invention
It can be reacted with corresponding ether ring, such as epoxides, especially ethylene oxide or propylene oxide in ring-opening reaction.
Preferred methacrylate is alkyl methacrylate, especially methacrylic acid methyl, ethyl, propyl,
Isopropyl, butyl ester, especially methacrylic acid methyl, normal-butyl, isobutyl group, sec-butyl ester, especially methyl methacrylate
Ester, n-BMA, Isobutyl methacrylate, hydroxy ester methacrylate derivative, such as methacrylic acid
Hydroxyl ethyl ester, preferably 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate, preferably methacrylic acid 2- hydroxypropyl esters
Or methacrylic acid 3- hydroxypropyl esters and other methacrylates such as ethyl methacrylate, methacrylic acid 2- ethyls
Own ester, isodecyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, first
Base acrylic acid 3,3,5- 3-methyl cyclohexanols ester, stearyl methacrylate, dimethylaminoethyl methacrylate, metering system
Sour dimethylamino propyl ester, methacrylic acid 2- tertiary butyl ammonia ethyl ester, ethyl triethylene glycol methacrylate, methacrylic acid four
Tetrahydrofurfuryl ester, butyldiglycol methacrylate, -350 methacrylate of methoxy poly (ethylene glycol), methoxy poly (ethylene glycol)
500 methacrylates, 750 methacrylate of methoxy poly (ethylene glycol), 1000 methacrylate of methoxy poly (ethylene glycol),
2000 methacrylate of methoxy poly (ethylene glycol), 5000 methacrylate of methoxy poly (ethylene glycol), methacrylic acid allyl
Ester, ethoxylation (optionally, for example, EO containing 25mol) C16-C18The metha crylic ester of fatty alcohol, methyl chloride propylene
Sour 2- trimethyl ammoniums ethyl ester；Ethylene glycol dimethacrylate, dimethacrylate, triethylene glycol dimethyl propylene
Olefin(e) acid ester, polyethylene glycol 200 dimethylacrylate, polyethylene glycol 400 dimethylacrylate, 1,3-BDO dimethyl propylene
Olefin(e) acid ester, 1,4-butanediol dimethylacrylate, 1,6-Hexanediol dimethacrylate, glycerine dimethacrylate,
Two urethane dimethylacrylates, Ethoxylated bisphenol A dimethylacrylates, ethoxylation (optionally, for example, containing 10EO)
Bisphenol a dimethacrylate；Trimethylol-propane trimethacrylate, wherein particularly preferred methyl methacrylate, first
Base butyl acrylate and hydroxy ester methacrylate derivative.
In one side according to the method for the present invention, the separation in method and step b) preferably includes following methods step：
B1a) use extractant extracting process step a3) in obtain or method and step a) in provide the first water phase at least
A part is to form the second water phase and include the extraction phase of at least one component ii.；
B1b) the second water phase and the extraction phase are at least partially separate；
In method and step b1a according to the method for the present invention) in, the first water of component i. and ii. are included with extractant extraction
At least part of phase, preferably all, to form extraction phase and the second water phase., it is preferred according to the present invention that by least one
At least part of component ii. is extracted into extraction phase, so that the dilution at least one group compared with the first water phase of the second water phase
Divide ii..Extraction is preferably under environment temperature or raised temperature, preferably at about 20 DEG C-about 65 DEG C, more preferably from about 30
It is carried out at a temperature of DEG C-about 60 DEG C, even more preferably about 40 DEG C-about 55 DEG C.Extraction is preferably liquid-liquid extraction.Extraction can
To just look at suitable any means by known to those skilled in the art, such as utilize extraction tower, scrubbing tower, phase separator
Or it is known to those skilled in the art just look at be suitable for liquid-liquid extraction miscellaneous equipment carry out.It has been found that being suitable for basis
The method and step b1a of the method for the present invention) extractant be organic solvent, ionic liquid and organic or inorganic oil.Suitable for root
According to the method and step b1a of the method for the present invention) extractant (especially organic solvent) be preferably characterized in that and have the following performance
At least one of, preferably at least two, more preferably at least three, more preferably all：
I) average k-value measured according to the method described in this article at 25 DEG C in system extractant-water for acetic acid exists
0.1-100, preferably 0.2-90, more preferable 0.3-80, even more preferably 0.3-70, in the range of more preferable 0.4-60；
Ii) it is no more than 2260kJ/kg, preferably more than 2000kJ/kg, preferably more than 1500kJ/kg do not surpass more preferably
1000kJ/kg is crossed, the vaporization enthalpy of 800kJ/kg is even more preferably no more than；
Iii) 35-140 DEG C, preferably 35-125 DEG C, more preferable 40-120 DEG C, even more preferably 40-110 DEG C of boiling point；
Iv) at 25 DEG C, preferably 35 DEG C, more preferable 45 DEG C, even more preferably at a temperature of 50 DEG C, it is no more than 150g/l, preferably
No more than 130g/l, more preferably no more than 110g/l, even more preferably it is no more than 100g/l, even more preferably no more than 90g/l's
Solubility in water.
Unless otherwise indicated, above-mentioned performance is measured under about 50 DEG C and environmental pressure.Term " k values " refers to distribution system
Number, the i.e. corresponding organic compound of instant component ii. are in the state of the equilibrium in organic (extraction) the mutually distribution between water phase
Ratio.It is more in water phase that k values more than 1 refer to that the ratio that corresponding organic compound is present in organic (extraction) phase is present in.Though
So have the effect of that the extractant of the k values less than 1 can be used for having reached I, but according to the method for the present invention, higher k values,
1 k values are greater than, are therefore preferred, because they show that organic compound is more completely extracted into from the first water phase
It takes in phase.Although up to 100 k values are possible, have and be up to about 5,10,20,30,40,50,60,70,80 or 90
The extractants of k values according to the present invention be also likely to be preferred.Lower k values, especially less than 5 and k within the above range
Value is for example, it is also possible to and it is acceptable, especially if extractant also has in other preferred properties in favourable scope
It is one or more.If extractant is organic solvent, vaporization enthalpy and boiling point are preferably as low as possible in actual limit, especially
It is so that extractant is preferably liquid at a temperature of extracting progress.Vaporization enthalpy therefore preferably not less than about 22kJ/mol and boiling
Preferably greater than 0 DEG C of point, operation temperature when more desirably not less than being extracted.Vaporization enthalpy is preferably no greater than the vaporization enthalpy of water
(2260kJ/kg or 40.65kJ/mol), to be reduced as far as possible in step b1b according to the method for the present invention) in the second water phase
By remaining any required energy input of residual extractant thermal release in the second water phase after being separated with extraction.Vaporization enthalpy
It is further preferably not higher than the vaporization enthalpy of at least one of organic compound of component ii., to be reduced as far as possible by extractant and group
Divide one or more required energy inputs of organic compound thermal release of ii..Particularly preferred vaporization enthalpy is not higher than methyl-prop
The vaporization enthalpy of at least one of olefin(e) acid, acrylic acid and acetic acid.For the same reason, and in order to facilitated extraction agent separation,
The boiling point of extractant is preferably shorter than the boiling point of at least one of organic compound of component ii., preferably shorter than methacrylic acid, third
The boiling point of at least one of olefin(e) acid and acetic acid is as low as possible preferably in preferred range.If ionic liquid or organic or nothing
Machine oil is used as extractant, then vaporization enthalpy and its boiling point are preferably as high as possible, and at least one of preferably higher than water and component ii. is organic
At least one of compound.Extractant preferably only has low solubility in water, especially under extraction temperature, and preferably
It is substantially or entirely not soluble in water and preferably substantially or completely miscible not with it, so as to realize extraction phase and second
Water phase is totally separated from as far as possible.
In step b1b according to the method for the present invention) in, the second water phase is separated with extraction at least partly.According to this
The step b1a of inventive method) extraction and method and step b1b) separation can utilize and known to those skilled in the art just look at
Come any means being suitble to, carried out preferably by counter-current extraction, wherein method and step b1a) and b1b) preferably in the same equipment
In, such as utilize extraction tower, Impulse packing or packed column, rotating extractor, especially with those of centrifugal force separate, washing
Tower, phase separator or is suitable for carrying out organic phase or ionic liquid miscellaneous equipment mutually separated from the water.If using organic
Solvent is as method and step b1a) in extractant, then can be by method and step b1b) in separation after obtain extraction phase burn
Change.Such incineration this have the advantage that substantially organic extraction phase serves as fuel, to reduce the demand of purchase fuel.Example
Such as, if fuel cost or related request, such as conveying be easy and/or cost is unfavorable and/or component ii. organises
It closes that one or more market values in object are low, especially the overall work required with their separation and/or purifying and takes
With compared to then this option may be preferred.
Second water phase is preferably comprised no more than 5.0 weight %, preferably more than 4.5 weight %, more preferably no more than 4.0 weights
% is measured, 3.5 weight %, more preferably no more than 3.0 weight %, even more preferably no more than 2.5 weight % are even more preferably no more than
The organic compound in addition to the extractant used in method and step b), the total weight based on second water phase.Second water
The amount of organic compound in phase in addition to extractant is preferably as low as possible, preferably 0 weight %, but 0.5 weight %, 0.8 weight
The lower limit of amount %, 1.0 weight % or 1.2 weight % may be acceptable.In second water phase in the total amount of organic compound (no
Including coming from method and step b1a) any residual extractant), it is however generally that, formaldehyde, which can account for, is up to about 1.5 weight %, base
In the total weight of the second water phase, remaining is by C2Or more advanced C- chains organic compound, especially C2-C6Or C2-C4Compound is constituted.
The total amount of such organic compound depends on method and step b1a) the extraction extraction step or extraction cycle that include number,
With the amount of the extractant used in this extraction.Greater number of extraction step leads to lower organic compound in the second water phase
Content, but general also require the longer time and/or multistage extraction and/or a greater amount of extractants, this may cause
Then the higher volume of extraction phase that must be further processed or incinerate.
In optional step c) according to the method for the present invention, by least one organic compound at least partly with second
Aqueous phase separation, to obtain the dilution third water phase of at least one organic compound compared with the second water phase.The third water phase
It preferably comprises and is no more than 3 weight %, preferably more than 2.8 weight %, more preferably no more than 2.5 weight % do not surpass even more preferably
Cross 2.2 weight %, more preferably no more than 2.0 weight % except method and step b1a) in organic compound in addition to the extractant that uses
Object, the total weight based on the third water phase.The amount of organic compound in third water phase is preferably as low as possible, preferably 0 weight
Measure %.If organic compound is present in third water phase, up to about 1.5 weight % can be in formaldehyde form, remaining part
Point except method and step b1a) in addition to the extractant that uses comprising C2Or more advanced C- chain compounds, especially C2-C6Or C2-C4Change
Close object.Therefore third water phase is preferably comprised less than 5000ppm, preferably smaller than 4000ppm, more preferably less than 3000ppm, preferably 0-
3000ppm's, more preferable 0-2500ppm, more preferable 0-2200ppm, most preferably not more than 2000ppm removes C1Compound (formaldehyde)
In addition and the organic compound in addition to the extractant used in method and step b), based on the total weight of the third water phase,
The lower limit of middle 500ppm or 1000ppm or 1500ppm or 1800ppm may be acceptable, this depends on third water phase
Estimated further application and/or processing.Separation in method and step c) is preferably thermal release, such as distillation or azeotropic steam
It evaporates, preferably under normal pressure.It is preferred that in method and step c), the remaining method that derives from the second water phase is detached to the maximum extent and is walked
Rapid b1a) residual extractant.If method and step b1a) in the extractant that uses form azeotropic mixture with water, separation can wrap
Include azeotropic distillation, such as the azeotropic distillation using entrainer.At a preferred aspect of step c) according to the method for the present invention
In, if using distillation is passed through in method and step c), especially with the separation that fractional distillation or rectifying carry out, then preferably in tower
Top detach low-boiling component, especially the boiling point component lower than extractant, extract extractant out in the side outlet of tower, it is any
Component ii. either together with extractant or tower another side outlet, preferably than extract out extractant side outlet it is low
Side outlet is extracted out.Any extractant so detached then can be recycled to step b1a according to the method for the present invention) in extraction
It takes, this corresponds to step h) according to the method for the present invention.If with the step in the identical phase of any extractant that detaches
This then can be mutually added to method and step b1b by one or more organic compounds of middle separation component ii.) in detach
In extraction phase.If one or more organic compounds of separation component ii. in the phase different from extractant, can be by this
The different phases of kind are directed to step d) or step f) according to the method for the present invention.It is preferred that step c) according to the method for the present invention is carried out,
organic solvents have been used as process steps in the process of the inventionb1a)extractant within,But if the method stepsb1a)in
Using ionic liquid or oil extraction, then it can also be carried out.
In this aspect according to the method for the present invention, the separation in method and step d) preferably includes following methods step：
D1a it includes at least one component ii.'s that) at least part of the extractant, which is separated with the extraction to obtain,
Extract；
D1b) optionally, the separation of at least part and the extract of at least one component ii..
In step d1a according to the method for the present invention) in, by method and step b1a) in the extractant that uses at least partly with
Extraction phase separation is to obtain the extract for including at least one component ii..If organic solvent is used as extractant, method and step
D1a the separation in) is carried out preferably by thermal release method.Suitable thermal release method is known to the skilled in the art,
Middle distillation, fractionation, rectifying and similar approach are according to currently preferred, wherein being preferably evaporated in vacuo.One or more separation
Method may include in steps of a method in accordance with the invention d1a) in.In preferred thermal release method, when as method and step
B1a when the organic solvent of the extractant in) has the boiling point lower than one or more component ii. to be separated, in destilling tower
Top, or in fractionating column or one or more upper positions of rectifying column, preferably in the top half of the tower, extractant is removed,
And in the one or more positions low relative to the position for removing extractant, or in the tower bottom, remove one or more components
Ii. or include the extract of at least one component ii..The organic solvent lower than at least one component ii. using boiling point is as just
Method step b1a) in extractant the advantages of be component ii. some or all, especially methacrylic acid and acrylic acid are heat
It is sensitive and as temperature increase is increasingly intended to dimerization, oligomeric or polymerization.The heat of these compounds at elevated temperatures
Processing is therefore general to require addition polymerization inhibitor.If more low-boiling extractant to be separated, and/or steamed if separation is vacuum
It evaporates, then this separation can carry out under the lower temperature of the boiling point less than respective components ii., to reduce the tendency of polymerization simultaneously
Therefore the needs to polymerization inhibitor are also reduced.
If ionic liquid or organic or inorganic oil are used as the extractant in method and step b), point in method and step e)
From preferably by being separated or evaporating, preferably carried out by the evaporation of one or more volatile components.
Method and step d1b) in separation be preferably thermal release method, preferably distill, be fractionated or rectifying, preferably vacuum steam
It evaporates, wherein at least part of at least one component ii. is detached from extract.Extract can be with for example, in addition to be separated
At least one component ii. except also include extractant or other component ii..If more than one component ii. is included in extraction
In object, such as two or more components ii., then likely in method and step d1b) in only detach a kind of component ii., or point
From two or more components ii..Distillation, fractionation or rectifying can be easily by art technologies as the selection of separation means
Personnel it is determining and depend primarily on the number of other compounds in the extract for waiting for therefrom detaching at least one component ii. and
The respective boiling point of amount and the component for being not intended to separation of one or more component ii. to be separated and extract, especially extracts
Take the boiling points of other components of object and the boiling point of at least one component ii. to be separated the degree of approach and, if to be separated be more than
A kind of component ii. is then the boiling point proximity to one another of component ii. to be separated.Another factor considered is to be separated
The required purity of at least one component ii..At least one component ii.'s is further purified in step f) according to the method for the present invention
In separation after it may be desirable or is even necessary.
In other side according to the method for the present invention, the separation in method and step b) preferably includes following methods step
Suddenly：
B2a) at least part of the water is from method and step a3) in crystallize at least part of the first water phase for obtaining
To form crystallization water phase and mother liquor as the second water phase, wherein the mother liquor includes at least one component ii.；
B2b) crystallization water phase and the mother liquor are at least partially separate.
In method and step b2a according to the method for the present invention) in, allow at least part of the first water phase to undergo crystallization to obtain
Water phase (water of wherein this phase exists in crystalline form) is crystallized, and includes the mother liquor of at least one component ii..Method and step
B2a the crystallization in) can be used for accomplished continuously or intermittently by well known by persons skilled in the art, preferably the method for continuous crystallisation, example
Such as dynamic or stationary crystallization or the combination of both, such as melt crystallization, crystallisation by cooling, fractional crystallization are scraped, layer crystallization hangs
Floating crystallization, film-falling crystallization and any combinations of similar approach or two or more in them carry out, wherein it is preferred that suspension melt
Crystallization, preferably with continuous crystallisation process.In one of step b) according to the method for the present invention preferred aspect, crystallization can be by
Two benches carry out, wherein in the first phase, Crystallization, such as formed on cooling surface, in second stage, allow this
A little crystal growths and size increase.The two stages can carry out in substantially the same region each other, or each stage can
To be carried out in individual region.If fruit suspension melt crystallization carries out in the method according to the invention, then preferred crystallization is extremely
Occur in a few crystallization and melting cycle.In a preferred aspect of suspension melt crystallization according to the present invention, use
At least part of at least part wash crystallization water of fusion-crystallization water.Suitable method is for example about acrylic acid and/or first
Base purifying acrylic acid and describe in WO 02/055469, WO 99/14181, WO 01/77056, US 5,504, in 247, it
The disclosure for being related to crystallization, suspension melt crystallization disclosed in especially WO 01/77056 and WO 02/055469 exists
This is incorporated by reference and is formed as a part for present disclosure.If one or more component ii. in water and the first water phase
Eutectic mixture is formed, in order to obtain the water as pure as possible in crystallization (second) water phase, water preferably only crystallizes out big
About eutectic point.
In step b2b according to the method for the present invention) in, by as the crystallization water phase of the second water phase at least partly with mother liquor
Separation.Separation can just look at suitable any means by known to those skilled in the art, preferably by filtering, centrifugation point
From, phase separation or at least one of other solid- liquid separation means, preferably filters, centrifuges or phase separation carries out, wherein
It may include the washing of crystal, such as washed at least one of mother liquor, fusion-crystallization water phase and water.Such washing-melting
Type crystallize and separation for example describe above with respect to method and step b2a) reference bibliography in.According to the method for the present invention
Step b2b) a preferred aspect in, using phase separation, preferably in scrubbing tower, such as disclosed in WO 01/77056
Phase separation in the scrubbing tower of type, wherein crystalline phase float on mother liquor and/or wherein, and/or are collected and/or are compacted, example
As using being moved up in the tower and allow mother liquor to pass through and the movable plate that keeps crystalline phase on the plate simultaneously, such as in
The plate of filter form, so that crystalline phase can remove at the top of the scrubbing tower or upper position, and mother liquor passes through the plate simultaneously
In phase separator, lower position removes compared with crystalline phase.It is still possible that the lower position in phase separator detaches knot
Crystalline phase, this is for example depending on the relative density for crystallizing water phase and mother liquor, or the equipment for crystallizing and/or detaching.In this side
In face, at least part of crystalline phase can be made to melt, such as in heat exchanger, and guide return to scrubbing tower as cleaning solution with
Washing is present in the crystalline phase in the scrubbing tower, preferably presses counter-current flow.In another of step c) according to the method for the present invention
In preferred embodiment, separation is carried out by centrifuging.In this embodiment, at least one of crystalline phase can be made
Divide melting, such as in heat exchanger, and guiding returns to centrifugal separation equipment and is present in the centrifugation as cleaning solution to wash
Crystalline phase in equipment.Because mother liquor compared with the first water phase depleted water and include greater proportion organic component, it is possible to
Will be in method and step b2b) in separation after obtain mother liquor incinerate.Such incineration has the following advantages, this with the first water
Fuel mutually organically substantially can be served as compared to the water content reduced, to reduce the needs to buying fuel.
For example, if fuel cost or related request, for example, conveying be easy and/or cost be unfavorable and/or component ii. it is organic
One or more market values is low in compound, especially the overall work required with their separation and/or purifying and
Expense is compared, then this option may be preferred.
In a preferred aspect according to the method for the present invention, step b2a) and b2b) continuously carry out.Crystallisation step
B2a) can be suitable for carrying out step b2a according to the method for the present invention) crystalline element in carry out, the crystalline element is optionally
Be suitable for carrying out step b2b according to the method for the present invention) separative element, such as above-mentioned washing unit or centrifugal separation equipment
Connection.Crystalline element may include one or two stage, correspond to method and step b2a) possible two stages.It is tying
In brilliant unit, or in the first stage of crystalline element, the first water phase is generally cooled such that water crystallizes out at least partly.
If crystal is formed in the cooling surface of crystalline element at least partly, they can be scraped.If single including crystallization
Member second stage, then the slurry of gained and then is optionally directed to the second stage, wherein preferably stir slurry and it is same
When more multicrystalline growth and/or crystalline size increase.Then it is single crystal/mother liquor slurry to be directed to separation from the crystalline element
Member, wherein solid crystal is detached at least partly and is optionally washed to remove impurity at least partly.It can make described appoint
At least part of the crystal of washing is selected to melt and can at least part of the puddle be directed to further side
Method step, or handled in further method and step, a for example, at least biologically pure processing is used as process water or guiding
At least one of to method and step a1) and a2), as described below, or it is used as cleaning solution, wherein likely processing as described below
The first part of the fused junction crystalline phase and using another part of the fused junction crystalline phase as the washing for washing crystal
Liquid.It is still possible that at least part of the crystal is supplied crystalline element as crystalline seed.It can also include melting step
Suddenly.Melt step can utilize can be at least one in the crystalline element and washing unit internal or external equipment into
Row.Crystalline element can be known to those skilled in the art and seem to be suitable for making water from the aqueous solution comprising organic component
Any crystalline element of crystallization.Suitable crystalline element, and be combined with washing and/or melt element crystalline element be can be from
Sulzer Chemtech AG, Switzerland or Niro Process Technology B.V., Holland are those of commercially available.Suitable knot
Brilliant unit, washing unit and melt element, and combination crystallization/washing/melt element example above with method and step
B2a it) is provided in the document of related reference.The centrifugal separation equipment for being suitable for according to the method for the present invention be those skilled in the art
Know.
Method and step b2a) and b2b) can be with, but do not necessarily result in water and be fully crystallized from the first water phase, so that mother liquor
Can be with, or even general includes a certain amount of water really.For example, if water with it is one or more in the component ii. of the first water phase
Eutectic mixture is formed, then this is especially the case.In this case, in order to obtain using up in crystallization (second) water phase
Possible pure water, water is preferably only to crystallize out about eutectic point, so that a part for water remains in mother liquor.Remain in mother
The ratio of water in liquid therefore depending on formed with water in the first water phase the respective components ii. of eutectic mixture type and
Amount and water and this or these components ii. corresponding eutectic point.In other side according to the method for the present invention, side
Separation in method step d) preferably includes at least one in following methods step：
D2a) method and step b2b) in the mother liquor that detaches at least partly be dehydrated to obtain the mother liquor that is at least partly dehydrated；
D2b) at least part and method and step b2b of at least one component ii.) in obtain mother liquor or and method and step
D2a the separation of the mother liquor being at least partly dehydrated obtained in).
In a preferred aspect according to the method for the present invention, by least the one of the water remained in after crystallisation in mother liquor
Part and method and step d2a) in mother liquor detach.Method and step d2b) in dehydration preferably by azeotropic distillation, it is preferable to use
The azeotropic distillation of entrainer carries out.It is contemplated that known to those skilled in the art and seem to be suitable for method and step b2b) in
Any entrainer that the mother liquor of separation is at least partly dehydrated.It is linear chain or branched chain alkane according to the especially preferred entrainer of the present invention
Hydrocarbon, especially heptane or hexane, cycloalkane, especially hexamethylene, acetic acid esters, especially isobutyl acetate or ethyl acetate, virtue
Compounds of group, especially toluene or benzene or CS2, CCl4Or bromomethane.
Method and step d2b) in separation be preferably thermal release method, preferably distill, be fractionated or rectifying, wherein will at least one
At least part of kind component ii. is detached with mother liquor or dehydration mother liquor.The mother liquor or dehydration mother liquor can be with for example, in addition to waiting for point
From at least one component ii. except also include from step a3 according to the method for the present invention) extractant or other components
ii..If more than one component ii. is included in the mother liquor or dehydration mother liquor, such as two or more components ii., then
Likely in method and step d2b) in only detach a kind of component ii., or detach two or more components ii..Distillation, fractionation
Or rectifying can easily be made by those skilled in the art as the selection of separation means and depend on many factors, such as wait for
With the number and amount and to be separated one of other compounds at least one component ii. mother liquors detached or dehydration mother liquor
The respective boiling point of the component for being not intended to separation of kind or various ingredients ii. and mother liquor or dehydration mother liquor, especially mother liquor are de-
The degree of approach of the boiling point of the boiling point of other components of jellyfish liquid and at least one component ii. to be separated and, if will separation it is more
In a kind of component ii., then there is the degree of approach of the boiling point of component ii. to be separated to each other.Another factor considered is to wait for point
From at least one component ii. required purity.
This aspect according to the method for the present invention, the method preferably further include following methods step：
E2) fusion-crystallization water phase of the melting of the crystallization water phase to obtain as third water phase.
The melting of crystallization water phase can be by known to those skilled in the art and seem that suitable any means carry out.It is special
Not, the temperature that crystallization water phase can be allowed to undergo it by melting, such as in fusion apparatus or heat exchanger.Method and step e2) in
Melting can be equivalent in method and step b2a) and description b2b) mentioned in melting and/or it can be another
Outer melting.Thus, for example, first melting may be in method and step b2a) and b2b) in the range of carry out, such as in order to provide
Cleaning solution for washing crystal.Then the cleaning solution itself is preferably tied on crystal at least partly when it contacts crystal
It is brilliant.It can make so to wash, the crystal then detached is in order to obtain so much washing-melting necessary to required crystal purity
It is melted again in cycle to provide cleaning solution.Once having obtained required purity, then the crystal can be made according to the present invention
The step e2 of method) in melting, and be further directed at least one of biologically pure processing (be used as process water) and side
At least one of method step a1) and a2).
Fusion-crystallization water phase or third water phase according to this aspect of the invention generally can be straight with enough purity
It is earthy to make process water or as method and step a1 according to the method for the present invention) or a2) in addition water.Particularly, described
Crystallization water phase or fusion-crystallization water phase are preferably comprised less than 5000ppm, preferably smaller than 4000ppm, more preferably less than 3000ppm,
It is preferred that 1500-2500ppm, more preferable 1800-2200ppm, the most preferably not more than organic compound of 2000ppm, based on corresponding
The total weight of water phase.The impurity that relatively low amount can be obtained is, for example, less than about 500ppm, or even less than 100ppm, 0ppm-
100ppm is recycled especially by the washing used in a large amount of steps of a method in accordance with the invention c)-melting.However, these
The impurity of relatively low amount normally only obtains together with the water of reduction amount.Biologically pure processing can optionally as process water or
As method and step a1) or a2) in addition water before carry out.If the water of the fusion-crystallization water phase will be for other purposes
Or be discharged into environment, then may preferably, but be not always necessary be it is such use or discharge before be biologically pure.
According to it is currently preferred be that the third water phase is allowed to undergo at least one of following procedure：It is directed at least one
At least one of biologically pure processing, is used as process water, and be directed to method and step a1) and a2).
Term " biologically pure processing " in the scope of the invention be intended to refer to the purity for improving water any processing, such as it is logical
Removing pollutant or impurity, preferably organic pollution are crossed, one or more biologic artifacts and/or microorganism or biology are utilized
Or biochemical activity substance, such as the substance derived from such organism or microorganism.Wait for the pollutant removed in this way and miscellaneous
Matter is usually the organic compound remained in third water phase.It is carried out by the digestion or decomposition of some or all organic compounds
It removes.The increased purity of water for example measures as follows：It is reduced by pollutant and/or impurity, and/or aerobic by the biochemistry of water
Measuring (BOD) or COD (COD) reduces, and is preferably reduced to mean that the waste water can reuse, such as industrial work
Skill water is used further to according to the method for the present invention, especially method and step a1) or one of a2) or two, or can be discharged into
Level in environment or water supply chain, this depends on reached purity.Biologically pure processing is known to the skilled in the art
And it can be with for example, being one or more in so-called activated sludge processing.Such processing is conventional and is art technology
Known to personnel.Biologically pure processing can be carried out by one or more stages, and can be continuous or discontinuous.
If at least one biologically pure processing of third water phase experience, this processing is allowed to be preferably aerobic treatment and anaerobism
At least one of processing.In an embodiment of the processing with two or more stages, for example, at the first anaerobism
Reason can be followed by aerobic treatment be carried out, and the first aerobic treatment can be followed by progress Anaerobic Treatment, or can use need to
The sequence of oxygen and/or Anaerobic Treatment, such as in sequential batch reactor like that.
If the separation in method and step d) according to the method for the present invention is thermal release, component is separated from each other may not
It is always feasible or e.g. in economics or technically actual, for example, if two or more components are with closely similar
Boiling point if.If the mother liquor or dehydration mother liquor that undergo method and step d) include larger amount of component, especially if a kind of
Or various ingredients ii. has similar boiling point at least one component ii. detached in method and step d) is stayed in, and make other side
The separation of just a kind of component ii. in method step d), which fine-tune, becomes more difficult, then is particularly likely to be such
Situation.Then may it is more suitable or it is more actual be in further method and step f) by two or more components
Ii. it detaches, wherein such adaptation required the particular separation of respective components ii. may be more prone to reach.Therefore, in basis
In the one side of the method for the present invention, at least one component ii. detached in method and step d) can be at least two component ii.
Mixture and in further method and step
F) at least one component ii. is preferably at least partly detached with this mixture.
The separation in method and step f) according to the method for the present invention may include one or more separating steps, such as hot point
From, as being discussed above to other separating steps according to the method for the present invention, chromatographic isolation, Chemical Decomposition, such as
By a kind of preferential reaction of component ii. to form the reaction that can be more easily detached with one or more other component ii.
Product, or by the reaction of two or more components ii. to form the reaction product that can be more easily separated from each other, or appoint
What it known to those skilled in the art just looks at suitable separation means.
In a preferred embodiment according to the method for the present invention, at least one organic compound of component ii. is excellent
At least one component ii. that choosing detaches in method and step f) at least partly is at least one having selected from carboxylic acid, aldehyde and ketone
Machine compound.In them, according to preferably at least a kind of component ii. of the present invention, preferably at least partly in method and step f)
At least one component ii. of separation, is at least one of acetic acid, acrylic acid, propionic acid and methacrylic acid.
If method and step d) and at least one of f) at least one component ii. for detaching be or comprising metering system
Acid adds at least part of this methacrylic acid phase then in a preferred embodiment according to the method for the present invention
Be added to method and step a2) in obtain thick water phase and/or method and step a3) in obtain thick organic phase in.For example, if method
Step d) and one or more of f) in the methacrylic acid that detaches do not have the purity needed for its final use, then this reality
The scheme of applying may be preferred.For example, if separated methacrylic acid is less than methyl together with one or more boiling points
Other components of acrylic acid detach together, then into thick water phase, addition may be preferred.For example, if except methacrylic acid with
Outer component have boiling point more higher than methacrylic acid, then into thick organic phase addition may be preferably as it is such compared with
Higher-boiling compound can be in method and step a4) in separation.Although methacrylic acid and other components, especially other components
Ii. relative scale can also play a role, but method and step e), at least one of f) and j) in at least one that detaches
The property of other components in component ii. determine mutually to add to which it is this in method and step e), f) and j) at least one
There is bigger weight in terms of the phase containing methacrylic acid of a middle separation.For example, if in method and step d) and f) at least
The methacrylic acid detached in one is purer, including for example, be no more than about 5 weight %, preferably no more than about 4 weight %,
Preferably no more than about 3 weight %, preferably no more than about 2 weight %, the impurity of about 2 weight % of preferably approximately 1 weight %-
Or other component ii., then this methacrylic acid is introduced into optional method and step a4) purification step may be preferred.
In other side according to the method for the present invention, allow method and step d) and at least one of f) in detach to
Few a kind of at least part or method and step a3 of component ii.) at least part experience method step of the first water phase for obtaining
Rapid g) esterification is to obtain the ester phase for including at least one ester.
If corresponding at least one component ii. is carboxylic acid, the step for may be preferred.The details of esterif iotacation step
With above to method and step a5 according to the method for the present invention) description those of it is identical.Instead of or in addition to obtain corresponding at least one
Other than kind of component ii. itself extraly, method and step d) and at least one of f) in the ester of at least one component ii. that detaches
Change may be preferred, this obtainable purity for example depending on separated respective components ii., respective components ii. and its
The market or other application that ester is compared.For example, if the first water phase only includes the impurity of small scale and/or the group for being not intended to separation
Ii., such as the total weight based on first water phase is divided to be less than about 6 weight %, preferably less than about 5 weight %, preferably
Less than about 4 weight %, more preferably less than about the impurity of 3 weight % and/or be not intended to separation component ii. impurity it is total
Amount in particular, for example, may be more prone to and respective sets based on the total weight of first water phase compared with component ii. itself
The impurity of the ester separation of point ii., then be included in method and step a3) at least one of the first water phase for obtaining component ii.
Esterification may be preferred.
Especially preferred ester group included in ester phase according to the present invention is in C1-C4Carboxylic acid and C1-C4Alcohol, wherein being based on
C2-C4The ester of carboxylic acid is preferred.In addition to together with method and step a5) mentioned by methacrylate other than especially preferred ester
Also methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate,
Methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, third
The secondary butyl ester of olefin(e) acid, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, propionic acid
Secondary butyl ester, preferred acetic acid esters and acrylate in them.
It is possible according to the invention that ester includes mutually at least two esters.If method and step d) and at least one of f)
At least one component ii. or method and step a3 of middle separation) in obtain the first water phase at least part include at least two
The component ii. to form ester, especially at least two kinds of carboxylic acids can be reacted, then it may is that.If can react to be formed
At least two components ii. of ester is especially difficult to detach, such as by heat or other means, for example, when their performance for example
Boiling point, the solubility in given solvent and/or volatility are very close, and their ester can be separated from each other less difficultly
When, then this embodiment may be preferred.
It may further include following methods step according to the method for the present invention
H) at least one ester is from being at least partially separate in the ester phase；
J) optionally, the purifying of at least one ester detached in method and step h).
In general, other than at least one ester, ester can also include mutually solvent, such as water or be suitable for esterification
At least one organic solvent or their mixture and unreacted component ii., it is possibly also another or
A variety of esters.Separation in method and step h) can be by known to those skilled in the art and seem to be suitable for corresponding esters and ester
Any separation means of phase separation.The example of suitable separation means is, for example, thermal release, such as distillation, fractionation or rectifying,
The separation means of different solubilities based at least one ester compared with other components of ester phase, solid- liquid separation means such as mistake
Filter etc..If necessary or wish, the purifying of at least one ester detached in method and step h) can also be carried out.Means of purification depends on
In ester, wherein for example, by hot means, by chromatography means, can be considered by washing or by the purifying of crystallization.
In a preferred embodiment according to the method for the present invention, method and step g), at least one of h) and j)
At least part of at least one ester of middle acquisition may be used as method and step b1a) in extractant.
In an embodiment according to the method for the present invention, this method is further comprising the steps of
Aa1) division of methyl tertiary butyl ether(MTBE) (MTBE) is to obtain at least one C4Compound and methanol,
The wherein described at least one C4At least part of compound is as raw material supply method step a1) and 1) in extremely
Few one gaseous oxidation.The division that MTBE is widely used as the raw material and MTBE of isobutene is well known in the art.
The division of MTBE can be carried out by any suitable means well known by persons skilled in the art.Suitable catalyst and reaction item
Part is described for example, in following documents：EP 1 149 814、WO 04/018393、WO 04/052809；Ullmann’s
Encyclopedia of Industrial Chemistry, the 5th edition, the A4 volumes, page 488；V.Fattore,M.Massi
Mauri, G.Oriani, G.Paret, Hydrocarbon Processing, in August, 1981, the 101-106 pages；Ullmann’s
Encyclopedia of Industrial Chemistry, the 5th edition, the A16 volumes, the 543-550 pages；A.Chauvel,
G.Lefebvre,“Petrochemical Processes,Technical and Economic Characteristics”,
Volume 1,Technip, Paris, 1989, page 213 and continued page；US 5,336,841、US 4,570,026
And references cited therein.The disclosure of these references be incorporated herein for reference and be formed as the present invention disclose in
A part for appearance.
Two kinds of primary products of MTBE divisions are C4Compound isobutene and methanol.Another C4The compound tert-butyl alcohol also may be used
It can be included in dissociative reaction product phase.It is any or both in isobutene and the tert-butyl alcohol to be used as raw material supply method step
A1), to constitute total C of the raw material for this method and step4The other C of compounds content or supplement derived from other source4
Content.The division and at least one C for being obtained in this way of one or more intermediate separation and/or purification step in MTBE4Chemical combination
Object is to method and step a1) in gaseous oxidation supply between be also possible, for example, with as far as possible by at least one C4Change
It closes object and methanol is separated from each other and is removed from the fission process any by-product that may negatively affect gaseous oxidation.Separation
And/or purification can be known to the skilled in the art and look like suitable any means.Suitable purification and separation
Method is for example, describe in 1 149 814A1 of EP, WO 04/018393A1 and WO 04/052809A1.Separating methanol it
Afterwards, can optionally will include then the C4Compound isobutene is purified as the split coil method of major constituent and is provided as raw material
To method and step a1).Suitable method of purification is known to the skilled in the art and preferably includes distillation, extraction, absorption, inhales
At least one of at least one of receive, chromatograph or wash, preferably distill and extract, preferably at least a kind of distillation and at least one
Kind extraction.Can at least partly by unreacted MTBE from the step in C4It is detached in compound phase.It can be optionally
The MTBE of separation is purified and is recycled to dissociative reaction at least partly.
In a preferred embodiment according to the method for the present invention, by method and step aa1) in obtain methanol supply
Method and step g)., can be by method and step aa1 in other side according to the method for the present invention) in obtain methanol supply
Method and step a5).Optionally the methanol can be purified, preferably by heat purifying such as distillation, fractionation or rectifying, be crystallized, extraction
It takes, tower or washing, more preferably at least single flash.The example of methanol purifying describes in EP 1 254 887.
The invention further relates to the Preparation equipments of at least one of methacrylic acid and methacrylate, include at least following
The component of fluid guiding connection each other：
A1) gaseous oxidation unit,
A2 it) is quenched unit,
A3) the first extraction cells,
A4) the first separative element,
A5) optionally, the first esterification unit,
B) the second separative element,
C) optionally, third separative element,
D) optionally, the 4th separative element,
Wherein the first separative element is the thermal release unit at least one outlet at bottom in the one third of its underpart,
At least one outlet at bottom is connected to the guiding of at least one entrance fluid of the second separative element.
It can be liquid that term " fluid guiding connection " is understood as referring to unit through connection to meet herein, gas, steam, surpass
The fluid of at least one of critical fluids or any other fluid can direct at least one other unit from a unit.This
It can be for example by via pipe or pipeline (such as the material by resistance to reaction reagent and leading condition, such as stainless steel or glass
Glass or any other suitable material well known by persons skilled in the art are made) direct connection reach, or it is each using being arranged in
Tank car or slot or reservoir between unit reach indirectly.If gaseous state should be kept by guiding gas and its, gas is guided
Device is preferably kept at the temperature higher than the dew point of the gas.If wanting direct fluids, the device for guiding the liquid is preferred
It maintains at solidification than component present in the liquid and/or the liquid and/or the high temperature of set point.This can be by means of
By the device for guiding corresponding gas or liquid it is heat-insulated and/or heating reach.All reactors, tower and other apparatus assemblies preferably by
Resistance to reaction reagent and their conditions for being undergone, for example, especially material manufacture of temperature and pressure condition.
Gaseous oxidation unit A1) preferably include at least one reactor for being suitable for carrying out gas phase reaction, especially pressure
Reactor, preferably at least a multitubular reactor, it is anti-for example formed as pipe and shell mould reactor and/or at least one plate
Device and/or at least one fluidized-bed reactor are answered, wherein multitubular reactor is preferred.Especially preferably at least one multitube
Reactor, wherein oxidation catalyst are arranged at least one pipe, preferably wherein the pipe be with oxidation catalyst filling or
Coating, preferably fill.According to currently preferred oxidation catalyst be it is related to the method for the present invention above mentioned by
Those.Reactor material should be patience to the reaction reagent of inside reactor and leading condition and preferably inert.It is suitble to
Reactor can be for example from MAN DWE GmbH, Deggendorfer Werft, Germany or from IHI Corporation, Japan
Commercially available and formation is known to the skilled person a part for common sense.
In two benches gaseous oxidation, gaseous oxidation unit may include at least two reaction zones, and each reaction zone includes
Oxidation catalyst.At least two reaction zone can be that at least two reaction zones in single-reactor or at least two are anti-
Answer device.Oxidation catalyst in first reaction zone is preferably by least one C4Compound, preferably isobutene and/or tert-butyl alcohol oxygen
It is melted into the oxidation catalyst of methacrolein, and the oxidation catalyst in second reaction zone is preferably suitable for methacrolein
It is oxidized to methacrylic acid.Suitable catalyst above with relatively refer to according to the method for the present invention.
In one of the present device preferred aspect, oxidant, preferably oxygen, preferably at least one source of air
At least one feedway of at least one feedway and water and/or steam is in fluid communication with gaseous oxidation unit.If
Gaseous oxidation unit includes at least the first zoneofoxidation and another zoneofoxidation, then the equipment for each zoneofoxidation may include to
A kind of few at least one feedway of at least one feedway and water and/or steam of oxidizer source.Equipment can be into one
Step includes the feedway of diluent, the diluent such as nitrogen, argon gas and/or carbon dioxide, preferably nitrogen or titanium dioxide
Carbon, such as from catalytic combustion unit (CCU) or hot fuel element (TCU), preferably downstream in the device in accordance with the invention
The carbonated recycling gas of CCU or TCU.Corresponding feedway should be by resistance to reaction reagent and leading condition
Material such as stainless steel or glass are made.In preferred design, oxygen, diluent and water are supplied into the C4Stream, then into
Enter corresponding reactor, so that preformed mixture enters reactor.
Step a1 according to the method for the present invention) preferably carried out in gaseous oxidation unit.
According in present device a preferred embodiment, it is quenched unit A2) it is wherein by gaseous oxidation phase
Condensation and/or the absorptive unit for absorbing and being formed liquid phase.It is preferred that making the methyl being present in the oxidation phase for leaving catalytic reaction zone
Acrylic acid is in quenching unit A2) in condensation and form solution, the preferred aqueous solution containing methacrylic acid as main oxidation product.
Can be in absorptive unit A2) in by unreacted methacrolein detach and if necessary, guide return to gaseous oxidation area
For further reacting.It is known to the skilled in the art suitable for according to the quenching unit of present device.According to this
The step a2 of inventive method) preferably quenching unit A2) in carry out.
According in present device a preferred embodiment, it is quenched unit A2) it is single followed by the first extraction
First A3).Will be quenched unit A2) in formed the aqueous solution containing methacrylic acid be directed to the first extraction cells A3), wherein providing
Organic solvent, methacrylic acid are preferably substantially extracted in the solvent.Organic solvent is preferably substantially unmixing with water
, so that forming at least partly the dilution water phase of methacrylic acid and the organic phase containing methacrylic acid.About preferably having
The details of solvent is in above method step a3) description in provide.Method and step a3) preferably in the first extraction cells into
Row.It is known to those skilled in the art and seem that the suitable any extraction cells of such extraction for methacrylic acid can be examined
Consider and be used as the first extraction cells A3).
Equipment according to the present invention is included in the first extraction cells A3) the first separative element A4 in downstream).If according to this
The equipment of invention is used to prepare methyl methacrylate, then the first separative element A4) preferably in the first esterification unit A5) it is upper
Trip, preferably in the first extraction cells A3) and the first esterification unit A5) between and with they fluid communication.First separative element A4)
It is preferably suitable for detaching methacrylic acid, preferably purify, in particular for by methacrylic acid and for the first extraction cells
A3 extractant separation), preferably also allows methacrylic acid and leaves the first extraction cells A3 according to present device)
Other components separation, the thick organic phase present in thick organic phase correspond to method and step a3 according to the method for the present invention) it is thick
Organic phase.First separative element A4) it is preferably thermal release unit, preferably include destilling tower, fractionating column, rectifying column and this field skill
Art personnel are known and seem the method and step a3 for being suitable for the method for the present invention) separation any other heat separation device in
It is at least one.First separative element A4) include more than one separation phase it is possible.First separative element A4) it preferably includes
At least one outlet at bottom, the outlet at bottom can be in the bottom of the first separative element or going out in the one third of its underpart
Mouthful.First separative element A4) this arrangement preferably allow for higher-boiling compound phase and thick organic phase separation, this corresponds to root
According to the method and step aa4 of the method for the present invention).At least one outlet at bottom preferably with the second separative element B) it is at least one
The guiding connection of entrance fluid.This fluid guiding connection can utilize first separative element at least one outlet at bottom and
Direct conduit between at least one entrance of second separative element reaches.Can also by least one intermediate equipment and/
Or component R) be arranged at least one outlet at bottom and the second separative element B of the first separative element) at least one entrance it
Between, a for example, at least other separation equipment, for example, at least one other thermal release equipment and/or at least one solid-liquid
Separation equipment and/or at least one mixing apparatus and/or at least one reservoir, such as in order to will be in the first separative element
A4 the higher-boiling compound detached in) mutually introduces the first water phase, preferred to can be by the higher-boiling compound phase and first
Water phase combines, and optionally by the component of the higher-boiling compound phase and/or the higher-boiling compound phase of the combination and the
One aqueous phase separation.It is known to those skilled in the art and seem any equipment for being suitable for the purpose and component may include
In equipment according to the present invention.
For purifying the first separative element A4) in the first optional purification unit of methacrylic acid for detaching can also cloth
Set in the first separative element A4) downstream.The first optional purification unit can be, for example, hot purification unit, such as distill
Tower, fractionating column, rectifying column etc., crystalline element or known to those skilled in the art and seem to be suitable for purifying methacrylic acid
Any other equipment.
Equipment according to the present invention may further include one between unit or component mentioned by any or all
A or multiple additional components, such as by the heat or stripper plant of the separation of high and/or low boiling component, solid/liquid separation fills
It sets, for example, at least a filter and/or centrifuge, and/or cooling and/or heating unit.In preferred design, for example,
For low-boiler destilling tower and optionally also have filter to be arranged in quenching unit downstream and extraction cells upstream.Two
In another preferred aspect of stage gas phase oxidation unit, quenching unit is arranged between this two benches.
Unreacted methacrolein can be single in quenching unit, the first extraction cells, the first separative element, the first purifying
It is detached in any of first or any of above other equipment component, and guides and return to gaseous oxidation unit so as to further anti-
It answers.
First esterification unit A5) the first separative element A4 can be arranged in) or the first optional purification unit downstream.It is right
First esterification unit A5) it is not subject to especially to limit and can be suitable for esterification to form methacrylic acid by methacrylic acid
Ester, preferably any unit of methyl methacrylate.It is preferably suitable for liquid phase esterification.First esterification unit A5) it preferably includes
Esterification catalyst, can be multiphase or homogeneous catalyst such as solid catalyst or liquid catalyst, and it is preferably acid from
Sub-exchange resin such as US 6,469,292, JP 1249743, those of described in EP 1 254 887 or with trade name(Rohm and Haas Corp.)、(Dow Corp.) or(Lanxess
AG) those of commercially available, or it is capable of the acid of catalytic esterification, such as sulfuric acid H2SO4。
Second purification unit can be arranged in the first esterification unit A5) downstream, so as to the metering system that will wherein generate
Acid esters purifies.The second optional purification unit can be, for example, hot purification unit, such as destilling tower, fractionating column, rectifying column etc.,
Crystalline element is known to those skilled in the art and seem to be suitable for purifying methacrylic acid system ester, especially metering system
Any other equipment of sour methyl esters.
Equipment according to the present invention further includes the second separative element B).Second separative element B) by the first extraction cells A3)
At least part for the water for including in first water phase of middle acquisition and the especially above-mentioned at least one of at least one organic compound
At least part of component ii. detaches, to obtain the second water phase and organic phase.Method and step b) according to the method for the present invention is preferred
In the second separative element B) in carry out.
According in present device a preferred embodiment, the second separative element B) include the second extraction cells
B1).Second extraction cells B1) it is used for extracting at least part of the first water phase with extractant to form the second water phase and extraction
Phase, and be preferably used for the extraction phase utmostly detaching the second water phase as far as possible in technology limit.Therefore, according to
At least method and step b1a of the method for the present invention) and preferred method steps b1a) and b1b) preferably in the second extraction cells B1) in,
Continuation mode is most preferably pressed to carry out.Second extraction cells B1) preferably include at least one extraction tower, scrubbing tower, phase separator or
It is known to those skilled in the art and seem to be suitable for liquid-liquid extraction, be preferably also adapted to by organic phase or ionic liquid phase with
Aqueous phase separation, be more preferably suitable for by continuation method extract and detach miscellaneous equipment, a for example, at least extraction tower, at least one
A Impulse packing and/or packed column, at least one rotating extractor, especially at least a rotation detached using centrifugal force
Turn extractor, at least one scrubbing tower and/or at least one phase separator.Second extraction cells B1) it is preferably able in environment temperature
Under degree, and in the temperature in addition to environment temperature, especially raised temperature, especially above and method and step b1a) and
B1b it) is relatively resistant at mentioned temperature and operation.
According in another of present device preferred embodiment, the second separative element includes
B2a) crystalline element, and
B2b) optionally, Crystallization Separation unit.
In crystalline element B2a) in, the first aqueous solution obtained in the first extraction cells is generally cooled such that water at least portion
It crystallizes out with dividing.Then the slurry that gained can be conveyed, optionally via parking cell T1) it is used for crystal growth, it is such as above-mentioned
To method and step b2a) and it is b2b) related described such, it is transported to crystal separative element B2b), such as scrubbing tower or centrifuge,
It is middle to detach solid crystal with mother liquor at least partly, it preferably washs to remove remaining impurity to greatest extent at least partly.
At least one fusion apparatus can also be included in the second separative element B2) in, and can be in crystalline element B2a) and Crystallization Separation
Unit B 2b) in it is at least one internal or external, preferably at least with Crystallization Separation unit B 2b) guided with fluid and/or solid
Connection.It is preferred that melting at least part of the crystal of the optionally washing at least one melt element and allowing the melting
Partial at least part be passed to next apparatus assembly or cleaning solution as the crystal in Crystallization Separation unit or this two
Kind situation.It is still possible that using one or more conduits by least part of the crystal from crystal separative element B2b)
Supply crystalline element B2a) and/or supply parking cell T1) it is used as crystalline seed.
It is known to those skilled in the art and seem any crystalline element, parking cell and the crystal that are suitable for above-mentioned purpose
Separative element can be used for equipment according to the present invention, wherein preferably allowing for the corresponding units of continuous crystallisation and separation.Crystallization is single
Member can be known to those skilled in the art and seem to be suitable for times for making water crystallize from the aqueous solution comprising organic component
What crystalline element, wherein it is preferred that suspension crystallization unit, it is even furthermore preferable that equipped with scraper so as to may be on it from crystal
The cooling surface of formation scrapes away the suspension crystallization unit of crystal at least partly.Parking cell (provided that) be preferably in a groove shape
Formula, is preferably equipped with agitating device, and equipped at least one entrance being connected to crystalline element fluid and/or solid guiding and
It is at least one to guide the outlet being connected to Crystallization Separation unit fluid and/or solid.Crystalline element, optionally together with parking cell
It is preferably suitable for carrying out step b2a according to the method for the present invention together).Crystal separative element is preferably suitable for carrying out according to this hair
The step b2b of bright method), and preferably scrubbing tower or centrifugal separation equipment.Suitable crystalline element, and it is combined with washing
And/or the crystalline element of melt element is, for example, such as works " Melt Crystallisation Technology ", author
G.F.Arkenbout, Technomic Publishing Co.Inc., Lancas ter Basel (1995), 265-288
Page, Chem.Ing.Techn. (72) (10/2000) have crystal in waterpower or machine washing tower described in 1231-1233
Downstream washing suspension crystallization unit.In general, any washing with forced conveyance melts scrubbing tower, such as
Chem.Ing.Techn.57 (1985) No.2, the 91-102 pages and Chem.Ing.Techn.63 (1991), No.9,881-
Described in page 891 and WO 99/6348 those.The example description of suitable washing melting tower EP 97405, US 4735781,
WO 00/24491、EP 920894、EP 398437、EP 373720、EP 193226、EP 191194、WO 98/27240、EP
305316, in US 4787985, and can be for example from TNO Institute in Apeldoorn, Holland, from Niro Process
Technology B.V., Hertogenbosch, NL, or from Sulzer Chemtech AG, Switzerland, TNO or Niro
Process Technology B.V., Holland commercially available from.Suitable crystalline element, washing unit and melt element, and combination
Other examples of crystallization/washing/melt element also above with method and step b2a) provide in the document relatively quoted.Properly
It is known to the skilled in the art as according to the centrifugal separation equipment of the crystal separative element in present device.
At least one incinerator or fuel element may include in equipment according to the present invention, such as by second extraction
The extraction phase obtained in unit or the mother liquor obtained from crystalline element and/or crystal separative element is taken to incinerate.
Equipment according to the present invention may further include third separative element C).Third separative element C) preferably especially wrap
It includes in equipment wherein according to the present invention includes embodiment of the extraction cells as the second separative element, but can also wrap
It includes in embodiment of the crystalline element as the second separative element to include in equipment wherein according to the present invention.Third separative element
C) be preferably used for method and step b1a) in any residual extractant for using and the second aqueous phase separation.Third separative element C) it can
To be other extraction cells, it is preferred that being thermal release unit, such as destilling tower, fractionating column, rectifying column etc., wherein this field
Technical staff is known and seems that any device for being suitable for such separation can be considered in the device in accordance with the invention.
Equipment according to the present invention can further include the 4th separative element D).Second separative element B wherein) packet
Include extraction cells B1a) embodiment in, the 4th separative element D) preferably include at least one thermal release equipment D1a) for will
At least part of the extractant is with extraction phase separation to obtain the extraction for including at least one component ii. according to the present invention
Object, this corresponds to method and step d1a).Can also include at least one other thermal release equipment D1b) so as to will be according to this hair
At least part of bright at least one component ii. is detached from the extract, this corresponds to method and step d1b).This field
Technical staff is known and seems to be suitable for carrying out method and step d1a) and the thermal release equipment of separation d1b) use can be considered
In at least one of equipment according to the present invention, such as distillation, fractionation or rectifying column etc..
In wherein the second separative element includes the embodiment of crystalline element and crystal separative element, the 4th separative element
At least one of D dewatering unit D2a) is preferably included) and other separative element D2b).Dewatering unit D2a) it is preferably suitable for
Carry out the method and step d2a of the method for the present invention).It is known to those skilled in the art and seem to be suitable for crystalline element and/or crystalline substance
The dewatering unit of the mother liquor detached in body separative element being at least partly dehydrated can be considered for equipment according to the present invention.Root
It is according to currently preferred dewatering unit, for example, filled with the dehydrating agent not reacted at least one component ii., such as molecule
The tower and distillation unit of sieve, are particularly adapted to the distillation unit of azeotropic distillation.Other separative element D2b) it is preferably suitable for
Carry out step d2b according to the method for the present invention), preferably thermal release unit.It is known to those skilled in the art and seem suitable
In carrying out method and step d1a) and the thermal release equipment of separation d1b) can be considered for equipment according to the present invention, such as steam
It evaporates, be fractionated or at least one of rectifying column etc..
Other separative element can also include in equipment according to the present invention.The one of preferred other separative element
A example be suitable for by least one component ii. from it is according to the present invention include at least two component ii. mixture, such as
The separative element of the mixture separation obtained in step d) according to the method for the present invention.Such other separative element is preferably heat
Separative element preferably includes at least one destilling tower, fractionating column, rectifying column etc..
Equipment according to the present invention is preferably in the 4th separative element D) and at least one other separative element at least
One and the first extraction cells A3) and/or the first separative element A4) between include at least one conduit, so as to by metering system
At least one of acid and phase containing methacrylic acid are from the 4th separative element D) and at least one other separative element in
At least one of at least one guiding returns to the first extraction cells A3) and the first separative element A4).
Equipment according to the present invention optionally includes at least one second esterification unit G) it is used at least one component ii.
Esterification, preferably in the second separative element B), third separative element C) and the 4th separative element D) at least one downstream.This hair
The method and step g) of bright method is preferably in the second esterification unit G) in carry out.Be related to the second esterification unit G) details with it is right above
In the first esterification unit A5) it is those of mentioned identical.
Equipment according to the present invention can also include at least one ester separative element H) so as to by one or more esters each other
Be at least partially separate, especially by least one ester and at least one second esterification unit G) in the ester that obtains mutually at least portion
Separation, this corresponds to the method and step h) of the method for the present invention.It is known to those skilled in the art and seem to be suitable for ester separation
Any equipment may be used as ester separative element H).The thermal release equipment and crystallizer of the type being already mentioned above, extraction are set
Standby, device for phase saparation is preferably as according to the ester separative element in present device.
At least one other purification unit J) it can also provide in the device in accordance with the invention, for second to be esterified
Unit G) in obtain or at least one ester separative element H) in one or more esters purifying for detaching.According to the method for the present invention
Method and step j) is preferably at least one other purification unit J) in carry out.The details of this other purification unit corresponds to
Those of purification unit mentioned by related to the first esterification unit.
If equipment according to the present invention can also be included in the second extraction cells B1 for including), with the second esterification unit
G), ester separative element H) and for purification of at least one ester other purification unit J) between at least one ester conduit.Institute
At least one ester conduit is stated to be used at least one ester from the second esterification unit G), ester separative element H) and for purifying at least one
The other purification unit J of kind of ester) at least one of direct into the second extraction cells B1a), wherein at least one ester can
To be optionally used as extractant.
According in the preferred aspect of present device, the equipment further includes in gaseous oxidation unit A1) on
The MTBE of trip divides unit AA1).It is familiar in the field of competence and shape for the division unit of MTBE divisions and suitable catalyst
As a part for common sense well known to those skilled in the art, for example, being described in Ullmann ' s Encyclopedia of
Industrial Chemistry, the 5th edition, the A4 volumes, page 488；V.Fattore、M.Massi Mauri、G.Oriani、
G.Paret, Hydrocarbon Processing, in August, 1981, the 101-106 pages；Ullmann’s Encyclopedia
Of Industrial Chemistry, the 5th edition, the A16 volumes, the 543-550 pages；A.Chauvel, G.Lefebvre,
" Petrochemical Processes, Technical and Economic Characteristics ", volume 1,Technip, Paris, 1989, page 213 and continued page；US 5,336,841, US 4,570,026 and wherein
In the bibliography of reference.
Isobutene separative element S1) be preferably placed in MTBE divisions unit AA1) gentle phase oxidation unit A1) and between and with
The guiding connection of each of which fluid.Isobutene separative element S1) it is used for isobutene phase, preferably also methanol phase, is catalyzed with second
The effluent of reaction zone detaches, which includes isobutene and methanol as major constituent.Isobutene separative element S1) can be
At least one in extractor, crystallizer, tower, distillation equipment, rectifying device, film, pervaporation equipment, phase separator and washing facility
Kind.Isobutene separative element S1) preferably include isobutene phase outlet and methanol phase outlet.The outlet of the isobutene phase is excellent
Choosing and gaseous oxidation unit A1) it connect, optionally connected via temporary location such as purification unit, heat exchanger and/or pressurizer.
The outlet of the methanol phase is preferably connect at least one of the first esterification unit and the second esterification unit, optionally in
Between methanol purification unit.It may include known to those skilled in the art and seem any equipment conduct for being suitable for purification of methanol
Methanol purification unit.The example of suitable purification unit preferably include at least one distillation equipment, crystallizer, extractor, tower or
Washing facility, more preferably at least a distillation equipment.The example of methanol purification unit describes in EP 1 254 887.
The invention further relates to according to the method for the present invention, wherein this method carries out in the device in accordance with the invention.
It is illustrated the present invention in more detail by attached drawing and non-limiting embodiment.
Description of the drawings
Fig. 1 schematically shows preferred embodiment of the process according to the invention in flow diagram form.
Fig. 2 schematically shows the implementations that wherein the second separative element B is the equipment according to the present invention of extraction cells
Scheme.
Fig. 3 schematically shows the implementation that wherein the second separative element B is the equipment according to the present invention of crystalline element
Scheme.
Fig. 4 shows the part of the method described in embodiment 1.
Embodiment according to fig. 2, by C4Compound imports in gaseous oxidation unit A1, and wherein it is urged in one or two benches
Change in gaseous oxidation and is oxidized to methacrylic acid.C4Compound, oxygen, steam and inert dilution gas enter gaseous oxidation list
The entrance of first A1 is not shown.C4Compound can divide unit AA1 (not shown) from MTBE, via isobutene separative element S1
(not shown) provides.The gaseous state methacrylic acid obtained in gaseous oxidation unit A1 is mutually directed to quenching unit via pipeline 1
A2, wherein it is cooled and is absorbed into water or water phase and forms the water phase containing methacrylic acid.It is single that quenching liquid enters quenching
The entrance of first A2 is not shown.Aqueous methacrylic acid is mutually directed to the first extraction cells A3 via pipeline 2, wherein being used as
It is extracted and forms organic phase and water phase (the first water phase according to the method for the present invention) by the organic solvent of extractant.The two phases
It is detached in the first extraction cells A3.
The organic phase is directed to the first separative element A4 from the first extraction cells A3 via pipeline 3, wherein it is steamed
It evaporates and detaches methacrylic acid and extractant and higher-boiling compound phase.Extractant can be recycled to via pipeline 6
One extraction cells A3.Can via pipeline 5 collect methacrylic acid and optionally one or more purification units in downstream (not
Show) in purifying, or it can be directed to the first esterification unit A5 via pipeline 4, optionally via purifying (not shown).
In first esterification unit A5, can by methacrylated, such as with methanol, such as in separative element S1 (not shown) with
The methanol of MTBE division phase separations, to form methyl methacrylate.Other alcohol as described above can also be used metering system
Acid is esterified in the first esterification unit A5.The ester generated in the first esterification unit A5 is collected via pipeline 7 and it can be optional
Ground polymerize in polymerized unit A6 (not shown), optionally has intermediate and/or downstream purifying.It will be in the first separative element A4
The higher-boiling compound of collection is mutually directed to the second separative element B, is optionally guided via combining unit R, if wherein it is uncommon
The water phase that can be detached with the first extraction cells A3 if prestige merges.
The water phase detached in first extraction cells A3 is directed to the second separative element B (the direct conduit not shown),
Optionally via pipeline 24 and combining unit R guidings, wherein it can mutually merge if desired with higher-boiling compound.
Combining unit R is can be omitted, water phase and higher-boiling compound mutually merge in the second separative element B directly to each other.
It is used as the water phase and higher boiling chemical combination of organic solvent extraction merging in the second separative element B of the second extractant
Object is mutually to form water phase (the second water phase for corresponding to the method for the present invention) and organic phase.The water phase is directed to via pipeline 9
Three separative element C, wherein the residual extractant from the second extraction step can be detached at least partly and optionally via pipe
Line 25 is recycled to the second separative element B.It can will remain water phase (the third water phase for corresponding to the method for the present invention) recycling, example
It is such as recycled to gaseous oxidation unit A1 (not showing conduit), is used as process water, is directed to biologically pure unit and (does not show
Go out) or via the discharge of pipeline 20.The organic phase detached in second separative element B can be directed to the 4th separation via pipeline 10
Cells D, wherein at least one component ii. can be detached.It can collect in the 4th separative element D and be detached at least via pipeline 11
At least part of component ii. a kind of simultaneously optionally purifies (not shown).If the separation component ii. in the 4th separative element D
Mixture, then this mixture can be directed to other separative element so that component ii. is separated from each other (not shown).
It, can will be this via pipeline 15 if detaching methacrylic acid in the 4th separative element D or containing the phase of methacrylic acid
Methacrylic acid or being mutually directed to the first extraction cells A3 or be directed to the first separation list via pipeline 16 containing methacrylic acid
First A4.At least part of at least one component ii. detached in 4th separative element D can also be directed to via pipeline 14
Second esterification unit G.Any of the organic phase detached in second separative element B and water phase or third can be detached single
The water phase detached in first C is directed to the second esterification unit G.In the second esterification unit G, with alcohol by least one component ii. esters
Change to form corresponding ester.If alcohol is methanol, this methanol can be with for example, via optionally having intermediate purification (not shown)
Separative element S1 from MTBE splitters AA1 import.If the ester obtained in the second esterification unit G includes mutually more than one ester,
At least one ester can be then detached in ester separative element H.It can will at least one in the ester purification unit J (not shown) in downstream
Kind ester purifying.Can will be obtained in one or more of second esterification unit G, ester separative element H and ester purification unit J to
A kind of few ester is directed to the second separative element B to be used as extractant.
Fig. 3 shows that wherein the second separative element B according to the present invention is another embodiment party of the equipment of crystalline element
Case.In this embodiment, it is related in the details of apparatus assembly A1 to A6, R, G, H, J, AA1 and S1 and the embodiment of Fig. 2
Identical and only different aspect is described below.It, will generally in crystalline element B2a in the exemplary embodiments of Fig. 2
Combined water phase is mutually cooled such that water crystallizes out at least partly with higher-boiling compound.If crystal is being tied at least partly
It is formed in the cooling surface of brilliant unit B 2a, then they can be scraped.Then it is single the slurry of gained to be optionally directed to stop
First T1 (not shown), wherein it is preferred that stir the slurry, while more multicrystalline growth and/or crystalline size increase.Then via
The slurry of crystal and mother liquor is directed to crystal separative element B2b by pipeline 9 from crystalline element B2a and/or parking cell T1, wherein
Solid crystal is detached with mother liquor at least partly and is optionally washed to remove impurity at least partly.It can be by the one of crystal
Part is back to crystalline element B2a from the B2b guidings of crystal separative element and/or (is not shown to parking cell T1 with serving as crystal seed
Conduit).
Can make the crystal of the optionally washing at least part melt and can be by least part of puddle
Recycling, such as is recycled to gaseous oxidation unit A1 (not showing conduit), is used as process water, as cleaning solution to wash
The crystal in crystal separative element B2a is washed, biologically pure unit (not shown) is directed to or is discharged via pipeline 20.It can be via
The mother liquor detached in crystal separative element B2b is directed to the 4th separative element D by pipeline 10, wherein at least one group can be detached
Divide ii..4th separative element D may include dewatering unit D2a and/or thermal release cells D 2b.If in the 4th separative element D
The mixture of middle separation component ii., then this mixture can be directed to another separative element so as to by component ii. each other
Detach (not shown).It, can be via if detaching methacrylic acid in the 4th separative element D or containing the phase of methacrylic acid
Pipeline 15 is by this methacrylic acid or being mutually directed to the first extraction cells A3 or guided via pipeline 16 containing methacrylic acid
To the first separative element A4.At least one component ii. detached in the 4th separative element D can be collected via pipeline 11 at least
A part simultaneously optionally purifies in other purification unit (not shown).Can also will be detached in 4th separative element D to
A kind of few at least part of component ii. is directed to the second esterification unit G via pipeline 14.It can be by Crystallization Separation unit B 2b
The mother liquor of middle separation is directed to the second esterification unit G.
Test method
The measurement of distribution coefficient (k values)
Water phase comprising predetermined amount acetic acid is merged with the organic solvent (extractant) of same volume.It is shaken at 50 DEG C
And/or the two phases are stirred 15-30 minutes to ensure to reach balanced distribution of the acetic acid in water phase and organic phase.Then allow this
Mixture detaches at 50 DEG C to be returned to organic phase with water phase and is mutually separated from each other the two.Pass through gas-chromatography (GC) or high pressure
Liquid chromatogram (HPLC) measures the amount of acetic acid present in the organic phase of separation.
·HPLC:Agilent 1200
Pump：Quaternary gradient pump
ο eluant, eluents：Acetonitrile KH2PO4(0.02mol/L)pH 2
■ gradients 3min 0%100%
■ 15min 50%50%
■ 30min 70%30%
ο flows：1.0ml/min
ο dwell times：30min
(the p ο st) time is run after ο：5min
ο control pressures：It is 190 bars, 250 bars maximum
Autosampler：Autosampler
ο volume injecteds：20μL
Column stove：Including column switching control
ο temperature：30℃
ο columns：Agilent SB-Aq
■ dimensions lengths 150mm, di4.6mm, 3.5 μm of materials
Detector MWD or DAD
ο UV 210nm, 241nm, 254nm, 265nm (DAD is preferred) GC:Perkin Elmer Autosystem
Autosampler：Perkin Elmer
ο cleaning solvents THF
1.0 μ L of ο volume injecteds
Syringe:
ο shunts split ratio 100
200 DEG C of ο temperature program(me)s
Flow constant pressure 12.0
Column stove：
ο column J＆W Scientific DB 225
ο dimensions lengths 30m, di0.25mm, 0.25 μm of material
ο temperature program(me)s
Rate temperature (DEG C) dwell time (min)
Initial 40 5.0
15 180 4.0
ο run times： 18.3min
Detector FID
260 DEG C of ο setting values
Specific implementation mode
Embodiment 1：
Embodiment 1 describes a part for method as shown in Figure 4.Contain 82.1 by what is generated on the first separative element A4
Weight %MAA, 14.3 weight % is various and part is unknown higher-boiling compounds (dimerization and oligomeric MAA, maleic acid, to benzene two
Formic acid, citraconic acid, polymer etc.) and 3.6 weight % polymerization inhibitors (mainly quinhydrones) higher-boiling compound phase with from the first extraction
Take the first water phase containing 0.6 weight %MAA and 5.0 weight % higher-boiling compounds that unit A3 is isolated by 1:80 higher boiling
The ratio between compound phase and first water phase merge in combining unit R.Measurement of concetration in the merging phase of gained is 1.6 weight %
MAA and 5.1 weight % higher-boiling compounds.The phase of the merging is extracted in the second separative element B with n-hexane.In organic phase
4.9 weight %MAA of middle generation, relative to the comparative situation when not merging the first water phase mutually with the higher-boiling compound
Lower 3.9 weight %MAA.
Claims (24)
1. the method for preparing at least one of methacrylic acid and methacrylate, including following methods step：
A1) at least one C4The gaseous oxidation of compound includes the reaction phase of methacrylic acid to obtain；
A2) quenching of the reaction phase is to obtain the thick water phase for including methacrylic acid；
A3) at least part of the methacrylic acid is extracted into organic solvent from the thick water phase comprising methacrylic acid
In, to obtain the thick organic phase and the first water phase that include methacrylic acid, wherein first water phase includes following components：
I. at least 65 weight %, preferably 65 weight %-99.9 weight %, more preferable 70 weight %-99.8 weight % water, then it is more excellent
75 weight %-99 weight %, more preferable 76 weight %-98.5 weight %, more preferable 77 weight %-98 weight % are selected, even more
It is preferred that 78 weight %-97.5 weight %, even more preferably 79 weight %-95 weight %, even more preferably 80 weight %-90 weight %
Water, based on the total weight of first water phase, and
Ii. it is no more than 35 weight %, preferably 0.1 weight %-35 weight %, preferably 0.2 weight %-30 weight %, more preferable 1 weight
%-25 weight % are measured, even more preferably 1.5 weight %-24 weight %, more preferable 2 weight %-23 weight %, even more preferably 2.5
Weight %-22 weight %, even more preferably 5 weight %-21 weight %, even more preferably at least the one of 10 weight %-20 weight %
Kind of organic compound, based on the total weight of first water phase,
The sum of the weight amount of wherein i. and ii. is 100 weight %；
A4) the separation of at least part of the methacrylic acid and the thick organic phase comprising methacrylic acid and optionally pure
Change；
A5) optionally, step a4) in obtain the methacrylic acid at least part of esterification；
B) be included in step a3) obtained in the first water phase in water at least part at least one component ii. extremely
At least part of separation, to obtain the second water phase and organic phase, wherein the organic phase includes at least one component ii., and
The wherein described second water phase at least one component ii. of dilution compared with the first water phase；
C) optionally, point of at least part of at least one organic compound and the second water phase obtained in method and step b)
From to obtain third water phase；
D) optionally, the separation of at least part of at least one component ii. and the organic phase obtained in method and step b).
2. the method for water phase of the processing comprising at least one organic compound, including following methods step：
A) the first water phase for including following components is provided
I. at least 65 weight %, preferably 65 weight %-99.9 weight %, more preferable 70 weight %-99.8 weight % water, then it is more excellent
75 weight %-99 weight %, more preferable 76 weight %-98.5 weight %, more preferable 77 weight %-98 weight % are selected, even more
It is preferred that 78 weight %-97.5 weight %, even more preferably 79 weight %-95 weight %, even more preferably 80 weight %-90 weight %
Water, based on the total weight of first water phase, and
Ii. it is no more than 35 weight %, preferably 0.1 weight %-35 weight %, preferably 0.2 weight %-30 weight %, more preferable 1 weight
%-25 weight % are measured, even more preferably 1.5 weight %-24 weight %, more preferable 2 weight %-23 weight %, even more preferably 2.5
Weight %-22 weight %, even more preferably 5 weight %-21 weight %, even more preferably at least the one of 10 weight %-20 weight %
Kind organic compound, the total weight based on first water phase；
The sum of the weight amount of wherein i. and ii. is 100 weight %；
B) at least part of the water in the first water phase provided in method and step a) is included in at least one component ii.'s
At least part of separation, to obtain the second water phase and organic phase, wherein the organic phase includes at least one component ii., and
And the wherein described second water phase at least one component ii. of dilution compared with the first water phase；
C) optionally, point of at least part of at least one organic compound and the second water phase obtained in method and step b)
From to obtain third water phase；
D) optionally, the separation of at least part of at least one component ii. and the organic phase obtained in method and step b).
3. according to the method for claim 1 or claim 2, wherein method and step a4) include following methods step：
Aa4) the separation of higher-boiling compound phase and thick organic phase.
4. method according to claim 3, wherein by least part introducing method step a3 of the higher-boiling compound phase)
The first water phase that is middle acquisition or being provided in method and step a).
5. according to the method for any one of the claims, the separation in wherein method and step b) includes following methods step：
B1a) use extractant extracting process step a3) in obtain or provided in method and step a) at least one of the first water phase
Point, to form the second water phase and include the extraction phase of at least one component ii.；
B1b) the second water phase and the extraction phase are at least partially separate.
6. method according to claim 5, the separation in wherein method and step d) includes following methods step：
D1a) the separation of at least part of the extractant and the extraction phase, to obtain comprising at least one component ii.
Extract；
D1b) optionally, the separation of at least part and the extract of at least one component ii..
7. according to claim 5 or the method for claim 6, wherein the third water phase includes to be no more than 3.0 weight %, preferably
No more than 2.8 weight %, more preferably no more than 2.5 weight %, even more preferably be no more than 2.2 weight %, more preferably no more than 2.0
Weight % except method and step b1a) in organic compound in addition to the extractant that uses, the gross weight based on the third water phase
Amount.
8. method as claimed in one of claims 1-4, the separation in wherein method and step b) includes following methods step：
B2a) at least part of the water is from method and step a3) in crystallize at least part of the first water phase for obtaining, with
Crystallization water phase is formed as the second water phase and mother liquor, wherein the mother liquor includes at least one component ii.；
B2b) crystallization water phase and the mother liquor are at least partially separate.
9. method according to claim 8, the separation in wherein method and step d) includes at least one in following methods step：
D2a) method and step b2b) in at least partly dehydration of mother liquor that detaches, to obtain the mother liquor that is at least partly dehydrated；
D2b) at least part and method and step b2b of at least one component ii.) in obtain mother liquor or with method and step d2a)
The separation for the mother liquor of middle acquisition being at least partly dehydrated.
10. according to claim 8 or the method for claim 9, further comprise following methods step：
E2) melting of the crystallization water phase is to obtain fusion-crystallization water phase as third water phase.
11. according to the method for any one of claim 7-10, wherein the third water phase or crystallization water phase include to be no more than
5000ppm, preferably more than 4000ppm, more preferably no more than 3000ppm, preferably 1500-2500ppm, more preferable 1800-
2200ppm, the most preferably not more than organic compound of 2000ppm, the total weight based on the third water phase.
12. according to the method for any one of the claims, wherein the third water phase is allowed to undergo at least one in following procedure
Kind：Be directed to the processing of at least one biologically pure, be used as process water, and be directed to method and step a1) and a2) at least one
It is a.
13. according to the method for any one of the claims, at least one component ii. detached in wherein method and step d) is
The mixture of at least two component ii., and wherein in method and step additionally below
F) at least one component ii. is detached from this mixture at least partly.
14. according to the method for any one of the claims, wherein at least one organic compound of component ii. is at least one
Organic compound of the kind selected from carboxylic acid, aldehyde and ketone.
15. according to the method for any one of the claims, wherein at least one component ii. is or comprising acetic acid, third
At least one of olefin(e) acid, propionic acid and methacrylic acid.
16. according to the method for any one of the claims, wherein method and step d) and at least one of f) in detach
At least one component ii. is or comprising methacrylic acid, and by least part side of being added to of the methacrylic acid
Method step a2) in obtain thick water phase or method and step a3) in obtain thick organic phase in.
17. according to the method for any one of the claims, wherein allow method and step d) and at least one of f) in detach
At least one component ii. or method and step a3) at least part experience following methods step of the first water phase for obtaining
Suddenly：
G) esterification is to obtain the ester phase for including at least one ester.
18. method according to claim 17, wherein the ester includes mutually at least two esters.
19. according to claim 17 or the method for claim 18, following methods step is also comprised：
H) at least one ester and the ester phase are at least partially separate；
J) optionally, the purifying of at least one ester detached in method and step h).
20. according to the method for any one of claim 17-19, wherein step g), at least one of h) and j) in obtain
At least part of at least one ester be used as method and step b1a) in extractant.
21. according to the method for any one of claim 17-20, wherein at least one ester group is in C1-C4Carboxylic acid and C1-C4
Alcohol.
22. according to the method for any one of the claims, following steps are also comprised：
Aa1) division of methyl tertiary butyl ether(MTBE) is to obtain at least one C4Compound and methanol,
The wherein described at least one C4At least one of at least part of compound is as raw material supply method step a1)
Gaseous oxidation.
23. method according to claim 22, wherein by method and step aa1) in the methanol supply method step g) that obtains.
24. the equipment for being used to prepare at least one of methacrylic acid and methacrylate includes at least following fluid each other
Guide the component of connection：
Gaseous oxidation unit (A1),
It is quenched unit (A2),
First extraction cells (A3),
First separative element (A4),
Optionally, the first esterification unit (A4),
Second separative element (B),
Optionally, third separative element (C),
Optionally, the 4th separative element (D),
Wherein described first separative element is thermal release unit, and in its underpart, one third includes at least one outlet at bottom,
At least one outlet at bottom is connected to the guiding of at least one entrance fluid of the second separative element (B).
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| CN201810206739.6A CN108373409A (en) | 2011-09-16 | 2011-09-16 | The preparation method of methacrylic acid and methacrylate |
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| CN201810206739.6A CN108373409A (en) | 2011-09-16 | 2011-09-16 | The preparation method of methacrylic acid and methacrylate |
| PCT/CN2011/079774 WO2013037134A1 (en) | 2011-09-16 | 2011-09-16 | Process for preparation of methacrylic acid and methacrylic acid esters |
| CN201180073459.9A CN103827071A (en) | 2011-09-16 | 2011-09-16 | Process for preparation of methacrylic acid and methacrylic acid esters |
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| JP (1) | JP6008969B2 (en) |
| KR (1) | KR101877597B1 (en) |
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| KR20140064861A (en) * | 2011-09-16 | 2014-05-28 | 에보니크 룀 게엠베하 | Process for preparation of methacrylic acid and methacrylic acid esters |
| JP6092221B2 (en) * | 2011-09-16 | 2017-03-08 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Method for producing methacrylic acid and methacrylic acid ester |
| WO2015012551A1 (en) * | 2013-07-22 | 2015-01-29 | 주식회사 엘지화학 | Method and apparatus for continuously recovering (meth)acrylic acid |
| KR101628287B1 (en) * | 2013-07-22 | 2016-06-08 | 주식회사 엘지화학 | Process for continuous recovering (meth)acrylic acid and apparatus for the process |
| US9718756B2 (en) * | 2013-07-23 | 2017-08-01 | Lg Chem, Ltd. | Method for continuously recovering (meth)acrylic acid and apparatus for the method |
| KR101601938B1 (en) * | 2013-08-30 | 2016-03-09 | 주식회사 엘지화학 | Process for continuous recovering (meth)acrylic acid and apparatus for the process |
| WO2024049105A1 (en) * | 2022-08-30 | 2024-03-07 | 주식회사 엘지화학 | Method for preparing high-purity (meth)acrylic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54119412A (en) * | 1978-03-06 | 1979-09-17 | Mitsubishi Chem Ind Ltd | Purification of methacrylic acid |
| CN101497563A (en) * | 2008-01-30 | 2009-08-05 | 赢创罗姆有限责任公司 | Process for preparation of high purity methacrylic acid |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5148614A (en) * | 1974-10-22 | 1976-04-26 | Japan Synthetic Rubber Co Ltd | METAKURIRUSANNOBUNRIKAISHUHO |
| JPS54115318A (en) * | 1978-02-28 | 1979-09-07 | Sumitomo Chem Co Ltd | Recovery of methacrylic acid |
| JPH03279344A (en) * | 1990-03-27 | 1991-12-10 | Tosoh Corp | Method for reducing acetic acid concentration in acetic acid waste water |
| DE19709392A1 (en) * | 1997-03-07 | 1998-09-10 | Basf Ag | Process for the extraction of (meth) acrylic acid |
| JP2002128728A (en) * | 2000-10-19 | 2002-05-09 | Mitsubishi Rayon Co Ltd | Method for purifying methacrylic acid |
| JP2002193875A (en) * | 2000-12-27 | 2002-07-10 | Mitsubishi Rayon Co Ltd | Method for recovering methacrylic acid |
| DE10242746B4 (en) * | 2002-09-13 | 2010-07-01 | Evonik Degussa Gmbh | Washing device, a process for cleaning a laundry and the use of the washing device |
| SI1995231T1 (en) * | 2007-05-25 | 2014-03-31 | Evonik Roehm Gmbh | Process for preparation of methyl methacrylate using recycled methanol |
| KR20140064861A (en) * | 2011-09-16 | 2014-05-28 | 에보니크 룀 게엠베하 | Process for preparation of methacrylic acid and methacrylic acid esters |
| JP6092221B2 (en) * | 2011-09-16 | 2017-03-08 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｒｏｅｈｍ ＧｍｂＨ | Method for producing methacrylic acid and methacrylic acid ester |
-
2011
- 2011-09-16 SG SG2014012587A patent/SG2014012587A/en unknown
- 2011-09-16 CN CN201810206739.6A patent/CN108373409A/en active Pending
- 2011-09-16 CN CN201180073459.9A patent/CN103827071A/en active Pending
- 2011-09-16 WO PCT/CN2011/079774 patent/WO2013037134A1/en active Application Filing
- 2011-09-16 MY MYPI2014000746A patent/MY161504A/en unknown
- 2011-09-16 JP JP2014530068A patent/JP6008969B2/en active Active
- 2011-09-16 KR KR1020147006620A patent/KR101877597B1/en active IP Right Grant
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2012
- 2012-09-12 TW TW101133297A patent/TWI627161B/en not_active IP Right Cessation
- 2012-09-15 SA SA112330845A patent/SA112330845B1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54119412A (en) * | 1978-03-06 | 1979-09-17 | Mitsubishi Chem Ind Ltd | Purification of methacrylic acid |
| CN101497563A (en) * | 2008-01-30 | 2009-08-05 | 赢创罗姆有限责任公司 | Process for preparation of high purity methacrylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014528935A (en) | 2014-10-30 |
| MY161504A (en) | 2017-04-14 |
| SA112330845B1 (en) | 2015-07-07 |
| WO2013037134A1 (en) | 2013-03-21 |
| KR20140060528A (en) | 2014-05-20 |
| JP6008969B2 (en) | 2016-10-19 |
| CN103827071A (en) | 2014-05-28 |
| TWI627161B (en) | 2018-06-21 |
| KR101877597B1 (en) | 2018-07-12 |
| TW201329035A (en) | 2013-07-16 |
| SG2014012587A (en) | 2014-06-27 |
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Address after: Darmstadt Applicant after: Roma Chemical Co.,Ltd. Address before: Darmstadt Applicant before: EVONIK ROHM GmbH |
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Application publication date: 20180807 |