CN1127747A - 粗(甲基)丙烯酸的提纯 - Google Patents
粗(甲基)丙烯酸的提纯 Download PDFInfo
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- CN1127747A CN1127747A CN95119688A CN95119688A CN1127747A CN 1127747 A CN1127747 A CN 1127747A CN 95119688 A CN95119688 A CN 95119688A CN 95119688 A CN95119688 A CN 95119688A CN 1127747 A CN1127747 A CN 1127747A
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- Prior art keywords
- acid
- methyl
- hydrazides
- aldehyde
- salt
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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 11
- 238000000746 purification Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000004821 distillation Methods 0.000 claims abstract description 20
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 40
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- -1 saturated aliphatic monocarboxylic acid Chemical class 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 150000002429 hydrazines Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 5
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 16
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 11
- 239000012808 vapor phase Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- OTXHZHQQWQTQMW-UHFFFAOYSA-N (diaminomethylideneamino)azanium;hydrogen carbonate Chemical compound OC([O-])=O.N[NH2+]C(N)=N OTXHZHQQWQTQMW-UHFFFAOYSA-N 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000006200 vaporizer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 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 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- AZVSIHIBYRHSLB-UHFFFAOYSA-N 3-furaldehyde Chemical compound O=CC=1C=COC=1 AZVSIHIBYRHSLB-UHFFFAOYSA-N 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- JSTCPNFNKICNNO-UHFFFAOYSA-N 4-nitrosophenol Chemical compound OC1=CC=C(N=O)C=C1 JSTCPNFNKICNNO-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical group CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- JGQGTUOVIVSFSM-UHFFFAOYSA-N NN.NNC(N)=N Chemical compound NN.NNC(N)=N JGQGTUOVIVSFSM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- IAKAIJRXUQFDRQ-UHFFFAOYSA-N but-2-enoic acid 2-methylprop-2-enoic acid Chemical compound C(C=CC)(=O)O.CC(C(=O)O)=C IAKAIJRXUQFDRQ-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 125000001589 carboacyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S203/00—Distillation: processes, separatory
- Y10S203/22—Accessories
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
在一种提纯粗(甲基)丙烯酸的方法中,在加有机羧酸酰肼之后,和如果需要,加有机磺酸后,蒸馏粗(甲基)丙烯酸。
Description
本发明涉及从催化气相氧化法生产的粗(甲基)丙烯酸中除去醛的方法。在该方法中,粗(甲基)丙烯酸与肼衍生物混合并从该混合物中蒸馏(甲基)丙烯酸。
文中所用的(甲基)丙烯酸代表丙烯酸或甲基丙烯酸。
(甲基)丙烯酸本身或其酯,在很广泛的应用如粘合剂中,对于聚合物的制备是特别重要的。
(甲基)丙烯酸尤其可以通过含3或4个碳原子的烷烃、烷醇、烯烃或烯醇的催化气相氧化获得,例如,通过丙烯、丙烯醛、叔丁醇、异丁烯、异丁烷、异丁醛或异丁烯醛的催化气相氧化可特别有利地获得。然而,其它可能的原料化合物是这样一些化合物,在气相氧化期间,从这些化合物实际上仅仅生成作为中间体的C4原料化合物。可举的一个例子是叔丁醇的甲醚。这些原料气体一般以惰性气体如氮气、CO2、饱和烃和/或蒸汽稀释,在升温下和如果需要在超大气压下,与氧混合后通过过渡金属混合氧化物催化剂,氧化成(甲基)丙烯酸并通过吸附于合适的吸附剂中(例如,水或70-75%(重量)二苯醚和25-30%(重量)联苯的混合物)从产物气流中分出(甲基)丙烯酸(参见,例如EP-A-297445和DE-C2136396)。
在通过提纯和/或蒸馏分离步骤(如经蒸馏,共沸蒸馏除去吸附剂水或从水溶液中提取酸和接着蒸馏除去提取剂)除去吸附剂(和如果需要,通过汽提如用空气,先解吸在吸附剂中溶解度低的污染物)后,得到一种酸,即文中所称的粗(甲基)丙烯酸。
由于在催化气相氧化过程中发生一些平行的次要反应,粗(甲基)丙烯酸不是纯产物。产物中含有各种污染物(一般为≤2%(重量),参EP-B 169254),包括与催化气相氧化原料化合物和所得(甲基)丙烯酸相关的为主的醛类化合物。因此,粗(甲基)丙烯酸一般含有甲醛、乙醛、丙烯醛、异丁烯醛、丙醛、正丁醛、苯甲醛、糠醛和巴豆醛、以及乙酸、甲酸和丙酸等污染物。
对于(甲基)丙烯酸的各种应用,粗(甲基)丙烯酸中所含的这些污染物有不利的影响(参见,例如DE-B 2207184)。因此,例如聚合物反应的引发时间,即达到聚合温度和聚合反应实际超始之间的时间,不能再现或聚合度降低。聚合物也可能倾向于腿色。
为了从粗(甲基)丙烯酸中除去污染物和将粗(甲基)丙烯酸转化为纯的(甲基)丙烯酸,发明人进行了深入的研究。一般是通过蒸馏进行,例如,通过两个相继的精馏步骤除去比(甲基)丙烯酸沸腾温度较高或较低的污染物(参见,例如,EP-B 102642)。
然而,问题是至少部分醛污染物的物理性质类似于(甲基)丙烯酸;要单独由精馏除去这些物质,必须利用并不经济的分离塔板数和/或不经济的回流比。
GB-B 1346737和DE-B 2207184公开一种提纯粗丙烯酸的方法,其中含-NH2基的化合物加到粗丙烯酸中并从此混合物中蒸馏丙烯酸。伯胺在很大程度上结合于污染物醛上,以致即便接着简单的蒸馏步骤,就污染物醛而言可获得高程度的分离。最小残余量的醛利用作为胺化合物的肼和苯肼可分出。不过,利用肼和苯肼的缺点是它们的毒性不能接受。因此,EP-A 270999据荐在蒸馏之前,混合粗(甲基)丙烯酸和脒基肼(氨基胍)和/或其盐(优选氨基胍碳酸氢盐),其量为每有1摩醛用1-3摩尔。然而,氨基胍和/或其盐的缺点是其与醛的反应比不完全使人满意。DE-A 4335172推荐在蒸馏前另外加一种有机磺酸以避免形成沉积物。JP-A117716/75推荐,在无胺化合物存在下,结合吩噻嗪/磺酸以减小丙烯酸的聚合倾向。
本发明的目的是要提供一种从催化气相氧化法生产的粗(甲基)丙烯酸中除去醛的方法,其中粗(甲基)丙烯酸与没有上述先有技术中肼化合物的缺点的肼衍生物混合,然后从混合物中蒸出(甲基)丙烯酸。
本发明达到了这一目的。本发明涉及从催化气相氧化法生产的粗(甲基)丙烯酸中除去醛的方法,其中粗(甲基)丙烯酸与肼衍生物混合并从该混合物中蒸馏(甲基)丙烯酸,其中所用肼衍生物是有机羧酸的酰肼。
有机羧酸酰肼的例子特别是半卡巴肼(氨基甲酸酰肼)和有1-10个碳原子的饱和脂族一元羧酸和/或二元羧酸的单酰肼和二酰肼。这些酰肼化合物特别是甲酸、乙酸、丙酸、丁酸和戊酸的酰肼。对于相应酰肼特别适合的饱和脂族二元羧酸是有4-8个碳原子的二元羧酸。己二酸和丁二酸的二酰肼尤其适合。当然,用羧酸酰肼的盐代替酰肼本身也是可能的。适合的盐例如是碳酸氢盐,硝酸盐,硫酸盐或氯化物,如半卡巴肼盐酸盐。
为了决定要加的羧酸酰肼的绝对量,必须知道的醛含量可按已知方法将醛转化成适当的衍生物后用高压液相色谱(HPLC)来测定。一般地,每摩尔醛污染物至少加0.5摩尔羧酸酰肼,但通常不大于5摩尔。所加羧酸酰肼的量较好是1-3摩尔和特别优选的1-2摩尔。
本发明中羧酸酰肼的加入最好在蒸馏前不久进行。换句话说,本发明中羧酸酰肼加到粗(甲基)丙烯酸中,该混合物放置一段时间(反应时间取决于温度,温度为20-100℃时,反应时间为几分钟至几小时,实践中,在室温下放置该混合物是有益的),然后再蒸留。本发明的羧酸酰肼可以加羧酸酰肼本身或其溶液(适合的溶剂例如是水或(甲基)丙烯酸)。
在蒸馏分离期间由于羧酰酰肼和/或其盐带来的沉积物迅速地复盖了蒸馏装置(特别是蒸发器表面),本发明的方法在一定程度上受到不利影响,因为在没有这些添加物的粗(甲基)丙烯酸的蒸馏中不存在这样的不利影响(尽管无这类添加物的蒸馏导致粗(甲基)丙烯酸中醛污染物的低分离程度)。
显然地,羧酸酰肼和/或其盐与醛污染物的直接反应产物和/或蒸馏期间由其形成的次级产物牵涉进了沉积物的形成。
因此,本发明的另一目的是提供一种从催化气相氧化法生产的粗(甲基)丙烯酸中除去醛的方法,在此方法中所说沉积物的形成被降低。
本发明达到了这一目的。本发明涉及从催化气相氧化法生产的粗(甲基)丙烯酸中除去醛的方法。在该方法中,粗(甲基)丙烯酸与本发明的羧酸酰肼和/或其盐混合,和从混合物中蒸馏(甲基)丙烯酸,其中在蒸馏处理前,除了向粗(甲基)丙烯酸中加羧酸酰肼和/或其盐外,至少加一种有机磺酸和/或其盐(特别是碱金属盐)如果有机磺酸是加到25℃的水中对降低其表面张力是在有益的。一般地,每加1摩尔羧酸酰肼化合物加至少0.1摩尔但通常不大于5摩尔的至少一种有机磺酸,上述量不发生不利影响。优选每加1摩尔羧酸酰肼化合物加0.5-2摩尔至少一种有机磺酸。有机磺酸的加入可以是羧酸酰肼加入之前,同时或之后。另外,有机磺酸可以加到蒸馏柱的塔盘上,柱顶或回流于蒸馏柱中。即使沉积物已经形成,有机磺酸的加入也是成功的。
适合的有机磺酸是例如通式为R1-SO3H的烷基磺酸,其中R1为C1-C20烷基。这些烷基磺酸的盐也适合,特别是碱金属盐。一种优选的代表是甲磺酸和其盐。
芳基磺酸及其盐也是适合的。适合的芳基磺酸化合物是甲苯磺酸如对甲苯磺酸,苯磺酸,苯酚磺酸,二甲苯磺酸,二丁基萘磺酸及其盐,特别是其碱金属盐。不过,特别适合的是烷基芳基磺酸及其盐,其中优选的是只有一个烷基取代基的。芳基优选的是苯环或萘环系统。
烷基有5-16个碳原子为好。
R2优选为C8-C12烷基。在通式如上的烷基苯磺酸化合物中,十二烷基苯磺酸及其盐特别重要。这特别适用于通式如下的十二烷基苯磺酸化合物,其中n和m是整数,其和必须为9。最通常地,芳基磺酸化合物优选以其全酸的形式,那芳基磺酸为优选的添加剂。按照本发明,烷基磺酸化合物和芳基烷基磺酸化合物都适合作要加的有机磺酸化合物。
当然,本发明的方法也可用于从不是粗(甲基)丙烯酸的(甲基)丙烯酸中除去醛。也即所说(甲基)丙烯酸由C3-C4化合物气相催化氧化之外的其它途径获得并由于其它原因为醛杂质污染。
按照本发明改进的粗(甲基)丙烯酸的蒸馏优选在减压下进行,≤100毫巴,一般为10-100毫巴较适合。相关的沸腾温度通常为70-105℃范围。
本发明的方法对于由异丁烯醛催化气相氧化起始制备粗甲基丙烯酸的情形特别重要,特别是当异丁烯醛以EP-B92097或EP-B58927所述方法,由叔丁醇,异丁烷或异丁烯的催化气相氧化生产或由甲醛与丙醛反应生产时,和当叔丁醇,异丁烷或异丁烯的催化气相氧化是在300-400℃下用通式I的催化活性组合物进行时,
Mo12BiaFebX1 cX2 dX3 eX4 fOn (I),其中
X1为镍和/或钴,
X2为铊,碱金属和/或碱土金属,
X3为磷,砷,硼,锑,锡,铈,铅,铌和/或钨,
X4为硅,铝,钛和/或锆,
a为0.5-5.0
b为0.01-3.0
c为3.0-10.0
d为0.02-2.0
e为0-5.0
f为0-10和
n为通式I中除氧之外其它元素的价数和数量决定的数字,除了特定的温度-时间外,其它条件与DE-A4023239所述相同,所得异丁烯醛不经中间体的提纯直接用于进一步的氧化反应。另外,当异丁烯醛催化气相氧化时,本发明方法特别适合,除了特定的温度-时间外,在200-350℃下以DE-A4132263所述方法或在250-400℃下以D-A4132648所述方法进行。
当然,本发明的方法在聚合抑制剂如空气,氢醌,氢醌一乙基醚,对亚硝基苯酚,对甲氧基苯酚或吩噻嗪的存在下进行。
基于粗(甲基)丙烯酸,它们通常以50-1000ppm的量使用。
本发明的方法在吩噻嗪和/或芳族羧基化合物如氢醌和氢醌-甲醚作为聚合抑制剂存在下特别有利。
本发明的方法一方面特别有效地从粗(甲基)丙烯酸中蒸馏除去醛污染物,另一方面大大地抑制了相关沉积物的形成,因此,本发明的方法不仅例如适合于分批操作,也特别适合于像DE-A 4201697所述那样连续操作。
实例1
含2-糠醛,3-糠醛和苯甲醛总量为420ppm的粗丙烯酸(基于粗丙烯酸计)在25℃下与1190ppm氨基胍碳酸氢盐混合,接着,在25℃下放置。上述醛的含量以气相色谱作为时间函数被测定。
所得结果如下:
时间(分钟) | 醛总量(ppm,基于粗丙烯酸) |
5 | 380 |
30 | 250 |
60 | 80 |
实例2
按照实例1,但以与1100ppm氨基胍碳酸氢盐等摩尔量的己二酸二酰肼代替氨基胍碳酸氢盐。所得结果如下:
时间(分钟) | 醛总量(ppm,基于粗丙烯酸) |
5 | 300 |
30 | 100 |
60 | 10 |
实例3
按照实例1,但以与1100ppm氨基胍碳酸氢盐等摩尔量的丁二酸二酰肼代替氨基胍碳酸氢盐。所得结果如下:
时间(分钟) | 醛总量(ppm,基于粗丙烯酸) |
5 | 20 |
30 | 10 |
60 | 10 |
实例4
一个蒸发器为以金属电热重沸器加热的玻璃对流-循环蒸发器的连续操作的玻璃精馏柱中,经蒸发器连续进料140ml/小时由DE-A4302991的实例B1所述的丙烯醛催化气相氧化所得的粗丙烯酸,接着,按DE-A21 36 396的实例B1所述方法进行。同样量的粗丙烯酸从蒸发器中蒸发。蒸发后的粗丙烯酸在精馏柱上冷凝并定量地回流回柱顶。通过从柱顶进料酚噻嗪的方法稳定精馏柱。在进料蒸发器之前,粗丙烯酸己与其重的1400ppm的己二酸二酰肼混合。精馏期间,在加热的重沸器上形成沉积物,在操作8小时后沉积物的量达到平衡。其结果示于下表中。该表也给出了在粗丙烯酸进料蒸发器之前,每摩尔己二酸二酰肼存在下直接混合1.5摩尔十二烷基苯磺酸的结果(40小时后)。
表不加十二烷基苯磺酸 8小时后,沉积物为2400mg加十二烷基苯磺酸 40小时后,沉积物<10mg
Claims (10)
1.一种通过混合(甲基)丙烯酸与肼衍生物并从该混合物中蒸馏(甲在)丙烯酸来提纯含醛的(甲基)丙烯酸的方法,其中所用肼衍生物是羧酸酰肼和/或其盐。
2.权利要求1的方法,其中所用的肼衍生物是有1-10个碳原子的饱和脂族一元羧酸和/或二元羧酸的酰肼。
3.权利要求1或2的方法,其中所用的羧酸酰肼是己二酸或丁二酸的酰肼。
4.权利要求1,2或3的方法,其中每摩尔醛污染物用0.5-5摩尔的有机羧酸酰肼化合物。
5.权利要求1-4的任一方法,其中醛污染的(甲基)丙烯酸是催化气相氧化法生产的粗(甲基)丙烯酸。
6.权利要求1-5的任一方去,该方法连续地进行。
7.权利要求1-6的任一方法,其中在蒸馏处理前,向醛污染的(甲基)丙烯酸中除了加羧酸酰肼和/或其盐之外,至少加一种有机磺酸和/或其盐。
8.权利要求1-7的任一方法,其中每加1摩尔羧酸酰肼最多加5摩尔至少一种有机磺酸和/或其盐。
9.权利要求1-8的任一方法,其中每摩尔醛污染物加1-3摩尔羧酸酰肼和/或其盐,和每加1摩尔羧酸酰肼加0.5-2摩尔至少一种有机横酸和/或其盐。
10.权利要求1-9的任一方法,其中所加磺酸化合物包括十二烷基苯磺酸。
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BE786398A (fr) | 1971-07-21 | 1973-01-18 | Basf Ag | Procede de preparation de l'acide acrylique anhydre |
US3725208A (en) * | 1971-08-20 | 1973-04-03 | Nippon Kayaku Kk | Process for purification of acrylic acid from aldehydes by distillation with a reagent |
JPS4831087A (zh) * | 1971-08-25 | 1973-04-24 | ||
CA962698A (en) | 1972-01-31 | 1975-02-11 | The Standard Oil Company | Process for purification of acrylic acid |
DE2235326A1 (de) * | 1972-07-19 | 1974-02-07 | Degussa | Verfahren zur reinigung 1,2-ungesaettigter carbonsaeuren |
JPS5837290B2 (ja) * | 1973-01-24 | 1983-08-15 | 旭化成株式会社 | アルデヒド、ケトンの除去方法 |
JPS50117716A (zh) | 1974-03-06 | 1975-09-16 | ||
JPS5223017A (en) * | 1975-08-13 | 1977-02-21 | Toagosei Chem Ind Co Ltd | Process for purification of (meth) acrylic acid or its esters |
DE3106557A1 (de) | 1981-02-21 | 1982-09-16 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von (alpha)-alkylacroleinen |
DE3213681A1 (de) | 1982-04-14 | 1983-10-27 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von (alpha)-alkylacroleinen |
JPS5944337A (ja) | 1982-09-06 | 1984-03-12 | Nippon Shokubai Kagaku Kogyo Co Ltd | メタクリル酸の精製方法 |
EP0169254B1 (en) | 1984-07-21 | 1987-11-11 | Mitsubishi Petrochemical Co., Ltd. | Process for purification of 1,2-unsaturated carboxylic acids and/or esters thereof |
JPS61218556A (ja) * | 1985-03-25 | 1986-09-29 | Nippon Shokubai Kagaku Kogyo Co Ltd | アクリル酸の精製方法 |
DE3641996A1 (de) | 1986-12-09 | 1988-06-16 | Basf Ag | Verfahren zum abtrennen von aldehyden aus (alpha),(beta)-olefinisch ungesaettigten carbonsaeuren |
DE3721865A1 (de) | 1987-07-02 | 1989-01-12 | Basf Ag | Verfahren zur herstellung von methacrylsaeure |
US5196578A (en) * | 1987-10-09 | 1993-03-23 | Mitsui Toatsu Chemicals, Incorporated | Purification process of methacrylic acid |
CA2030310A1 (en) * | 1989-12-22 | 1991-06-23 | Ronald E. Macleay | Derivatives of n-hals-substituted amic acid hydrazides |
DE4023239A1 (de) | 1990-07-21 | 1992-01-23 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von propen oder iso-buten zu acrolein oder methacrolein |
DE4132263A1 (de) | 1991-09-27 | 1993-04-01 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von acrolein zu acrylsaeure |
DE4132684A1 (de) | 1991-10-01 | 1993-04-08 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von methacrolein zu methacrylsaeure |
DE4201697A1 (de) | 1992-01-23 | 1993-07-29 | Basf Ag | Verfahren zur reinigung von rohsaeuren (alpha),(beta)-monoethylenisch ungesaettigter carbonsaeuren |
DE4302991A1 (de) | 1993-02-03 | 1994-08-04 | Basf Ag | Multimetalloxidmassen |
EP0613924B1 (en) * | 1993-03-02 | 2000-05-17 | Bridgestone Corporation | Method of production of natural rubber treated with viscosity stabilizers |
DE4335172A1 (de) | 1993-10-15 | 1995-04-20 | Basf Ag | Verfahren zur Reinigung von Roh-(Meth)acrylsäure |
-
1994
- 1994-11-23 US US08/347,131 patent/US5482597A/en not_active Expired - Fee Related
-
1995
- 1995-11-14 SG SG1996007648A patent/SG50646A1/en unknown
- 1995-11-14 DE DE59502240T patent/DE59502240D1/de not_active Expired - Lifetime
- 1995-11-14 DK DK95117892T patent/DK0713854T3/da active
- 1995-11-14 EP EP95117892A patent/EP0713854B1/de not_active Expired - Lifetime
- 1995-11-14 ES ES95117892T patent/ES2117349T3/es not_active Expired - Lifetime
- 1995-11-15 CA CA002162950A patent/CA2162950A1/en not_active Abandoned
- 1995-11-16 CZ CZ953021A patent/CZ302195A3/cs unknown
- 1995-11-22 JP JP7304529A patent/JPH08208558A/ja not_active Withdrawn
- 1995-11-23 CN CN95119688A patent/CN1127747A/zh active Pending
- 1995-11-23 KR KR1019950043110A patent/KR960017611A/ko not_active Application Discontinuation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101555200B (zh) * | 2003-11-26 | 2012-11-14 | 罗姆和哈斯公司 | 生产水含量减少的(甲基)丙烯酸的方法 |
CN1305832C (zh) * | 2003-11-28 | 2007-03-21 | 三菱化学株式会社 | (甲基)丙烯酸的提纯方法 |
CN103282339A (zh) * | 2010-12-29 | 2013-09-04 | 罗门哈斯公司 | 减少(甲基)丙烯酸生产工艺中设备结垢的方法 |
CN103282339B (zh) * | 2010-12-29 | 2015-06-03 | 罗门哈斯公司 | 减少(甲基)丙烯酸生产工艺中设备结垢的方法 |
Also Published As
Publication number | Publication date |
---|---|
US5482597A (en) | 1996-01-09 |
DK0713854T3 (da) | 1998-10-19 |
ES2117349T3 (es) | 1998-08-01 |
EP0713854B1 (de) | 1998-05-20 |
DE59502240D1 (de) | 1998-06-25 |
CA2162950A1 (en) | 1996-05-24 |
EP0713854A1 (de) | 1996-05-29 |
SG50646A1 (en) | 1998-07-20 |
JPH08208558A (ja) | 1996-08-13 |
KR960017611A (ko) | 1996-06-17 |
CZ302195A3 (en) | 1996-06-12 |
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