CN101829591A - Be used for and prepare the method and the method that be used to prepare methacrylic acid of methacrylic acid with catalyst regeneration - Google Patents
Be used for and prepare the method and the method that be used to prepare methacrylic acid of methacrylic acid with catalyst regeneration Download PDFInfo
- Publication number
- CN101829591A CN101829591A CN201010127653A CN201010127653A CN101829591A CN 101829591 A CN101829591 A CN 101829591A CN 201010127653 A CN201010127653 A CN 201010127653A CN 201010127653 A CN201010127653 A CN 201010127653A CN 101829591 A CN101829591 A CN 101829591A
- Authority
- CN
- China
- Prior art keywords
- water
- catalyst
- molybdenum
- methacrylic acid
- soluble serous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- 238000000034 method Methods 0.000 title claims abstract description 56
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 230000008929 regeneration Effects 0.000 title claims description 15
- 238000011069 regeneration method Methods 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 78
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 63
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011733 molybdenum Substances 0.000 claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 238000002360 preparation method Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000006866 deterioration Effects 0.000 claims abstract description 34
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 26
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 7
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 7
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052787 antimony Inorganic materials 0.000 claims description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000001282 iso-butane Substances 0.000 claims description 6
- 235000013847 iso-butane Nutrition 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 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 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000001590 oxidative effect Effects 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000005342 ion exchange Methods 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000009418 renovation Methods 0.000 description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 9
- 239000011964 heteropoly acid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000005078 molybdenum compound Substances 0.000 description 6
- 150000002752 molybdenum compounds Chemical class 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 210000002966 serum Anatomy 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000006392 deoxygenation reaction Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- -1 molybdate compound Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910000025 caesium bicarbonate Inorganic materials 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical group [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide 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
- C07C51/16—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
A kind of be used to regenerate comprise heteropoly compound prepare methacrylic acid with the method for catalyst, described heteropoly compound contains phosphorus, molybdenum and is selected from least a element X in the group of being made up of potassium, rubidium, caesium and thallium, wherein said method comprises the following steps: that deterioration catalyst, nitrate ion, ammonium ion and the water of the preparation that is used for methacrylic acid that (I) will reclaim from the preparation technology of methacrylic acid mix to form water-soluble serous A, and wherein the atomic ratio with described element X and molybdenum is adjusted to 2: 12 to 4: 12; (II) initial compounds and the water with described heteropoly compound mixes to form water-soluble serous B, and wherein the atomic ratio with described element X and molybdenum is adjusted to 0: 12 to 0.5: 12; (III) the water-soluble serous B that obtains in the water-soluble serous A that obtains in the step (I) and the step (II) is mixed, dry and the calcining with mixture then, wherein constituting the described element X in the heteropoly compound of regenerated catalyst and the atomic ratio of molybdenum is 0.5: 12 to 2: 12.
Description
Technical field
The present invention relates to a kind of being used for by regenerating and handle and will prepare the method for methacrylic acid usefulness catalyst regeneration and a kind ofly be used to use the regenerated catalyst that obtains by this renovation process to prepare the method for methacrylic acid to comprising the deterioration catalyst (dead catalyst) of heteropoly compound that contains phosphorus, molybdenum and be selected from least a element X of the group of forming by potassium, rubidium, caesium and thallium.
Background technology
Be known that, be used for preparing the catalyst of heteropoly compound that contains phosphorus, molybdenum comprising of methacrylic acid and be selected from least a element X of the group of forming by potassium, rubidium, caesium and thallium, when when using methacrolein etc. to use as the gas phase catalytic oxidation reaction of raw material is medium-term and long-term, its catalytic activity reduces owing to thermic load etc.
Renovation process as the deterioration catalyst, JP-A-2008-80232, JP-A-2008-86928 and JP-A-2008-93595 disclose the method with the deterioration catalyst regeneration of being used for that comprises the following steps: mix to obtain water-soluble serous with nitrate ion and ammonium ion the deterioration catalyst, dry described slurries are to obtain dry catalyst, the catalyst of calcining drying then.
Yet the regenerated catalyst that obtains by conventional method is not always satisfactory aspect the catalytic activity.
Summary of the invention
An object of the present invention is to provide a kind of method that is used for preparing methacrylic acid usefulness catalyst regeneration, described method can be recovered the catalytic activity of this catalyst satisfactorily.
Another object of the present invention provides a kind of method that is used to use the regenerated catalyst that obtains by renovation process of the present invention with high conversion and highly-selective preparation methacrylic acid.
In order to realize above purpose, the invention provides a kind of be used for regenerating comprise contain phosphorus, molybdenum and be selected from the group of forming by potassium, rubidium, caesium and thallium at least a element X heteropoly compound prepare methacrylic acid with the method for catalyst, wherein said method comprises the following steps (I) to (III), and the atomic ratio of element X in the heteropoly compound of formation regenerated catalyst and molybdenum (X: Mo) be 0.5: 12 to 2: 12:
Step (I): will mix from deterioration catalyst, nitrate ion, ammonium ion and the water that the preparation technology of methacrylic acid reclaims, wherein with the atomic ratio (X: Mo) be adjusted to 2: 12 to 4: 12 of element X and molybdenum to form water-soluble serous A;
Step (II): the initial compounds of described heteropoly compound and water are mixed to form water-soluble serous B, wherein with the atomic ratio (X: Mo) be adjusted to 0: 12 to 0.5: 12 of element X and molybdenum;
Step (III): the water-soluble serous B that obtains in the water-soluble serous A that obtains in the step (I) and the step (II) is mixed the dry and calcining with mixture then.
In a preferred embodiment, the water-soluble serous A that obtains in step (I) contains 0.1 to 3.0 mole ammonium ion by per 1 mole nitrate ion.
In a further preferred embodiment, the liquid phase of the water-soluble serous A that obtains in step (I) has the pH below 8.
In embodiment preferred again, heteropoly compound also comprises vanadium and is selected from least a element in the group of being made up of copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium.
The present invention also provides a kind of method that is used to prepare methacrylic acid, and described method comprises the following steps:
To prepare the methacrylic acid catalyst regeneration by renovation process according to the present invention, then
In the presence of described regenerated catalyst, at least a compound that is selected from the group of being made up of methacrolein, isobutylaldehyde, iso-butane and isobutyric acid is carried out gas phase catalytic oxidation reaction.
In the time will preparing methacrylic acid according to the present invention and use catalyst regeneration, can recover catalytic activity satisfactorily.And, when using the regenerated catalyst that obtains by renovation process of the present invention, can be with high conversion ratio and high selection rate (selectivity) preparation methacrylic acid.
The specific embodiment
Below, will describe the present invention in detail.
Of the present invention being used for comprises preparing the method for methacrylic acid with catalyst regeneration: to the dead catalyst that reclaims from process for preparation of methacrylic acid, i.e. and the deterioration catalyst processing of regenerating, thus obtain regenerated catalyst.
Preparation methacrylic acid that can be by renovation process of the present invention regeneration is to comprise the catalyst that contains phosphorus, molybdenum and be selected from the heteropoly compound of at least a element X in the group of being made up of potassium, rubidium, caesium and thallium with catalyst (below be sometimes referred to as " target catalyst ").This catalyst can comprise the salt of free heteropoly acid or heteropoly acid.Wherein, the catalyst that comprises the acid salt (part neutralization salt) of heteropoly acid is preferred, and the catalyst that comprises the acid salt of Keggin type heteropoly acid is preferred.Preferably, heteropoly compound also contains vanadium and is selected from least a element in the group of being made up of copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium (below be sometimes referred to as " element Y ").
Constitute the heteropoly compound of preparation methacrylic acid, under the state of fresh catalyst before use, preferably have following composition formula (1) with catalyst (target catalyst):
P
aMo
bV
cX
dY
eO
x (1)
Wherein P, Mo and V represent phosphorus, molybdenum and vanadium respectively; X represents to be selected from least a element (element X) in the group of being made up of potassium, rubidium, caesium and thallium; Y represents to be selected from least a element (element Y) in the group of being made up of copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium; O represents oxygen; A, b, c, d and e are the numbers that satisfies 0＜a≤3,0≤c≤3,0＜d≤3 and 0≤e≤3 when b is 12; And x is the value of determining according to the oxidation state of other element.
Especially, in constituting the composition of preparation methacrylic acid with the heteropoly compound of catalyst (target catalyst), the atomic ratio of element X and molybdenum (X: Mo) be preferably 0.5: 12 to 2: 12.
Prepare the method preparation that methacrylic acid can for example comprise the following steps by any conventional method with catalyst (target catalyst): the compound that will contain the various elements in the above-mentioned element that constitutes described heteropoly compound separately (for example, the oxyacid of each element, oxysalt, oxide, nitrate, carbonate, bicarbonate, hydroxide or halide) mix, mixture moulding (molding) is become the shape of expectation and the mixture of calcining moulding.The example of phosphorus-containing compound comprises phosphoric acid, phosphate etc., and the example of molybdate compound comprises molybdic acid, molybdate for example ammonium molybdate, molybdenum oxide, molybdenum chloride etc.; The example of vanadium-containing compound comprises vanadic acid, vanadate (metavanadate) for example ammonium vanadate (ammonium metavanadate), vanadium oxide, vanadium chloride etc.; The examples for compounds that contains element X comprises: oxide is potassium oxide for example, rubidium oxide and cesium oxide, and nitrate is potassium nitrate for example, rubidium nitrate, cesium nitrate and thallium nitrate, carbonate is potash for example, rubidium carbonate and cesium carbonate, bicarbonate be saleratus and caesium bicarbonate for example, and hydroxide is potassium hydroxide for example, rubidium hydroxide and cesium hydroxide, halide is potassium chloride for example, rubidium chloride, cesium fluoride, cesium chloride, cesium bromide and cesium iodide etc.The examples for compounds that contains element Y comprises oxyacid, oxysalt, oxide, nitrate, carbonate, hydroxide and halide.
Usually, when will having target catalyst that aforesaid preferred catalyst forms when being used for the preparation of methacrylic acid under the fresh catalyst state before using, catalytic activity may reduce owing to thermic load etc. sometimes.According to renovation process of the present invention, the deterioration catalyst that such catalytic activity is reduced is used as the catalyst that will regenerate and handle, with two kinds water-soluble serous be that slurries A and slurries B mix, and dry and calcining, thereby with the atomic ratio (X: Mo) be adjusted in the above-described scope of element X and molybdenum with mixture.
According to renovation process of the present invention, (I) to (III) obtains regenerated catalyst by above-mentioned steps.
In step (I), deterioration catalyst, nitrate ion, ammonium ion and water are mixed with preparation slurries A, and with the atomic ratio of element X in the slurries that obtain and molybdenum (X: Mo) be adjusted in 2: 12 to 4: 12 the scope, preferably in 2.5: 12 to 3.5: 12 scope.Improve conversion ratio and the selection rate that realizes by the regenerated catalyst that obtains by mixed nitrate radical ion and ammonium ion in this step.
In order to supply with nitrate ion, except that the nitrate that contains the element that constitutes the target catalyst, for example can be with nitric acid and nitrate such as ammonium nitrate effect nitrate ion source.In order to supply with ammonium ion, except that the ammonium salt that contains the element that constitutes the target catalyst, for example can be with ammonia and ammonium salt such as ammonium nitrate, ammonium carbonate, carbonic hydroammonium and ammonium acetate as ammonium ion source.Preferably, will contain the nitrate of the element that constitutes the target catalyst and ammonium salt as nitrate ion source and ammonium ion source.More preferably, use nitric acid, ammonia and ammonium nitrate, thus with the rate regulation of nitrate ion and ammonium ion in the scope of the following stated.
In step (I) among the water-soluble serous A of preparation, be preferred 0.1 to 3.0 mole by the amount of the ammonium ion of every mole nitrate ion, more preferably 0.5 to 2.5 mole.When the amount of ammonium ion is outside above scope, may recover catalytic activity unsatisfactoryly.
In preparation during water-soluble serous A, should in above-mentioned scope (X among the water-soluble serous A and the ratio of Mo), regulate the element X that contains among the water-soluble serous A and the atomic ratio (X: Mo) of molybdenum.Especially, can contain the compound (containing element X compound) of element X and at least a atomic ratio of regulating in the molybdenum compound by adding.The amount of this compound can be determined by following method: the catalyst of analyzing regeneration deterioration catalyst before with fluorescent X-ray analysis, ICP emission spectrometry etc. is formed (kind and the amount that constitute element), form with catalyst based on the deterioration catalyst, will be at the atomic ratio (X: Mo) regulate in the above range of element X in the composition after adding contains element X compound and/or molybdenum compound and molybdenum.Usually, add the compound that contains element X by the amount of considering the molybdenum in the deterioration catalyst.Even molybdenum is owing to by using thermic load due to this catalyst etc. and disperse or dissipation in that the preparation of methacrylic acid being medium-term and long-term, according to the amount that reduces of element X and/or molybdenum, the composition of deterioration catalyst also can fall into the X of above-described water-soluble serous A sometimes: within the scope of Mo ratio.Under these circumstances, can neither add the compound that contains element X, also not add molybdenum compound.
Can and contain in the compound of element X from the above-mentioned molybdate compound that can the target Preparation of catalysts, use and suitably select one or more compounds, as molybdenum compound of supplying with for the preparation of water-soluble serous A and the compound that contains element X.
When the water-soluble serous A of preparation,, in case of necessity, can add the compound of the element that contains the formation catalyst except that molybdenum and element X based on the composition of deterioration catalyst.As the compound of the element that contains the formation catalyst except that molybdenum and element X, can from the compound that contains each element that the target Preparation of catalysts, uses, suitably select one or more compounds.
Usually can be with deionized water as the water that will supply with the preparation that is used for water-soluble serous A.Based on the molybdenum among the water-soluble serous A of the gained of 1 weight portion, i.e. the gross weight of molybdenum that contains in the deterioration catalyst and the molybdenum that in the molybdenum compound of supplying with, contains, the amount of the water of supply is generally 1 to 20 weight portion.
When the water-soluble serous A of preparation, the order by merging of above-mentioned every kind of component is not particularly limited, and can be provided with arbitrarily.
When the water-soluble serous A of preparation, the deterioration catalyst can former state mix, or can hot preliminary treatment.
The hot pretreated temperature of deterioration catalyst is not particularly limited, and is preferably 350 to 600 ℃.The heat treated processing time is not particularly limited, and is generally 0.1 to 24 hour, is preferably 0.5 to 10 hour.Hot preliminary treatment can for example be carried out in the atmosphere of oxygen-containing gas at oxidizing gas, or can for example carry out in the atmosphere of nitrogen at non-oxidizing gas.
When the deterioration catalyst that uses in the preparation at water-soluble serous A was preformed catalyst, this preformed catalyst can be used as it is, or in case of necessity, can pulverize in advance by conventional method.When in preformed catalyst (preformed catalyst of deterioration), containing when being useful on the fiber that strengthens catalyst etc., preferably regulate degree of grinding, make fiber etc. not be cut off or damage, because if fiber etc. are cut off or damage, then the intensity of catalyst may deterioration.
When the deterioration catalyst that uses in to the preparation at water-soluble serous A carried out pulverization process and hot preliminary treatment, the order of these processing was not particularly limited, although pulverization process was carried out before hot preliminary treatment usually.
The liquid phase of the water-soluble serous A that obtains in step (I) preferably has the pH below 8.When the liquid phase of water-soluble serous A has when surpassing 8 pH, recover catalytic activity unsatisfactorily.
In step (II), the initial compounds and the water that constitute the heteropoly compound of target catalyst are mixed, make the atomic ratio of element X in the slurries that obtain and molybdenum (X: Mo) be adjusted in 0: 12 to 0.5: 12, in preferred 0: 12 to 0.3: 12 scope, to prepare water-soluble serous B.
In the preparation of water-soluble serous B, with at least a compound that contains molybdenum and the optional compound that contains element X initial compounds, make the element X in containing the compound of molybdenum and the atomic ratio (X: Mo) within above-mentioned scope (X among the water-soluble serous B and the ratio of Mo) of molybdenum as heteropoly compound.Therefore, if with the atomic ratio (X: Mo) be adjusted to 0: 12, then needn't mix the compound that contains element X of element X and molybdenum.
As molybdenum compound of in the preparation of water-soluble serous B, supplying with and the compound that contains element X, can from molybdate compound that can the target Preparation of catalysts, use and the compound that contains element X, suitably select one or more compounds.
When the water-soluble serous B of preparation, in case of necessity, can add the compound of the element that contains the formation catalyst except that molybdenum and element X.As the compound of the element that contains the formation catalyst except that molybdenum and element X, can from the compound that contains each element that the target Preparation of catalysts, uses, suitably select one or more compounds.
Usually can be with deionized water as the water that will in the preparation of water-soluble serous B, supply with.Molybdenum among the water-soluble serous B that obtains based on being present in of 1 weight portion, the amount of the water of mixing is generally 1 to 20 weight portion.
When the water-soluble serous B of preparation, the order by merging of above-mentioned every kind of component is not particularly limited, and can be provided with arbitrarily.
In step (III), at first, water-soluble serous A that will obtain in step (I) and the water-soluble serous B that obtains in step (II) mix.Can regulate the mixing ratio of water-soluble serous A and water-soluble serous B, make and to consider the molybdenum that in two kinds of slurries, contains and the amount of element X, the element X in the heteropoly compound that constitutes the regenerated catalyst that finally obtains and the atomic ratio (X: Mo) be 0.5: 12 to 2: 12 of molybdenum.
When with water-soluble serous A and water-soluble serous B mixing, order by merging, temperature and stirring condition are not particularly limited, and can be provided with arbitrarily.
When mixing water-soluble serous A and water-soluble serous B, or when the mixture of water-soluble serous A of ageing and B as described below or after the mixture of water-soluble serous A of ageing and B as described below, if necessary, can mix the compound that contains the element that constitutes the target catalyst, particularly contain the compound of element Y.In this case, the compound that preferably will contain the element that the constitutes catalyst compound etc. that for example contains element Y adds with the form of the waterborne suspension of this compound.Can suitably select their amount, make the heteropoly compound of the regenerated catalyst that formation finally obtains have the preferred composition of the target catalyst under the fresh catalyst state before the use.
In step (III), secondly, will be by mixing the mixed serum drying that water-soluble serous A and water-soluble serous B obtain.Drying means is not particularly limited, and can adopts normally used in this technical field method, for example be evaporated to dried, spray-drying, drum drying and flash drying.Drying condition is not particularly limited, and they can suitably select, thereby reduce water content in the mixed serum satisfactorily.For example, baking temperature is usually less than 300 ℃.
Before drying as mentioned above, preferably by following method ageing by mixing the mixed serum that water-soluble serous A and water-soluble serous B obtain: in closed container at the heating of the temperature more than 100 ℃ mixed serum.With the mixed serum ageing time, can recover catalytic activity effectively.The upper limit of ageing temperature is preferably below 200 ℃, more preferably below 150 ℃.In order to recover catalytic activity satisfactorily, digestion time was generally more than 0.1 hour, and is preferred more than 2 hours, and considers productivity ratio, and it was preferably below 20 hours.
In step (III), calcine the desciccate that obtains later in drying subsequently.Calcining can be undertaken by normally used in the art method, and is not particularly limited.For example, it can be in common calcining heat more than 300 ℃, for example for example carries out in the atmosphere of nitrogen in the atmosphere of oxygen or at non-oxidizing gas at oxidizing gas.Preferably, in order to recover catalyst life satisfactorily, in the atmosphere of oxidizing gas or non-oxidizing gas, calcine by multistep method.More preferably, use two-stage process, described two-stage process is included in first calcining step that carries out in the atmosphere of oxidizing gas and second calcining step that carries out in the atmosphere of non-oxidizing gas.
The oxidizing gas that uses in calcine technology contains the oxidisability material.The preferred embodiment of this gas is an oxygen-containing gas.Concentration of oxygen in the oxygen-containing gas is generally about 1 to about 30 volume %.As the source of oxygen, can use air or pure oxygen, and if necessary, it can use inert gas dilution.Oxidizing gas can randomly contain water.Yet the concentration of the water in the oxidizing gas is generally below the 10 volume %.Oxidizing gas is preferably air.Usually, the calcining of carrying out in the atmosphere of oxidizing gas is carried out in the stream of oxidizing gas.Temperature in the calcining step that carries out in the atmosphere of oxidizing gas is generally 360 to 410 ℃, preferred 380 to 400 ℃.
The non-oxidizing gas that uses in method for calcinating is substantially free of for example oxygen of oxidisability material.The instantiation of non-oxidizing gas comprises inert gas for example nitrogen, carbon dioxide, helium, argon etc.Non-oxidizing gas randomly can contain water.Yet the concentration of the water in the non-oxidizing gas is generally below the 10 volume %.Especially, preferably nitrogen is used as non-oxidizing gas.Usually, the calcining of carrying out in the atmosphere of non-oxidizing gas is carried out in the stream of non-oxidizing gas.Temperature in the calcining step that carries out in the atmosphere of non-oxidizing gas is generally 420 to 500 ℃, preferred 420 to 450 ℃.
Before calcine technology, preferably the desciccate that drying is obtained later on is in the atmosphere of oxidizing gas or non-oxidizing gas, in about 180 to 300 ℃ heat treatment (calcining in advance).
In case of necessity, before calcining or calcining in advance, the desciccate that drying can be obtained later on is molded into the shape of expectation, for example ring, pellet, ball, cylinder etc.Moulding can for example compressing tablet or extrusion molding carry out by any conventional method.For moulding, in case of necessity, can in the product of drying, add entry, shaping assistant or pore former.The example of shaping assistant comprises ammonium nitrate and ceramic fibre and glass fibre.Especially, preferably use ammonium nitrate, reason is that it except the effect of playing shaping assistant, also plays the effect of pore former.
Preferably, the preformed catalyst that subsequently forming method by is before obtained carries out temperature-humidity regulation.When before calcining or calcining in advance, preformed catalyst being carried out temperature-humidity regulation, can obtain more stable catalyst.Particularly, carry out temperature-humidity regulation by following method: it is that 40 to 100 ℃ and relative humidity are that 10 to 60% atmosphere is lasted about 0.5 to 10 hour that preformed catalyst is exposed to temperature.Adjusting can for example be carried out in the container with controlled temperature and humidity, or is undertaken by preformed catalyst being blowed the gas with controlled temperature and humidity.When regulating, usually air is used as atmosphere gas, can use for example nitrogen of inert gas simultaneously.
Renovation process of the present invention can prepare the regenerated catalyst that catalytic activity is recovered satisfactorily.This regenerated catalyst contains heteropoly compound, as the target catalyst, and can comprise the salt of free heteropoly acid or heteropoly acid.Wherein, the catalyst that comprises the acid salt of heteropoly acid is preferred, and the catalyst that comprises the acid salt of Keggin type heteropoly acid is preferred.The element X in the heteropoly compound of formation regenerated catalyst and the atomic ratio (X: Mo) be 0.5: 12 to 2: 12, and preferably, this catalyst has the preferred composition identical with the preferred composition of above-mentioned target catalyst of molybdenum.
Usually, of the present invention being used for is applied to the deterioration catalyst that used in the preparation of methacrylic acid with preparing the method for methacrylic acid with catalyst regeneration.In addition, renovation process of the present invention for example can be applied to the catalyst that also uses in the preparation of methacrylic acid, the loss powder that for example in the preparation process of fresh catalyst, produces (loss powder), or do not have the catalyst of desirable properties.Under these circumstances, can obtain excellent effect with the same under situation with the deterioration catalyst regeneration.
The method that is used to prepare methacrylic acid according to the present invention comprises: the preparation methacrylic acid by renovation process regeneration of the present invention with catalyst in the presence of, the compound that is selected from the group of being made up of methacrolein, isobutylaldehyde, iso-butane and isobutyric acid (below be sometimes referred to as " methacrylic acid raw material ") is carried out gas phase catalytic oxidation reaction.Use can prepare methacrylic acid with high conversion and high selectivity by the regenerated catalyst of method regeneration of the present invention.
Methacrylic acid is usually by following method preparation: catalyst is packed in the multitubular reactor of fixed bed, and supply with the initial admixture of gas that contains oxygen and methacrylic acid usefulness raw material, but can also use the reaction system such as fluid bed or moving bed.As source of oxygen, use air usually.Except that oxygen and methacrylic acid with the raw material, initial admixture of gas can also contain nitrogen, carbon dioxide, carbon monoxide, steam etc.
Methacrylic acid can need not to be with raw material has highly purified purified material.For example, methacrolein can be the reaction product gas that contains methacrolein that the gas phase catalytic oxidation reaction by the isobutene or the tert-butyl alcohol obtains.Initial admixture of gas can contain a kind of methacrylic acid with raw material or two or more methacrylic acid raw materials.
With the kind of raw material etc., can select to be used to prepare the reaction condition of the method for methacrylic acid according to the methacrylic acid that contains in the initial admixture of gas arbitrarily.For example, when using methacrolein as raw material, react under following condition usually: the concentration of the methacrolein in the initial admixture of gas is 1 to 10 volume %, and the concentration of steam is 1 to 30 volume %, the mol ratio of oxygen and methacrolein is 1 to 5, and air speed is 500 to 5000h
-1(based on standard state), reaction temperature are that 250 to 350 ℃ and reaction pressure are 0.1 to 0.3MPa.When iso-butane is used raw material as methacrylic acid, usually react under following condition: the concentration of the iso-butane in the initial gas is 1 to 85 volume %, water vapor concentration is 3 to 30 volume %, and the mol ratio of oxygen and iso-butane is 0.05 to 4, and air speed is 400 to 5000h
-1(based on standard state), reaction temperature are that 250 to 400 ℃ and reaction pressure are 0.1 to 1MPa.When isobutylaldehyde or isobutyric acid use raw material as methacrylic acid, adopt and the substantially the same reaction condition of employed reaction condition when methacrolein is used as raw material.
Embodiment
Below, explain the present invention in more detail by reference example, the scope that described embodiment does not limit the present invention in any way.
The air of Shi Yonging contains the water (corresponding to the water content of atmosphere) of 3.5 volume % in an embodiment, and the nitrogen that uses does not in an embodiment have water basically.
The catalyst that obtains in the following example analysis is carried out as follows and estimate.
Catalyst is formed (ratio that constitutes the element of catalyst) by being determined by following methods analyst catalyst: fluorescent X-ray analysis, use the fluorescent X-ray analysis instrument of being made by Rigaku Corporation, ZSX Primus II.
The activity of such catalysts test
With the catalyst internal diameter of packing into of nine grams (9g) is in the glass microreactor of 16mm, and the initial gas that the nitrogen of the steam of molecular oxygen that will be by mixing the methacrolein by 4 volume % that methacrolein, air, steam and nitrogen prepares, 12 volume %, 17 volume % and 67 volume % is formed is with 670h
-1Air speed be fed in the reactor, and reacted 1 hour in 355 ℃ furnace temperature (being used to heat the temperature of the stove of microreactor).Then, the initial gas that will have composition same as described above is fed in the microreactor with air speed same as described above, and begins reaction once more 280 ℃ furnace temperature.From the reaction begin once more react 1 hour after, (gas after the reaction) takes a sample to giving vent to anger, and, calculate conversion ratio (%), the selection rate (%) of methacrylic acid and the yield of methacrylic acid of methacrolein by following equation by gc analysis.
Conversion ratio (%)=[(molal quantity of the methacrolein of reaction)/(molal quantity of the methacrolein of charging)] * 100
Selection rate (%)=[(molal quantity of the methacrylic acid of generation)/(molal quantity of the methacrolein of reaction)] * 100
Yield (%)=[(molal quantity of the methacrylic acid of generation)/(molal quantity of the methacrolein of supply)] * 100
Reference example 1
The preparation of fresh catalyst
At being heated in 40 ℃ the ion exchange water of 224kg, the cesium nitrate [CsNO of dissolving 38.2kg
3], the 75 weight % orthophosphoric acid of 27.4kg and the 70 weight % nitric acid of 25.2kg, with preparation liquid α.Individually, with the Ammonium Molybdate Tetrahydrate [(NH of 297kg
4)
6Mo
7O
244H
2O] be dissolved in being heated in 40 ℃ the ion exchange water of 330kg, subsequently with the ammonium metavanadate [NH of 8.19kg
4VO
3] be suspended in wherein, with preparation liquid β.
After when stirring and the temperature of liquid α and β remained on 40 ℃, dropwise joining liquid α among the liquid β, mixture was further stirred 5.8 hours at 120 ℃ in closed container, then to the antimony trioxide [Sb that wherein adds 10.2kg
2O
3] with the Gerhardite [Cu (NO of 10.2kg
3)
23H
2O] suspension in the ion exchange water of 23kg.Mixture in closed container at 120 ℃ stirred 5 hour thereafter.With the slurries that obtain spray dryer drying.The ceramic fibre, the ammonium nitrate of 13 weight portions and the ion exchange water of 9.7 weight portions that in the resulting dried powder of 100 weight portions, add 4 weight portions, and the mixture that obtains is mediated and be squeezed into the formation cylinder, described cylinder has the diameter of 5mm and the height of 6mm separately.With the product of moulding dry 3 hours of the relative humidity of 90 ℃ temperature and 30%, then 435 ℃ of calcinings 3 hours in nitrogen stream, and further 390 ℃ of calcinings 3 hours in air stream.After this, with the catalyst recovery of moulding and as fresh catalyst.
Fresh catalyst comprises the heteropoly compound that contains phosphorus, molybdenum, vanadium, antimony, copper and caesium respectively with 1.5,12,0.50,0.5,0.3 and 1.4 atomic ratio.The result of the active testing of fresh catalyst is presented in the table 1.
Reference example 2
Deterioration (giving up) Preparation of catalysts
In the gas phase catalytic oxidation reaction of methacrolein, use special time so that the deterioration catalyst to be provided the fresh catalyst of preparation in the reference example 1.The heteropoly compound that constitutes the deterioration catalyst contains phosphorus, molybdenum, vanadium, antimony, copper and caesium (beyond the deoxygenation) with 1.3,9.6,0.48,0.5,0.3 and 1.4 atomic ratio respectively.The result of deterioration activity of such catalysts test is presented in the table 1.
Embodiment 1
Step (I): the preparation of water-soluble serous A
The deterioration catalyst that obtains in reference example 2 of one hectogram (100g) is joined in the ion exchange water of 200g, and stir the mixture.Then, in order to compensate the not enough element that the deterioration catalyst is compared with fresh catalyst, with the molybdenum trioxide (MoO of 15.8g as the molybdenum source
3), the ammonium metavanadate as the vanadium source as the 75 weight % orthophosphoric acid in phosphorus source and 0.1g of 1.3g adds wherein, adds the cesium nitrate of 17.9g and the ammonium nitrate (NH of 27.0g subsequently
4NO
3).Mixture is heated to 70 ℃, and mixture is remained on identical temperature lasts 1 hour.Then, to the ammoniacal liquor of the 25 weight % that wherein add 6.23g, and with mixture remain on 70 ℃ 1 hour.Mixture in closed container at 120 ℃ stirred 5 hour, to form water-soluble serous A1 thereafter.The ammonium ion among the water-soluble serous A1 and the mol ratio of nitrate ion are 1.0: 1, and the liquid phase of water-soluble serous A1 has 2.8 pH.The metallic element that contains among the water-soluble serous A1 is that the atomic ratio of phosphorus, molybdenum, vanadium, antimony, copper and caesium is respectively 1.5,12,0.50,0.5,0.3 and 3.2, and the atomic ratio of caesium and molybdenum is 3.2: 12.
Step (II): the preparation of water-soluble serous B
Being heated in 40 ℃ the ion exchange water of 105g, the 75 weight % orthophosphoric acid of dissolving 12.9g and the 67.5 weight % nitric acid of 12.3g are to form liquid a.Individually, being heated in 40 ℃ the ion exchange water of 165g, the Ammonium Molybdate Tetrahydrate of dissolving 139g, the ammonium metavanadate with 3.85g is suspended in wherein then, to form liquid b.Stirring and the temperature of liquid a and liquid b being remained in 40 ℃, in liquid b, dropwise add liquid a, to form water-soluble serous B1.The metallic element that contains among the water-soluble serous B1 is that the atomic ratio of phosphorus, molybdenum and vanadium is respectively 1.5,12 and 0.50, and the ratio of antimony, copper and caesium all is zero (0), thereby the atomic ratio of caesium and molybdenum is 0: 12.Step (III): the mixing of water-soluble serous A and water-soluble serous B
The water-soluble serous B1 of whole amount is mixed with the water-soluble serous A1 of whole amount, then mixture was stirred 5 hours at 120 ℃ in closed container.Then, in mixture, add the antimony trioxide of 4.80g and the suspension of Gerhardite in the ion exchange water of 11.0g of 4.76g, and mixture was further stirred 5 hours at 120 ℃ in closed container.With resulting mixed serum 135 ℃ of dryings.The ceramic fibre, the ammonium nitrate of 14 weight portions and the ion exchange water of 7.4 weight portions that in the desciccate that obtains of 100 weight portions, add 2 weight portions, and mixture is mediated and be squeezed into the formation cylinder, described cylinder has the diameter of 5mm and the height of 6mm separately.With the preformed catalyst that obtains dry 3 hours of the relative humidity of 90 ℃ temperature and 30%, calcined 4 hours in air stream at 390 ℃ then, and further in nitrogen stream, calcined 4 hours, reclaim preformed catalyst at last to obtain regenerated catalyst (1) at 435 ℃.
Regenerated catalyst (1) comprises heteropoly compound, and the metallic element beyond the deoxygenation that contains in heteropoly compound is that the atomic ratio of phosphorus, molybdenum, vanadium, antimony, copper and caesium is respectively 1.5,12,0.50,0.5,0.3 and 1.4, and the atomic ratio of caesium and molybdenum is 1.4: 12.The result of the active testing of regenerated catalyst (1) is presented in the table 1.
Embodiment 2
With with the step (1) of embodiment 1 in identical mode prepare water-soluble serous A2, difference is that the amount of the 25 weight % ammoniacal liquor that use in the preparation with the water-soluble serous A in the step (I) of embodiment 1 is changed into 2.74g from 6.23g.The ammonium ion among the water-soluble serous A2 and the mol ratio of nitrate ion are 0.9: 1, and the liquid phase of water-soluble serous A2 has 1.6 pH.The atomic ratio of the metallic element that contains among the water-soluble serous A1 of preparation among the atomic ratio of the metallic element that contains in the water-soluble serous A2 atomic ratio of molybdenum (caesium with) and the embodiment 1 is identical.
Then, use water-soluble serous A2 with the step (II) of embodiment 1 in the water-soluble serous B1 for preparing of identical mode, with the step (III) of embodiment 1 in identical mode prepare regenerated catalyst (2).
Regenerated catalyst (2) comprises heteropoly compound, metallic element beyond the deoxygenation in the heteropoly compound is that the atomic ratio of phosphorus, molybdenum, vanadium, antimony, copper and caesium is respectively 1.5,12,0.50,0.5,0.3 and 1.4, and the atomic ratio of caesium and molybdenum is 1.4: 12.The result of the active testing of regenerated catalyst (2) is presented in the table 1.
Embodiment 3
The deterioration catalyst for preparing in reference example 2 of one hectogram (100g) is joined in the ion exchange water of 200g, and stir the mixture.In order to compensate the not enough element that the deterioration catalyst is compared with fresh catalyst, with adding wherein of the molybdenum trioxide of 15.8g, 1.3g, mixture is heated to 40 ℃ then as the 75 weight % orthophosphoric acid in phosphorus source and the ammonium metavanadate of 0.1g as the vanadium source as the molybdenum source., add the 25 weight % ammoniacal liquor of 37.6g and mixture at 40 ℃ kept 1 hour, add the 67.5 weight % nitric acid of 19.1g, and mixture was kept 1 hour at 40 ℃ thereafter.Then, the aqueous solution that the cesium nitrate that is heated to 40 ℃ 17.9g is dissolved in the ion exchange water of 54g joins in the mixture, and mixture was kept 15 minutes at 40 ℃, to form water-soluble serous A3.The ammonium ion among the water-soluble serous A3 and the mol ratio of nitrate ion are 1.9: 1, and the liquid phase of water-soluble serous A3 has 6.3 pH.The metallic element that contains among the water-soluble serous A3 is that the atomic ratio of phosphorus, molybdenum, vanadium, antimony, copper and caesium is respectively 1.5,12,0.50,0.5,0.3 and 3.2, and the atomic ratio of caesium and molybdenum is 3.2: 12.
Then, use water-soluble serous A3 with the step (II) of embodiment 1 in the water-soluble serous B1 for preparing of identical mode, with the step (III) of embodiment 1 in identical mode prepare regenerated catalyst (3).
Regenerated catalyst (3) comprises heteropoly compound, metallic element beyond the deoxygenation in the heteropoly compound is that the atomic ratio of phosphorus, molybdenum, vanadium, antimony, copper and caesium is respectively 1.5,12,0.50,0.5,0.3 and 1.4, and the atomic ratio of caesium and molybdenum is 1.4: 12.The result of the active testing of regenerated catalyst (3) is presented in the table 1.
Comparative example 1
The deterioration catalyst for preparing in reference example 2 of two hectograms (200g) is joined in the ion exchange water of 400g, and stir the mixture.Then, in order to compensate the not enough element that the deterioration catalyst is compared with fresh catalyst, with adding wherein of the molybdenum trioxide of 31.5g, 2.7g, add the ammonium nitrate of 69.2g subsequently as the 75 weight % orthophosphoric acid in phosphorus source and the ammonium metavanadate of 0.2g as the vanadium source as the molybdenum source.Mixture is heated to 70 ℃, and remains on identical temperature and last 1 hour., add the ammoniacal liquor of the 25 weight %s of 41.2g, and mixture was kept 1 hour at 70 ℃ thereafter.Mixture was stirred 5 hours at 120 ℃ in closed container, to form water-soluble serous C1.The ammonium ion among the water-soluble serous C1 and the mol ratio of nitrate ion are 1.7: 1, and the liquid phase of water-soluble serous C1 has 4.2 pH.The metallic element that contains among the water-soluble serous C1 is that the atomic ratio of phosphorus, molybdenum, vanadium, antimony, copper and caesium is respectively 1.5,12,0.5,0.5,0.3 and 1.4, and the atomic ratio of caesium and molybdenum is 1.4: 12.
With water-soluble serous C1 135 ℃ of dryings to obtain desciccate.The ceramic fibre, the ammonium nitrate of 14 weight portions and the ion exchange water of 7.4 weight portions that in the desciccate of 100 weight portions, add 2 weight portions, and mixture mediated be squeezed into cylinder then, described cylinder has the diameter of 5mm and the height of 6mm separately.With the preformed catalyst that obtains dry 3 hours of the relative humidity of 90 ℃ temperature and 30%, then 390 ℃ of calcinings 4 hours in air stream, and further 435 ℃ of calcinings 4 hours in nitrogen stream.After this, reclaim the regenerated catalyst (C1) of preformed catalyst to obtain being used for comparison.
Regenerated catalyst (C1) comprises heteropoly compound, metallic element beyond the deoxygenation in the heteropoly compound is that the atomic ratio of phosphorus, molybdenum, vanadium, antimony, copper and caesium is respectively 1.5,12,0.5,0.5,0.3 and 1.4, and the atomic ratio of caesium and molybdenum is 1.4: 12.The result of the active testing of regenerated catalyst (C1) is presented in the table 1.
Table 1
Claims (5)
1. one kind is used to regenerate and prepares methacrylic acid with the method for catalyst, described preparation methacrylic acid comprises heteropoly compound with catalyst, described heteropoly compound contains phosphorus, molybdenum and is selected from least a element X in the group of being made up of potassium, rubidium, caesium and thallium, wherein said method comprises the following steps (I) to (III), and the atomic ratio of described element X in the heteropoly compound of formation regenerated catalyst and molybdenum (X: Mo) be 0.5: 12 to 2: 12:
Step (I): will mix from deterioration catalyst, nitrate ion, ammonium ion and the water that the preparation technology of methacrylic acid reclaims, wherein with the atomic ratio (X: Mo) be adjusted to 2: 12 to 4: 12 of described element X and molybdenum to form water-soluble serous A;
Step (II): the initial compounds of described heteropoly compound and water are mixed to form water-soluble serous B, wherein with the atomic ratio (X: Mo) be adjusted to 0: 12 to 0.5: 12 of described element X and molybdenum;
Step (III): the water-soluble serous B that obtains in the water-soluble serous A that obtains in the step (I) and the step (II) is mixed the dry and calcining with mixture then.
2. method according to claim 1, wherein the water-soluble serous A that obtains in step (I) contains 0.1 to 3.0 mole described ammonium ion by per 1 mole described nitrate ion.
3. method according to claim 1 and 2, wherein the liquid phase of the water-soluble serous A that obtains in step (I) has the pH below 8.
4. according to each described method in the claim 1 to 3, wherein said heteropoly compound also comprises vanadium and at least a element that is selected from the group of being made up of copper, arsenic, antimony, boron, silver, bismuth, iron, cobalt, lanthanum and cerium.
5. method that is used to prepare methacrylic acid, described method comprises the following steps:
To prepare the methacrylic acid catalyst regeneration by method according to claim 1, then
In the presence of described regenerated catalyst, at least a compound that is selected from the group of being made up of methacrolein, isobutylaldehyde, iso-butane and isobutyric acid is carried out gas phase catalytic oxidation reaction.
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| JP2009-055727 | 2009-03-09 | ||
| JP2009055727A JP5335490B2 (en) | 2009-03-09 | 2009-03-09 | Method for regenerating catalyst for methacrylic acid production and method for producing methacrylic acid |
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| JP (1) | JP5335490B2 (en) |
| KR (1) | KR101640255B1 (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086874A (en) * | 2013-01-09 | 2013-05-08 | 烟台万华聚氨酯股份有限公司 | Utilization method of tertiary butyl alcohol coproduced by using device for producing epoxypropane by using propene and iso-butane cooxidation method |
| CN103861640A (en) * | 2014-03-13 | 2014-06-18 | 万华化学集团股份有限公司 | Heteropolyacid catalyst and preparation method thereof |
| CN109999869A (en) * | 2013-09-11 | 2019-07-12 | 三菱化学株式会社 | The manufacturing method of methacrylic acid catalyst for producing |
| CN110142063A (en) * | 2018-02-11 | 2019-08-20 | 中国科学院大连化学物理研究所 | For iso-butane Selective Oxidation metering system acid catalyst and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4900449B2 (en) | 2009-10-30 | 2012-03-21 | 住友化学株式会社 | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid |
| JP2013000734A (en) | 2011-06-22 | 2013-01-07 | Sumitomo Chemical Co Ltd | Method for regenerating catalyst for producing methacrylic acid and method for producing methacrylic acid |
| JP2014226614A (en) * | 2013-05-23 | 2014-12-08 | 住友化学株式会社 | Method for producing catalyst for producing methacrylic acid, and method for producing methacrylic acid |
| JP6803238B2 (en) * | 2017-01-10 | 2020-12-23 | セイコーインスツル株式会社 | A method for producing a porous carbon material, a method for producing a porous activated carbon material, and a method for producing an electrode material. |
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| JPH067685A (en) * | 1992-06-25 | 1994-01-18 | Mitsubishi Rayon Co Ltd | Regeneration of deteriorated catalyst |
| TW524719B (en) * | 2000-04-06 | 2003-03-21 | Nippon Catalytic Chem Ind | Method for regenerating heteropolyacid catalyst and method for producing methacrylic acid |
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| JP3887511B2 (en) * | 1999-05-19 | 2007-02-28 | 三菱レイヨン株式会社 | Catalyst production method |
| JP2008000709A (en) * | 2006-06-23 | 2008-01-10 | Mitsubishi Rayon Co Ltd | Manufacturing method of heteropoly-acid based catalyst for manufacturing methacrylic acid |
| JP2008000710A (en) * | 2006-06-23 | 2008-01-10 | Mitsubishi Rayon Co Ltd | Manufacturing method of heteropolyacid based catalyst for manufacturing methacrylic acid |
| JP4715699B2 (en) * | 2006-09-27 | 2011-07-06 | 住友化学株式会社 | Method for regenerating catalyst for methacrylic acid production and method for producing methacrylic acid |
| JP4715707B2 (en) | 2006-10-03 | 2011-07-06 | 住友化学株式会社 | Method for regenerating catalyst for methacrylic acid production and method for producing methacrylic acid |
| JP4951457B2 (en) * | 2007-06-20 | 2012-06-13 | 三菱レイヨン株式会社 | Raw material for production of methacrylic acid catalyst, production method thereof, production method of methacrylic acid synthesis catalyst, and production method of methacrylic acid |
-
2009
- 2009-03-09 JP JP2009055727A patent/JP5335490B2/en not_active Expired - Fee Related
-
2010
- 2010-03-05 SG SG201001597-2A patent/SG165247A1/en unknown
- 2010-03-08 DE DE102010010588A patent/DE102010010588A1/en not_active Withdrawn
- 2010-03-08 KR KR1020100020328A patent/KR101640255B1/en active IP Right Grant
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| JPH067685A (en) * | 1992-06-25 | 1994-01-18 | Mitsubishi Rayon Co Ltd | Regeneration of deteriorated catalyst |
| TW524719B (en) * | 2000-04-06 | 2003-03-21 | Nippon Catalytic Chem Ind | Method for regenerating heteropolyacid catalyst and method for producing methacrylic acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103086874A (en) * | 2013-01-09 | 2013-05-08 | 烟台万华聚氨酯股份有限公司 | Utilization method of tertiary butyl alcohol coproduced by using device for producing epoxypropane by using propene and iso-butane cooxidation method |
| CN109999869A (en) * | 2013-09-11 | 2019-07-12 | 三菱化学株式会社 | The manufacturing method of methacrylic acid catalyst for producing |
| CN103861640A (en) * | 2014-03-13 | 2014-06-18 | 万华化学集团股份有限公司 | Heteropolyacid catalyst and preparation method thereof |
| CN110142063A (en) * | 2018-02-11 | 2019-08-20 | 中国科学院大连化学物理研究所 | For iso-butane Selective Oxidation metering system acid catalyst and preparation method thereof |
| CN110142063B (en) * | 2018-02-11 | 2021-12-17 | 中国科学院大连化学物理研究所 | Catalyst for preparing methacrylic acid by selective oxidation of isobutane and preparation method thereof |
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| DE102010010588A1 (en) | 2010-11-18 |
| KR20100101533A (en) | 2010-09-17 |
| KR101640255B1 (en) | 2016-07-15 |
| JP2010207694A (en) | 2010-09-24 |
| SG165247A1 (en) | 2010-10-28 |
| JP5335490B2 (en) | 2013-11-06 |
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Effective date of abandoning: 20100915 |
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