WO2011121976A1 - 回収触媒からの触媒の製造方法 - Google Patents
回収触媒からの触媒の製造方法 Download PDFInfo
- Publication number
- WO2011121976A1 WO2011121976A1 PCT/JP2011/001820 JP2011001820W WO2011121976A1 WO 2011121976 A1 WO2011121976 A1 WO 2011121976A1 JP 2011001820 W JP2011001820 W JP 2011001820W WO 2011121976 A1 WO2011121976 A1 WO 2011121976A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- solution
- producing
- heteropolyacid
- component
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 350
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 54
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 25
- 239000008187 granular material Substances 0.000 claims abstract description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 22
- 239000011733 molybdenum Substances 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000007254 oxidation reaction Methods 0.000 claims description 39
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 25
- 229910052785 arsenic Inorganic materials 0.000 claims description 21
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 229910052787 antimony Inorganic materials 0.000 claims description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 18
- 238000007493 shaping process Methods 0.000 abstract description 2
- 230000006735 deficit Effects 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 101
- 238000006243 chemical reaction Methods 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 28
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 239000000706 filtrate Substances 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 229940076286 cupric acetate Drugs 0.000 description 7
- 229960004643 cupric oxide Drugs 0.000 description 7
- 239000011265 semifinished product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 3
- 229940000488 arsenic acid Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 150000003475 thallium Chemical class 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
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a method for producing a regenerated heteropolyacid catalyst from a recovered heteropolyacid catalyst, wherein the regenerated catalyst is produced using a waste catalyst as a raw material or a part of the raw material. It relates to a manufacturing method.
- Patent Document 1 and Patent Document 2 technologies for recycling a heteropolyacid catalyst for producing methacrylic acid are described in, for example, Patent Document 1 and Patent Document 2. These include dissolving a used heteropolyacid catalyst for producing methacrylic acid and using the solid recovered as a raw material for the catalyst for producing methacrylic acid, and liquid recovered from cesium salt, potassium salt, thallium salt and rubidium salt. A method of adding at least one selected to form a precipitate and using it as a raw material for a catalyst for producing methacrylic acid is described. The recovered solid content is equivalent to an unused catalyst by the method described in these specifications. It is described that it is reproduced to the performance of.
- Patent Document 3 a catalyst containing molybdenum used in the reaction is dispersed in water, and an alkali metal compound and / or ammonia water is added to adjust the pH to 6.5 or less to form a precipitate.
- the production method of the catalyst which uses as the raw material of the catalyst for methacrylic acid production is shown.
- Patent Document 4 prepares a catalyst having the same performance as an unused catalyst by dissolving and / or decomposing a heteropolyacid catalyst whose activity has been reduced in an aqueous medium and treating it with an inorganic ion exchanger. In addition, it is described that the catalyst life is approaching that of an unused catalyst.
- JP 2008-710 A Japanese Patent Laid-Open No. 2008-709 Japanese Patent No. 3887511 Japanese Patent No. 3298978
- All of the recovered catalysts described in the above prior art are used as a spent catalyst for the gas phase oxidation catalyst, and there are no related catalysts recovered from the catalyst production process.
- a catalyst manufacturing process mainly a drying process using a spray dryer, a molding process, a firing process, and the like, the catalyst is lost outside the process due to the scattering of the catalyst and the adhesion to the container, and a certain degree of catalyst loss occurs. They were calculated and charged from the beginning, and the catalyst lost in these processes was conventionally discarded.
- catalysts that have been rejected due to problems such as quality, work-in-progress products (including semi-finished products) that have become fractional due to charging and are often discarded.
- the unused recovered catalyst from the manufacturing process and / or the used catalyst recovered for regeneration (hereinafter also referred to simply as recovered catalyst) are usually tens of thousands of reaction tubes simultaneously with the unused catalyst.
- recovered catalyst In a reactor for the production of methacrylic acid.
- the regenerated catalyst and the unused catalyst there is a difference in the reaction between the two when they are filled in the reaction tube as they are. Variations in activity occur between them, and further variations in catalyst life occur, resulting in inconveniences such as a decrease in overall yield. For this reason, in order to use them together, it is necessary to uniformly mix the two, and an extra work that is not necessary when using only an unused catalyst is required.
- Patent Documents 1 to 3 and the like recover the heteropolyacid catalyst component once dissolved as a precipitate (solid) and reuse it.
- a device such as a centrifugal separator is required and a long time decantation is required.
- it is not necessarily satisfactory from the objective of the same performance as an unused catalyst.
- the present inventors have found that the substance to be regenerated (a catalyst that has been discarded due to scattering in the manufacturing process, a catalyst that has been rejected due to quality problems, etc., A solution portion obtained by dispersing and / or dissolving an unused recovered catalyst such as a work-in-process product or a recovered used catalyst that has become a surplus due to charging or filling, etc. in an aqueous solvent. It is possible to produce a heteropolyacid catalyst that solves the above problems by treating the solution in a specific process as it is and producing the catalyst as it is from the resulting solution without separating the catalyst component as a solid content. As a result, the present invention has been completed. That is, the present inventors have found that the method can be applied not only to unused recovered catalyst from the production process but also to the production of a catalyst using a used catalyst as a raw material.
- the present invention (1) In producing a regenerated heteropolyacid catalyst from a heteropolyacid catalyst containing the recovered molybdenum, phosphorus, vanadium or copper as an essential component, the catalyst comprises the following steps. Production method, Step a) A step of preparing a solution A by mixing a heteropolyacid catalyst with an aqueous solvent and removing components insoluble in the solvent, Step b) a step of measuring the molar content of at least one component of molybdenum, phosphorus, vanadium or copper contained in the solution A; Step c) A step of oxidizing the heteropolyacid by adding hydrogen peroxide water to the solution A or the solution obtained in the following step d.
- Step d) The difference between the molar content obtained in step b and the theoretical molar value of the element required to prepare the target regenerated catalyst is determined, and an insufficient amount of catalyst component is obtained in solution A or step c.
- Step e) A step of drying the solution obtained through Steps a to d to prepare catalyst granules D.
- Step f) A step of preparing the molded catalyst E by molding the catalyst granules D and then firing them.
- the heteropolyacid catalyst further contains one or more selected from the following X and / or one or more selected from Y, and in step b), at least one of molybdenum, phosphorus, vanadium, copper, X or Y
- X alkali metal, alkaline earth metal or ammonia
- Y silver, zirconium, arsenic, boron, germanium, tin, lead, chromium, bismuth, cobalt, nickel, cerium, tungsten, iron, aluminum, magnesium, antimony, niobium, manganese Or titanium.
- the heteropolyacid catalyst is represented by the following general formula: Mo a P b V c Cu d X e Y f O g (Wherein Mo, P, V, and Cu represent molybdenum, phosphorus, vanadium, and copper, respectively.
- X is at least one selected from the group consisting of alkali metals, alkaline earth metals, and ammonia
- Y is silver
- Each represents at least one selected from the group consisting of zirconium, arsenic, boron, germanium, tin, lead, chromium, bismuth, cobalt, nickel, cerium, tungsten, iron, aluminum, magnesium, antimony, niobium, manganese and titanium;
- the heteropolyacid catalyst is a catalyst for producing methacrylic acid by gas phase partial oxidation reaction of methacrolein. Production method.
- the heteropolyacid catalyst is a recovered product of the waste catalyst produced in the production process of the gas phase oxidation catalyst for producing methacrylic acid from methacrolein, or a recovered product of the work product of the gas phase oxidation catalyst.
- a recovered heteropolyacid-based material specifically, a recovered heteropolyacid-based catalyst
- a catalyst having almost the same performance as an unused catalyst with good reproducibility Therefore, the waste catalyst generated in the manufacturing process, for example, the catalyst that has been lost due to scattering, etc., the catalyst that has been discarded due to quality problems, etc.
- Catalyst which is not strictly a waste catalyst generated from the manufacturing process, but is included here because it is common in terms of unused waste catalyst in the present invention), or is discarded due to fractions due to charging, etc.
- It is possible to reuse unused catalyst recovered products (including unused recovered catalysts) such as work-in-process products (including semi-finished products) and efficiently reuse used catalysts, thereby improving the basic unit of catalyst production. Can measure.
- heteropolyacid catalyst (substance to be regenerated) (hereinafter also referred to as “substance M”) containing, as essential components, recovered molybdenum, phosphorus, vanadium or copper, preferably these four elements, used as a raw material in the present invention
- substance M can be a recovered heteropolyacid-based catalyst containing molybdenum, phosphorus, vanadium and copper as essential components used in a gas phase oxidation reaction.
- the substance M is a catalyst that is lost in the catalyst manufacturing process due to scattering, adhesion to the container, etc., and is conventionally discarded (work-in-process products and semi-finished products including semi-finished products), quality, etc.
- In-process products including semi-finished products and / or unused recovered catalysts such as final catalysts (ie, waste catalysts or work-in-process produced in the gas-phase oxidation catalyst production process)
- the recovered product ie, waste catalysts or work-in-process produced in the gas-phase oxidation catalyst production process
- the recovered product and the deteriorated catalyst (used catalyst) used in the oxidation reaction can be specifically mentioned.
- the “work in process” as used in the present specification means a catalyst in a stage containing the catalyst component of the target catalyst (preferably including all active components), but not yet a complete target catalyst.
- a slurry containing a catalyst component, a dried product thereof, an unfired coating catalyst, a calcined catalyst (semi-finished product) after the first calcination can be raised.
- the substance M may be composed of only a catalytically active component, but usually contains an inert component such as a carrier other than the catalytically active component and the catalytically active component, impurities mixed during recovery, and the like.
- the oxidation reaction include a gas phase oxidation reaction for partially oxidizing methacrolein to obtain methacrylic acid, and the substance M used as a raw material of the present invention is a production of a heteropolyacid catalyst used in the reaction.
- the recovered catalyst from the process and the used recovered catalyst are particularly preferred.
- the heteropolyacid catalyst to be regenerated may further contain other active components as necessary in addition to the above essential components.
- the type of the other active ingredient and the use ratio thereof are appropriately determined according to the use conditions of the catalyst so that a catalyst exhibiting optimum performance can be obtained.
- the other active ingredients include the following X and / or Y.
- X At least one selected from the group consisting of alkali metals, alkaline earth metals and ammonia.
- Y at least one selected from the group consisting of silver, zirconium, arsenic, boron, germanium, tin, lead, chromium, bismuth, cobalt, nickel, cerium, tungsten, iron, aluminum, magnesium, antimony, niobium, manganese and titanium .
- the X component is preferably cesium and / or ammonia.
- the Y component is preferably arsenic, antimony, and / or cerium.
- a catalyst containing these preferred X component and / or preferred Y component is one of the preferred catalysts.
- a catalyst containing no X component is also a preferred catalyst.
- the catalyst does not contain the X component and the Y component, or does not contain the X component, and the Y component is at least one selected from the group consisting of arsenic, antimony, and cerium (preferably the Y component is arsenic). Or any one or both of antimony).
- Mo a is a specific catalyst heteropolyacid catalyst P b V c Cu d X e Y f O g (Wherein Mo, P, V, and Cu represent molybdenum, phosphorus, vanadium, and copper, respectively.
- X represents at least one element (or molecule) selected from alkali metal, alkaline earth metal, and ammonia
- Y represents Is at least one selected from the group consisting of silver, zirconium, arsenic, boron, germanium, tin, lead, chromium, bismuth, cobalt, nickel, cerium, tungsten, iron, aluminum, magnesium, antimony, niobium, manganese or titanium
- e is usually 0 or more and 4 or less
- f is usually 0 or more and 5 or less
- g is a numerical value determined by the oxidation state of each element.
- the catalyst represented by these can be mentioned.
- preferred X component is cesium and / or ammonia.
- a preferred Y component is at least one selected from the group consisting of arsenic, antimony and cerium.
- One of the preferred catalysts is a catalyst containing the above preferred components as X and / or Y as described above.
- one of the more preferable catalysts is a catalyst that does not contain X in the above general formula, and more preferably a catalyst in which Y is a component listed as preferable above.
- the catalyst does not contain an X component and the Y component is at least one selected from the group consisting of arsenic, antimony and cerium (preferably the Y component is either arsenic or antimony or both). is there.
- Step a) First, in step a), the substance M, which is the regeneration target substance, is mixed with an aqueous solvent to remove components insoluble in the solvent, and a solution A containing the active component element of the catalyst is prepared.
- the catalyst component contained in the substance M is generally highly soluble in water. However, when impurities such as an insoluble carrier or insoluble dust mixed during collection are contained, they are dispersed without being dissolved.
- the substance M is preferably a heteropolyacid catalyst that does not contain a water-insoluble component in the catalyst active component.
- aqueous solvent used in the present invention ion-exchanged water and / or distilled water usually not containing an organic solvent is suitable. However, in some cases, ethanol or the like can be appropriately added to this. By adding ethanol, solubility may be improved. Therefore, in some cases, an aqueous solvent such as a water-ethanol mixed solvent is also preferable.
- the amount of the solvent used is preferably about 0.5 to 2 times by weight with respect to the substance M. If the amount of the solvent is too small, the catalyst component may not be sufficiently dissolved. If the amount is too large, it is difficult to obtain an effect commensurate with it.
- the mixing of the substance M and the aqueous solvent may be any method as long as both can be mixed uniformly. Usually, it can carry out by adding the substance M gradually, stirring an aqueous solvent. Usually, it can be performed at room temperature.
- the mixing time of the substance M and the aqueous solvent is not particularly limited as long as the catalyst component to be recovered in the substance M is dissolved. Since the heteropolyacid catalyst component in the substance M is easily dissolved in water, it is usually preferably about 1 to 30 minutes. During this time, it is preferable to stir to such an extent that the inside of the dissolution tank becomes uniform. After stirring, the solution portion and the insoluble component are separated. It may be separated immediately after stirring, or may be separated after standing for about 1 to 30 minutes.
- Separation of the solution portion and insoluble matter can be performed by a conventional method of solid-liquid separation.
- insolubles can be separated and removed most commonly by filtration.
- the insoluble matter may be removed by using both pumping of the supernatant solution portion and filtration.
- the insoluble matter may be discarded as it is, but in order to improve the recovery rate of the catalyst components remaining in the insoluble matter after filtration, the insoluble matter after filtration is about 1 to 5 times with an aqueous solvent (preferably water).
- the washing operation is repeated about 1 to 3 times, or the insoluble matter is mixed with an aqueous solvent (preferably water) and separated, and the separation operation is carried out about 1 to 5 times (preferably about 1 to 3 times). ) You may repeat.
- the recovery of the catalyst component typified by molybdenum contained in the insoluble matter is improved by repeating the washing with the aqueous solvent or mixing and separating into the aqueous solvent about 1 to 3 times. Therefore, it is preferable to perform the above operation a plurality of times.
- the solution obtained by these operations can be combined with the solution portion obtained by the first operation to form a solution A containing a catalyst component. If the solute concentration in the solution A is too low, the catalyst recovery efficiency is lowered. Therefore, the solute concentration in the solution A is preferably about 10 to 40% by weight, more preferably 20 to 30% by weight with respect to the total amount of the solution A. Degree.
- Step b) is a step of measuring the molar content of at least one component of molybdenum, phosphorus, vanadium or copper contained in the solution A.
- the substance M is a catalyst comprising a water-soluble heteropolyacid that does not contain a poorly water-soluble salt such as a cesium salt, particularly a catalyst recovered from its manufacturing process (also referred to as a manufacturing process recovery catalyst), it is used in the reaction. It should have the same composition ratio as the unused catalyst. However, according to the study by the present inventors, the regenerated catalyst prepared by dissolving the process recovery catalyst did not exhibit the same performance as the unused catalyst.
- the concentration of the catalyst component contained in the solution A is quantitatively analyzed, and the composition ratio of the active component element of the regenerated catalyst is set to the composition ratio of the target catalyst. It became necessary to align.
- the concentration of the catalyst component contained in the solution A can be measured by a known method.
- a measurement solution can be taken from the solution A, and the concentration of the catalyst component contained in the measurement solution can be quantitatively analyzed by ICP emission analysis, atomic absorption analysis, fluorescent X-ray analysis, or the like. These methods are preferable from the viewpoint that simple and accurate measurement can be performed. Quantification of the catalyst component can be performed only when the shortage component is known in advance. However, it is usually impossible to predict the excess or deficiency of the active component element in the recovered catalyst. Preference is given to all active component elements of the catalyst.
- Step c) is a step of adding hydrogen peroxide water to the solution A to oxidize the recovered catalyst component (heteropolyacid) (also referred to as a hydrogen peroxide addition step or a step of obtaining the solution (B) for convenience).
- the recovered catalyst from the production process is not used, the solution A obtained by dissolving the catalyst exhibits a dark green to blue color which is a reduced color of heteropolyacid. According to the study by the present inventors, even if this solution is used as it is, it is difficult to obtain a regenerated catalyst having performance equivalent to that of an unused catalyst.
- the performance of the active component in the recovered catalyst is returned to the performance of the active component in the target unused catalyst by adding hydrogen peroxide water to the solution (A) and oxidizing the recovered heteropolyacid.
- the concentration of the hydrogen peroxide used is usually 5 to 30% by weight.
- the amount of hydrogen peroxide to be used varies depending on the composition of the heteropolyacid and the history of the substance M, but cannot be generally stated, but is about 5 to 20% by weight with respect to the substance M. The amount of use tends to decrease as the temperature of the solution A increases.
- the oxidation reaction with hydrogen peroxide solution may be carried out at room temperature, but the temperature of the solution A is raised in the range of about 40 to 100 ° C., preferably about 40 to 95 ° C., more preferably about 60 to 95 ° C. in advance. It is preferable to gradually add hydrogen peroxide so as to maintain the temperature. Since the oxidation reaction with hydrogen peroxide is exothermic, care is taken so that the temperature of the solution A does not rise too much.
- the solution obtained by oxidation with the hydrogen peroxide solution is referred to as an oxidized solution (solution B). Note that the step b and the step c may be the step c and the step b.
- Step d is a step of making the composition ratio of the catalytic active component element contained in the solution A coincide with the composition ratio (theoretical value) of the active component element of the target catalyst using the quantitative analysis result in step b (component adjustment) Also called a process).
- the active component element and the amount to be added to the solution A (or solution B) are calculated from a comparison between the composition ratio of the catalytic active component element and the composition ratio of the active component element of the target catalyst in the quantitative analysis result.
- Components (additional components) and additional addition amounts to be added to the solution A (or solution B) calculated from the difference between the quantitative analysis result in step b and the theoretical value of the target catalyst composition are added as additional raw materials.
- the additional raw material a compound containing an additional component element can be appropriately selected. It is preferable to use the same raw material compound used for producing the target catalyst. In addition, let the said theoretical value be preparation molar ratio of the raw material element at the time of manufacturing a target catalyst. Further, the solute concentration (total concentration of catalyst components) contained in the solution obtained after adding and dissolving the additional raw material is preferably 5 to 15% by weight, more preferably about 10% by weight with respect to the total amount of the solution ( For example, about 8 to 12% by weight). If necessary, it is preferable to add pure water to adjust the solute concentration in the solution to the above range.
- the step c (hydrogen peroxide addition step) and the step d (component adjustment step) may be performed before the step d and after the step c.
- the steps b to d do not necessarily have the order described above.
- the execution order of the process b and the process c can be changed, and the execution order of the process c and the process d can be changed.
- Step e) Catalyst granules D can be obtained by drying the solution (also referred to as solution C) obtained through steps a) to d) by a known method. Although a drying means is not specifically limited, For example, it is preferable to dry using a spray dryer. Step f) In this step, the catalyst granules D are molded to obtain a molded catalyst E. About the shape of the shaping
- the molding method is not particularly limited, and a method for molding an oxidation catalyst used for producing (meth) acrylic acid, for example, an extrusion granulation method, a tableting method, a coating method and the like can be employed.
- a catalytically active component is supported on a spherical carrier of about 2 to 4 mm, particularly an inert carrier such as silica or alumina, together with a binder of water or / and an organic binder (for example, ethanol) as necessary.
- a supported catalyst having a particle diameter of 3 to 6 mm can be obtained.
- the supported catalyst is preferable from the viewpoint of reaction performance, heat removal efficiency, and the like.
- the substance M may contain a carrier or an organic binder, but there is no problem in the present invention.
- a carrier such as an aqueous ethanol solution
- the solution A may be removed by heating before adding hydrogen peroxide in step c. If the carrier is insoluble, it is recovered as an insoluble matter in step a.
- the shaped catalyst E regenerated by the present invention can be used alone or together with an unused target catalyst.
- it is used for the gas phase partial oxidation reaction of methacrolein by a known method.
- the molded catalyst E alone or together with an unused target catalyst is packed in a shell-and-tube reactor so as to have a bed height of 2 to 5 m, and methacrolein is 2 to 6% by volume.
- a gas in which 2.0 times mole or more of oxygen relative to the methacrolein and 3.0 times mole or more of water vapor relative to the methacrolein coexist with the catalyst at a space velocity of 600 h ⁇ 1 to 1800 h ⁇ 1.
- methacrolein it is preferable to perform the gas phase partial oxidation reaction of methacrolein in an atmosphere of a reaction temperature of 260 to 360 degrees and an atmospheric pressure of about 100 kPaG.
- the methacrolein used is not necessarily a pure product, and may contain carbon monoxide, carbon dioxide, aldehydes, carboxylic acids, and aromatic compounds as organic impurities.
- the period of use of the catalyst varies depending on the reaction conditions and cannot be generally stated, but is usually 1 to 4 years.
- methacrylic acid is converted from methacrolein.
- a used catalyst degraded catalyst
- methacrylic acid is converted from methacrolein.
- It may be an unused recovered catalyst such as a waste catalyst generated in the manufacturing process of the gas phase oxidation catalyst for manufacturing or a recovered product of work-in-process.
- the waste catalyst generated in the production process include an unused catalyst (a waste catalyst) that has been conventionally treated as a waste.
- a catalyst lost outside the process in the catalyst manufacturing process for example, a catalyst lost due to scattering or adhering to a container, for example, an in-process product adhering to a container, an in-process item scattered during spray drying, a container, etc.
- a catalyst such as a semi-finished product before or after the first calcination that has adhered to the surface), or a catalyst that has been discarded due to a fraction due to filling or the like.
- examples of work-in-progress of the gas phase oxidation catalyst include work-in-process and the like that have become surplus due to fractions due to charging and the like.
- the “theoretical value” is a raw material element charging molar ratio for producing a target catalyst.
- the preferred embodiments of the present invention are summarized as follows.
- (I) An embodiment in which the heteropolyacid catalyst recovered for regeneration is a production process recovery catalyst or a used catalyst.
- conversion rate of methacrolein ⁇ (number of moles of methacrolein supplied ⁇ number of moles of unreacted methacrolein) / number of moles of methacrolein supplied ⁇ ⁇ 100
- Methacrylic acid yield ⁇ (number of moles of methacrylic acid produced-number of moles of methacrylic acid supplied) / number of moles of methacrolein supplied ⁇ X100
- Methacrylic acid selectivity ⁇ (number of moles of methacrylic acid produced ⁇ number of moles of methacrylic acid supplied) / (number of moles of methacrolein supplied ⁇ number of moles of unreacted methacrolein) ⁇ X100
- Example 1 10000 ml of room temperature distilled water was charged with 1000 g of molybdenum trioxide, 96.09 g of 85 wt% phosphoric acid aqueous solution, 37.91 g of vanadium pentoxide, 65.73 g of 60 wt% aqueous arsenic acid, 22.1 g of cupric oxide, and 95 with stirring. The solution was heated to 95 ° C. and dissolved at 95 ° C. over 10 hours while heating under reflux to obtain a reddish brown solution. This was dried with a spray dryer to obtain catalyst granules. 70 parts by weight of a strength improving material was mixed with 500 parts by weight of the obtained catalyst granules.
- a silica / alumina inert carrier particle size: 3.5 mm
- the molded product thus obtained was calcined at 300 ° C. for 5 hours to obtain a heteropolyacid catalyst 1 (hereinafter referred to as catalyst 1).
- the average particle diameter of the obtained catalyst was 4.3 mm.
- the composition ratio of the obtained heteropolyacid catalyst excluding oxygen was 0.6 with respect to molybdenum 10, vanadium 1.2, phosphorus 1.2, arsenic 0.4, and copper 0.4.
- the catalyst production described above was continuously performed, and at that time, the catalyst (substance M) lost mainly due to scattering or adhering to the container was recovered from the drying process, the molding process, and the firing process using a spray dryer. . 1000 g of substance M was added to 1000 g of pure water, and suction filtration was performed using a back paper stirred for 3 minutes. An operation of adding 1000 g of pure water while leaving the filtration residue in Nutsche and performing suction filtration again was performed three times for convenience. All of the obtained filtrates were combined to obtain a filtrate (solution A). The final solid content was about 200 g, and qualitative analysis by fluorescent X-ray analysis was mainly composed of silica and alumina.
- the weight of the filtrate (solution A) collected in the above step was measured, and 100 g of the filtrate was sampled and transferred to a jacket-type kettle and heated and stirred at 90 ° C. for 15 minutes.
- the powder obtained by drying the sampled filtrate (solution A) by an evaporator was quantitatively analyzed by fluorescent X-ray analysis.
- the weight was 12.0 g of molybdenum trioxide, 2.5 g of vanadium pentoxide, and 0.7 g of cupric oxide.
- the reaction bath temperature was lowered to 310 ° C., and the reaction results were measured.
- the high-temperature reaction treatment is an accelerated test for seeing deterioration of catalyst activity or the like in a severe test.
- the results of the oxidation reaction of catalyst 1 and catalyst E1 are shown in Table 1.
- Example 2 1000 g of molybdenum trioxide, 88.1 g of 85 wt% phosphoric acid aqueous solution, 37.9 g of vanadium pentoxide, 82.2 g of 60 wt% aqueous arsenic acid solution, 55.5 g of cupric acetate, 10.2 g of antimony trioxide in 10000 ml of distilled water at room temperature was heated to 95 ° C. with stirring, and dissolved over 10 hours at 95 ° C. with heating under reflux to obtain a reddish brown solution. This was dried with a spray dryer to obtain catalyst granules. 70 parts by weight of a strength improving material was mixed with 500 parts by weight of the obtained catalyst granules.
- catalyst 2 a heteropolyacid catalyst (hereinafter referred to as catalyst 2).
- the average particle diameter of the obtained catalyst was 4.3 mm.
- the composition ratio of catalyst 2 excluding oxygen was 0.6 for vanadium, 1.1 for phosphorus, 0.5 for arsenic, 0.4 for copper, and 0.1 for antimony with respect to molybdenum 10.
- the catalyst production described above was continuously performed, and at that time, the catalyst (substance M) lost mainly due to scattering or adhering to the container was recovered from the drying process, the molding process, and the firing process using a spray dryer. . 1000 g of substance M was added to 1000 g of pure water, and suction filtration was performed using a back paper stirred for 3 minutes. An operation of adding 1000 g of pure water while leaving the filtration residue in Nutsche and performing suction filtration again was performed twice for convenience. All of the obtained filtrates were combined to obtain a filtrate (solution A). The final solid content was about 200 g, and qualitative analysis by fluorescent X-ray analysis was mainly composed of silica and alumina.
- the weight of the filtrate (solution A) collected above was measured, and 100 g of the filtrate was sampled and transferred to a jacket-type kettle, and heated and stirred at 90 ° C. for 15 minutes.
- the powder obtained by drying the sampled filtrate (solution A) with an evaporator was quantitatively analyzed by fluorescent X-ray analysis.
- the components and weight to be added to return the theoretical value of the catalyst before the intended use Were molybdenum trioxide 27.0 g, vanadium pentoxide 2.0 g, and cupric acetate 2.5 g. Since the solution A had an ethanol odor, 6000 g of pure water was added to the solution A, and the mixture was further heated and stirred at 90 ° C. for 2 hours.
- Example 3 To 1000 ml of distilled water at room temperature, 1000 g of molybdenum trioxide, 112.1 g of 85 wt% phosphoric acid aqueous solution, 75.8 g of vanadium pentoxide, 22.11 g of cupric oxide were charged, and the temperature was raised to 95 ° C. with stirring and heated to reflux. However, it melt
- the catalyst production described above was continuously performed, and at that time, the catalyst (substance M) lost mainly due to scattering or adhering to the container was recovered from the drying process, the molding process, and the firing process using a spray dryer. . 1000 g of substance M was added to 1000 g of pure water, and suction filtration was performed using a back paper stirred for 3 minutes. An operation of adding 1000 g of pure water while leaving the filtration residue in Nutsche and performing suction filtration again was performed three times for convenience. All of the obtained filtrates were combined to obtain a filtrate (solution A). The final solid content was about 200 g, and qualitative analysis by fluorescent X-ray analysis was mainly composed of silica and alumina.
- the weight of the filtrate (solution A) collected in the above step was measured, and 100 g of the filtrate was sampled and transferred to a jacket-type kettle and heated and stirred at 90 ° C. for 15 minutes.
- the components and weight to be added were 27.0 g of molybdenum trioxide, vanadium pentoxide 2 0.0 g and cupric acetate 2.5 g. Since the solution A had an ethanol odor, after adding 5000 g of pure water to the solution A, it was further heated and stirred at 90 ° C. for 2 hours.
- Example 4 To 20000 ml of distilled water at room temperature, 2000 g of molybdenum trioxide, 192.18 g of 85 wt.% Phosphoric acid aqueous solution, 75.82 g of vanadium pentoxide, 131.46 g of 60 wt.% Arsenic acid aqueous solution, and 44.2 g of cupric oxide were charged with stirring. The solution was heated to 95 ° C. and dissolved at 95 ° C. for 10 hours while heating under reflux to obtain a reddish brown solution. This was dried with a spray dryer to obtain catalyst granules. To 1000 parts by weight of the obtained catalyst granules, 140 parts by weight of a strength improver was mixed.
- the supported catalyst thus obtained was calcined at 300 ° C. for 5 hours to obtain a heteropolyacid catalyst (hereinafter referred to as catalyst 4).
- the average particle diameter of the obtained catalyst was 4.3 mm.
- the composition ratio of the obtained heteropolyacid catalyst excluding oxygen was 0.6 with respect to molybdenum 10, vanadium 1.2, phosphorus 1.2, arsenic 0.4, and copper 0.4.
- the catalyst 4 was packed in a steel reaction tube with an inner diameter of 29.4 mm equipped with a thermocouple protection tube with an outer diameter of 6 mm for measuring the hot spot temperature so that the packed bed height was 350 cm.
- a reaction product gas obtained by oxidizing isobutylene with molecular oxygen in the presence of a composite oxide catalyst mainly composed of molybdenum, bismuth, cobalt, and iron was used.
- the composition (molar ratio) of the reaction product gas was 3.21% methacrolein, 8.99% oxygen, 71.54% nitrogen, 14.46% water vapor, 0.12% methacrylic acid, and other 1.68. %Met.
- the reaction product gas was supplied to the reaction tube so that the space velocity was 800 h ⁇ 1 .
- the partial oxidation reaction of methacrolein was continued while adjusting the reaction bath temperature so that the methacrolein conversion was 75% ⁇ 2%.
- the outlet pressure of the reactor was adjusted to 0.5 kG (50 kPaG).
- the reaction bath temperature was 297 ° C.
- the methacrolein conversion rate was 77%
- the hot spot temperature was 317 ° C.
- the methacrylic acid selectivity was 81.5%.
- the spent catalyst was extracted from the reaction tube and recovered in its entirety.
- the weight of the filtrate (solution A) collected in the above step was measured, and 100 g of the filtrate was sampled and transferred to a jacket-type kettle. After adding 5000 g of pure water to solution A, IXE- manufactured by Toagosei Co., Ltd. 69 g of 300 was added, and suction filtration was performed using a back paper stirred for 30 minutes.
- the components and weight to be added were 174.3 g of molybdenum trioxide, vanadium pentoxide 3 .86 g, 0.23 g of 85% by weight phosphoric acid aqueous solution, and 0.37 g of cupric acetate.
- the solution A was transferred again to a jacket-type kettle, and heated and stirred at 90 ° C. for 2 hours to remove ethanol. Thereafter, 900 ml of 30% by weight hydrogen peroxide water was gradually added while stirring was continued. As a result, the solution A changed from a dark green to an orange transparent solution B.
- Example 1 a molded catalyst E5 was prepared in the same manner as in Example 1 except that molybdenum trioxide, vanadium pentoxide, and copper oxide were not added. Table 1 shows the results of partial oxidation reaction of methacrolein of E5 catalyst.
- Comparative Example 2 A molded catalyst E6 was prepared in the same manner as in Example 1 except that the solution B was not prepared and molybdenum trioxide, vanadium pentoxide, and copper oxide were not added. Table 1 shows the results of partial oxidation reaction of methacrolein of E6 catalyst.
- the target catalyst and the regenerated catalyst can be used in any of methacrolein conversion, methacrolein selectivity, and methacrolein yield after 3 hours, and after high temperature treatment.
- the regenerated catalyst obtained by the present invention has a performance equivalent to that of the unused target catalyst, and even if used together with the unused target catalyst, there is no problem. It turns out that there is no catalyst.
- Test Example 2 The catalyst E2 (regenerated supported catalyst) obtained in Example 2 was packed into a steel reaction tube having an inner diameter of 29.4 mm and equipped with a thermocouple protection tube having an outer diameter of 6 mm for measuring the hot spot temperature.
- the layer height was 350 cm.
- the composition (molar ratio) of the reaction product gas was 3.21% methacrolein, 8.99% oxygen, 71.54% nitrogen, 14.46% water vapor, 0.12% methacrylic acid, and 1.68% others. there were.
- the reaction product gas was supplied to the reaction tube so that the space velocity was 1000 h ⁇ 1 .
- the partial oxidation reaction of methacrolein was continued while adjusting the reaction bath temperature so that the methacrolein conversion was 75% ⁇ 2%.
- the outlet pressure of the reactor was adjusted to 0.5 kG (50 kPaG).
- the reaction bath temperature was 300 ° C.
- the hot spot temperature was 315 ° C.
- the methacrolein conversion rate was 77.5%
- the methacrylic acid selectivity was 83.9%.
- Each of the regenerated catalysts obtained by the production method of the present invention has the same performance as that of the unused target catalyst, there is no problem when used with the unused target catalyst, and the production method is simple. Both the production process recovery catalyst and the used catalyst can be effectively utilized.
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Abstract
Description
また、特許文献3には反応に使用したモリブデンを含有する触媒を、水に分散し、アルカリ金属化合物および/またはアンモニア水を添加しpHを6.5以下にすることで沈殿物を形成させそれをメタクリル酸製造用触媒の原料とする触媒の製造方法が示されている。
特許文献4には反応に使用して活性が低下したヘテロポリ酸系触媒を水性媒体に溶解および/または分解させ無機系イオン交換体で処理することで未使用触媒と同等の性能を有する触媒を調製でき、またその触媒寿命も未使用触媒に近づいている旨が記載されている。
また、特許文献4の方法においては、イオン交換体での処理により、高活性に再生されているが、未使用触媒と同一性能という目的からすると、必ずしも満足すべきものでは無い。
(1) 回収されたモリブデン、リン、バナジウムまたは銅を必須の成分として含有するヘテロポリ酸系触媒を原料として、再生ヘテロポリ酸系触媒を製造するにあたり、以下の工程からなることを特徴とする触媒の製造方法、
工程a) ヘテロポリ酸系触媒を水性溶媒と混合し、溶媒に不溶の成分を除去することにより溶液Aを調製する工程、
工程b) 溶液Aに含まれるモリブデン、リン、バナジウムまたは銅のうち少なくとも1つの成分の含有モル量を測定する工程、
工程c) 溶液A若しくは下記工程dで得られた溶液に過酸化水素水を添加してヘテロポリ酸を酸化する工程、
工程d) 工程bで得られた含有モル量と目的再生触媒を調製するために必要とする元素のモル理論値との差分を求め不足している量の触媒成分を溶液A若しくは工程cで得られた溶液に添加し、追加原料成分を含む溶液を調製する工程、
工程e) 工程a~工程dを経て得られた溶液を乾燥し触媒顆粒Dを調製する工程、
工程f) 触媒顆粒Dを成型し、次いで焼成することで成型触媒Eを調製する工程。
(2) ヘテロポリ酸系触媒が更に下記Xから選ばれる1種以上および/またはYから選ばれる1種以上を含み、工程b)において、モリブデン、リン、バナジウム、銅、XまたはYのうち少なくとも1つの成分の含有量を測定する上記(1)記載の製造方法、
X:アルカリ金属、アルカリ土類金属またはアンモニア
Y:銀、ジルコニウム、砒素、ホウ素、ゲルマニウム、錫、鉛、クロム、ビスマス、コバルト、ニッケル、セリウム、タングステン、鉄、アルミニウム、マグネシウム、アンチモン、ニオブ、マンガンまたはチタン。
MoaPbVcCudXeYfOg
(式中Mo、P、V、およびCuはモリブデン、リン、バナジウム、および銅をそれぞれ表す。Xはアルカリ金属、アルカリ土類金属及びアンモニアからなる群から選ばれる少なくとも1種を、Yは銀、ジルコニウム、砒素、ホウ素、ゲルマニウム、錫、鉛、クロム、ビスマス、コバルト、ニッケル、セリウム、タングステン、鉄、アルミニウム、マグネシウム、アンチモン、ニオブ、マンガン及びチタンからなる群から選ばれる少なくとも1種をそれぞれ表し、a~gの各記号は元素の原子比であり、a=10とした時、bは0.1~6、cが0.1~6、dが0.1~4.0、eが0~4、fが0~5であり、gは各々の元素の酸化状態によって定まる数値である)
で表される触媒である上記(1)又は(2)に記載の触媒の製造方法。
(4) ヘテロポリ酸系触媒がメタクロレインの気相部分酸化反応によりメタクリル酸を製造するための触媒であることを特徴とする上記(1)~(3)の何れか一項に記載の触媒の製造方法。
(5) ヘテロポリ酸系触媒がメタクロレインからメタクリル酸を製造するための気相酸化触媒の製造工程で生じた廃棄触媒の回収品、又は該気相酸化触媒の仕掛品の回収品であることを特徴とする上記(1)~(4)の何れか一項に記載の触媒の製造方法。
(7) Yがアンチモンおよび/または砒素である上記(2)~(6)の何れか一項に記載の触媒の製造方法。
(8) Xを含まない触媒である上記(2)~(5)の何れか一項に記載の触媒の製造方法。
(9) eが0であり、Yが砒素、アンチモン及びセリウムからなる群から選ばれる少なくとも1種の元素である上記(3)~(5)又は(7)の何れか一項にに記載の触媒の製造方法。
(10) 成型触媒Eが、不活性担体に触媒顆粒Dを、液状バインダーを用いてコーティングした成型触媒であることを特徴とする上記(1)~(9)の何れか一項に記載の触媒の製造方法。
本発明で原料として使用する、回収されたモリブデン、リン、バナジウムまたは銅、好ましくはこれらの4元素、を必須の成分として含有するヘテロポリ酸系触媒(再生対象物質)(以下物質Mともいう)としては、気相酸化反応に用いられる、モリブデン、リン、バナジウムおよび銅を必須成分として含有する回収ヘテロポリ酸系触媒を挙げることができる。該物質Mとしては、具体的には触媒製造工程で、飛散や容器への付着等により、工程外に失われ、従来廃棄されていた触媒(半製品を含む仕掛品及び最終触媒等)、品質上又は仕込みや充填等の問題から廃棄されていた仕掛品(半製品も含む)及び/又は最終触媒等の未使用回収触媒(即ち、気相酸化触媒の製造工程で生じた廃棄触媒又は仕掛品の回収品)、及び、酸化反応に使用し、劣化した触媒(使用済み触媒)等を具体的に挙げることができる。
なお、本明細書で言う「仕掛品」は、目的触媒の触媒成分を含む(好ましくは全活性成分を含む)が、まだ、完全な目的触媒となっていない段階の触媒を意味し、例えば、触媒成分を含むスラリー、その乾燥品、未焼成のコーティング触媒、最初の焼成を終わった焼成触媒(半製品)等を上げることができる。
物質Mは、触媒活性成分のみからなっていてもよいが、通常、触媒活性成分と触媒活性成分以外の担体等不活性成分、回収時に混じる不純物などが含まれている。
酸化反応としてはメタクロレインを部分酸化してメタクリル酸を得るための気相酸化反応を挙げることが出来、本発明の原料として使用する物質Mとしては、該反応に使用されるヘテロポリ酸触媒の製造工程からの回収触媒及び使用済み回収触媒が特に好ましい。
X:アルカリ金属、アルカリ土類金属及びアンモニアからなる群から選ばれる少なくとも1種。
Y:銀、ジルコニウム、砒素、ホウ素、ゲルマニウム、錫、鉛、クロム、ビスマス、コバルト、ニッケル、セリウム、タングステン、鉄、アルミニウム、マグネシウム、アンチモン、ニオブ、マンガン及びチタンからなる群から選ばれる少なくとも1種。
上記X成分としてはセシウム、および/またはアンモニアが好ましい。上記Y成分としては砒素、アンチモン、および/またはセリウムが好ましい。これらの好ましいX成分および/又は好ましいY成分を含む触媒は好ましい触媒の一つである。また、X成分を含有しない触媒も好ましい触媒の1つである。より好ましい触媒としては、X成分及びY成分を含有しないか、又は、X成分を含有せず、Y成分として、砒素、アンチモン、およびセリウムからなる群から選ばれる少なくとも一種(好ましくはY成分が砒素又はアンチモンの何れか一方若しくは両者)である触媒である。
MoaPbVcCudXeYfOg
(式中Mo、P、V、およびCuはモリブデン、リン、バナジウム、および銅をそれぞれ表す。Xはアルカリ金属、アルカリ土類金属、アンモニアから選ばれる少なくとも1種の元素(又は分子)を、Yは銀、ジルコニウム、砒素、ホウ素、ゲルマニウム、錫、鉛、クロム、ビスマス、コバルト、ニッケル、セリウム、タングステン、鉄、アルミニウム、マグネシウム、アンチモン、ニオブ、マンガンまたはチタンからなる群から選ばれる少なくとも1種の元素をそれぞれ表す。元素記号右の添字は各元素の原子比であり、a=10とした時、bは0.1以上で6以下、好ましくは0.3以上で4.0以下、cが通常0.1以上で6以下、好ましくは0.3以上で3.0以下、dが通常0.1以上で4.0以下、好ましくは0.2以上で1.0以下、eが通常0以上で4以下、fが通常0以上で5以下であり、gは各々の元素の酸化状態によって定まる数値である。)
で表される触媒を挙げることができる。
上記一般式において、好ましいX成分はセシウムおよび/またはアンモニアである。好ましいY成分は砒素、アンチモンおよびセリウムからなる群から選ばれる少なくとも一種である。好ましい触媒の1つは上記の通り、X及び/又はYとして、上記の好ましい成分を含む触媒である。また、より好ましい触媒の1つは上記一般式において、Xを含まない触媒であり、更に好ましくは、Yが上記好ましいとして挙げた成分である触媒である。最も好ましくは上記一般式において、X成分が含まれず、Y成分が砒素、アンチモンおよびセリウムからなる群から選ばれる少なくとも一種(好ましくはY成分が砒素又はアンチモンの何れか一方若しくは両者)である触媒である。
工程a)
まず、工程a)において再生対象物質である物質Mを水性溶媒と混合して、溶媒に不溶な成分を除き、上記触媒の活性成分元素を含む溶液Aを調製する。
物質Mに含まれる触媒成分は一般に水への溶解性が高いが、不溶性の担体や回収時に混入する不溶性のゴミ等の不純物が含まれる場合、それらが溶解せずに分散する。 本発明においては物質Mとしては、触媒活性成分に、水に難溶性成分を含まないヘテロポリ酸触媒が好ましい。
本発明で使用する水性溶媒としては、通常有機溶媒を含まないイオン交換水および/または蒸留水が適当である。しかし、場合によって、これにエタノールなどを適宜添加して使用することも出来る。エタノールを添加することにより、溶解性が向上する場合がある。従って、場合により、水-エタノール混合溶媒などの水性溶媒も好ましい。
使用する溶媒の量は物質Mに対して重量比で0.5倍から2倍程度が好ましい。溶媒が少なすぎると該触媒成分の溶解を十分に行えない場合があり、多すぎても、それに見合った効果が得られにくい。
物質Mと水性溶媒の混合時間は、物質M中の回収する触媒成分が溶解される時間で有れば特に限定されない。物質M中のヘテロポリ酸触媒成分は、水に溶解し易いことから、通常1分から30分程度が好ましい。この間、溶解槽内が均一になる程度に攪拌することが好ましい。攪拌後、溶液部分と不溶成分を分離する。撹拌後直ぐに分離しても、また、1分から30分間程度静置した後、分離してもよい。この溶液部分と不溶分の分離は、通常の固液分離の常法で行うことができる。例えば、最も一般的には濾過により、不溶分を分離除去することが出来る。静置して不溶分を沈殿させた場合は、上澄みの溶液部分のポンプによるくみ上げと濾過を併用して、不溶分を除去してもよい。不溶分はそのまま廃棄してもかまわないが、濾過後の不溶分中に残る触媒成分の回収率を向上させるため、濾過後の不溶分を、水性溶媒(好ましくは水)で1~5回程度、好ましくは1~3回程度洗浄する操作を繰り返すか、又は、該不溶分を再度水性溶媒(好ましくは水)と混合し、分離する操作を1から5回程度(好ましくは1~3回程度)繰り返してもよい。通常、上記の不溶分の水性溶媒での洗浄又は水性溶媒への混合分離を1ないし3回程度繰り返すことで、不溶分中に含まれるモリブデンに代表される触媒成分の回収率が向上する。従って、上記操作を複数回実施するのが好ましい。これらの操作で得られた溶液分は、最初の操作で得られた溶液部分と一緒にして、触媒成分を含む溶液Aとすることが出来る。
溶液Aにおける溶質濃度が低すぎると、触媒の回収効率が下がるので、溶液Aにおける溶質濃度は、溶液Aの総量に対して、10~40重量%程度が好ましく、より好ましくは20~30重量%程度である。
工程b)は、溶液Aに含まれるモリブデン、リン、バナジウムまたは銅のうち少なくとも1つの成分の含有モル量を測定する工程である。
物質Mが、セシウム塩等の水難溶性塩を含まない水溶性のヘテロポリ酸からなる触媒、特にその製造工程から回収された触媒(製造工程回収触媒とも言う)である場合、反応には使用されていないので、未使用触媒と同一の組成割合を有するはずである。しかしながら、本発明者らの検討によると、該工程回収触媒を溶解して、それから製造された再生触媒は未使用触媒と同一の性能を示さなかった。原因を追及したところ、その原因の1つが、溶液(A)に含まれるモリブデン、リン、バナジウムまたは銅、及び任意成分の組成割合が、再生する目的触媒の組成比とは異なってしまっていることによるものであることを見いだした。そのため、再生触媒の性能を未使用の触媒の性能と同等にするには、溶液Aに含まれる触媒成分の濃度を定量分析し、再生触媒の活性成分元素の組成割合を、目的触媒の組成比に揃える必要性が生じた。
溶液Aに含まれる触媒成分の濃度の測定は、公知の方法で実施することが出来る。例えば、溶液Aから測定用溶液をとり、該測定用溶液に含まれる触媒成分の濃度を、ICP発光分析、原子吸光分析、蛍光X線分析などで定量分析することができる。これらの方法は簡便で正確な測定を行えるという面から好ましい。
触媒成分の定量は、不足成分が予め判っているときは、その成分含量だけでもよいが、通常、回収触媒における活性成分元素の含量の過不足を予測することは出来ないため、定量分析は目的触媒の活性成分元素の全てに対して行うのが好ましい。
工程c)は溶液Aに過酸化水素水を添加して、回収触媒成分(ヘテロポリ酸)の酸化を行う工程(便宜上過酸化水素添加工程又は溶液(B)を得る工程とも言う)である。
製造工程からの回収触媒は未使用であるにもかかわらず、該触媒を溶解して得られる溶液Aはへテロポリ酸の還元色である濃い緑色から青色を呈する。本発明者らの検討によれば、この溶液をそのまま使用しても、未使用触媒と同等の性能を有する再生触媒を得ることは難しい。しかしながら、該溶液(A)に、過酸化水素水を添加して、回収ヘテロポリ酸の酸化を行うことにより、回収触媒における活性成分の性能を、目的の未使用触媒における活性成分の性能に戻すことができる。
使用する過酸化水素水の濃度は通常5から30重量%である。使用する過酸化水素の量は、ヘテロポリ酸の組成や物質Mの履歴により異なる為一概には言えないが、物質Mに対して5から20重量%程度である。
溶液Aの温度が高いほど使用量が減少する傾向にある。過酸化水素水による酸化反応は常温で行ってもよいが、予め40~100℃程度、好ましくは40~95℃程度、より好ましくは60~95℃程度の範囲に溶液Aの温度を上げて、その温度を保持するように、過酸化水素水を徐々に添加するのが好ましい。過酸化水素による酸化反応は発熱を伴うため溶液Aの温度が上昇し過ぎないように注意する。
上記の過酸化水素水での酸化で得られた溶液を、酸化済み溶液(溶液B)とする。
なお、上記工程bと工程cは、工程cが先で、工程bが後であってもよい。
工程dは工程bでの定量分析結果を用いて、溶液Aに含まれる触媒活性成分元素の組成割合を、目的触媒の活性成分元素の組成割合(理論値)に一致させる工程である(成分調整工程とも言う)。
該定量分析結果における触媒活性成分元素の組成割合と、目的触媒の活性成分元素の組成割合との比較から、溶液A(又は溶液B)に添加すべき活性成分元素及び添加量を算出する。
工程bでの定量分析結果と、目的触媒組成の理論値との差から算出された溶液A(又は溶液B)に追加すべき成分(追加成分)及び追加添加量を、追加原料として添加する。追加原料としては追加成分元素を含有する化合物を適宜選定することが出来る。好ましくは目的触媒を製造するのに使用したものと同一の原料化合物を使用するのが好ましい。
なお、前記理論値は、目的触媒を製造する際の原料元素の仕込みモル比とする。 また、追加原料を投入及び溶解後に得られる溶液に含まれる溶質濃度(触媒成分の合計濃度)は、該溶液の総量に対して、5~15重量%が好ましく、より好ましくは10重量%程度(例えば8~12重量%程度)である。必要に応じて、純水を追加して、該溶液における溶質濃度を上記範囲に調整するのが好ましい。 なお、上記工程c(過酸化水素添加工程)と工程d(成分調整工程)は、工程dが先で、工程cが後であってもよい。
上記したところから明らかなように、工程bから工程dは必ずしも上記した順番でなくとも良い。例えば工程bと工程cの実施順を入れ替えること、工程cと工程dの実施順を替えることが出来る。
以上工程a)~工程d)を経て得られた溶液(溶液Cともいう)を公知の方法で乾燥することで触媒顆粒Dを得ることが出来る。
乾燥手段は特に限定されないが、例えば噴霧乾燥機を用いて乾燥するのが好ましい。
工程f)
触媒顆粒Dを成型して成型触媒Eを得る工程である。
成型触媒Eの形状については例えば円柱状、打錠状、球状、リング状等の形状が適宜選択可能である。成型方法は特に限定されず、(メタ)アクリル酸を製造するために使用される酸化触媒の成形方法、例えば、押出造粒法、打錠法、コーティング法などの方法を採用することが出来る。コーティング法の場合、2~4mm程度の球状担体、特にシリカやアルミナ等の不活性担体に触媒活性成分を、必要に応じて、水又は/及び有機バインダー(例えばエタノールなど)のバインダーと共に、担持させ、粒径3~6mmの担持触媒とすることが出来る。本発明においては、該担持触媒が反応成績、除熱効率などの面から好ましい。
なお、該工程回収触媒が担持触媒で、担持工程において有機バインダーを使用する場合、物質Mに担体や有機バインダーが含まれる場合があるが、特に本発明においては支障は無い。例えば、水溶性の有機バインダー、例えばエタノール水溶液であれば工程cにおいて、過酸化水素を添加する前に溶液Aを加熱して除去すれば良い。また、担体等の不溶性のものであれば工程aで不溶分として回収される。
触媒の使用期間は前記反応条件により異なるため一概には言えないが、通常1年から4年である。
なお、本明細書において、前記「理論値」は、目的とする触媒を製造するための原料元素仕込みモル比とする。
(I) 再生のために回収されたヘテロポリ酸系触媒が、製造工程回収触媒又は使用済み触媒である態様。
(II) 上記触媒が、メタクロレインの気相部分酸化反応によるメタクリル酸製造用触媒である上記(I)に記載の態様。
(III) 上記触媒が前記一般式(1)において、eが0であり、Yが砒素、アンチモン及びセリウムからなる群から選ばれる少なくとも1種の元素である上記(I)又は(II)に記載の態様。
(IV) 前記一般式(1)において、Yが砒素又はアンチモンである上記(III) に記載の態様。
(V)上記触媒が前記一般式(1)で表されるヘテロポリ酸触媒であり、a=10とした時、bが0.3~4.0、cが0.3~3.0、dが0.2~1.0、eが0、fが、Yの総量を示し、0~3である上記(I)~(IV)の何れか一項に記載の態様。
(VI) 前記工程aにおける水性溶媒が水である上記(I)~(V)の何れか一項に記載の態様。
(VII) 前記工程dを工程bの後に行う以外は、工程b又は工程c、工程c又は工程dを任意の順序で行う上記(I)~(VI)の何れか一項に記載の態様。
(VIII) 前記工程a~eを、a,b,c、d及びeの順序で行う上記(I)~(VII)の何れか一項に記載の態様。
(IX) 成型触媒Eが担持触媒である上記(I)~(VIII) の何れか一項に記載の態様。
以下の実施例において、転化率および収率は次の通りに定義される。
・メタクロレイン転化率={(供給したメタクロレインモル数-未反応メタクロレインモル数)/供給したメタクロレインモル数}×100
・メタクリル酸収率={(生成したメタクリル酸モル数-供給したメタクリル酸モル数)/供給したメタクロレインモル数 }X100
・メタクリル酸選択率={(生成したメタクリル酸モル数-供給したメタクリル酸モル数)/(供給したメタクロレインモル数-未反応メタクロレインモル数)} X100
室温の蒸留水10000mlに三酸化モリブデン1000g、85重量%燐酸水溶液96.09g、五酸化バナジウム37.91g、60重量%砒酸水溶液65.73g、酸化第二銅22.1gを仕込み、攪拌しながら95℃まで昇温し、加熱還流しながら95℃で10時間かけて溶解し、赤褐色の溶液を得た。これをスプレードライヤーで乾燥し、触媒顆粒を得た。
得られた触媒顆粒500重量部に、強度向上材70重量部を混合した。これを430重量部のシリカ・アルミナ不活性担体(粒径3.5mm)に80重量%エタノール水溶液をバインダーとして担持した。
こうして得た成型物を300℃で5時間焼成しヘテロポリ酸触媒1(以下触媒1という)を得た。得られた触媒の平均粒径は4.3mmであった。得られたヘテロポリ酸触媒の、酸素を除く組成比はモリブデン10に対しバナジウム0.6、リンが1.2、砒素が0.4、銅が0.4であった。
サンプリングしたろ液(溶液A)をエバポレーターにて乾燥して得られた粉末を蛍光X線分析にて定量分析したところ、目的の使用前の触媒の理論値に戻すために、追加すべき成分および重量は、三酸化モリブデン12.0g、五酸化バナジウム2.5g、酸化第二銅0.7gであった。
サンプリングした残りの溶液Aに純水5000gを追加し、さらに90℃で加熱攪拌しながら30重量%の過酸化水素水300mlを徐々に添加したところ、溶液Aは濃い緑色から橙色の透明な溶液Bに変化した。溶液Bに、三酸化モリブデン12.0g、五酸化バナジウム2.5g、酸化第二銅0.7gを添加して90℃にて30分間加熱攪拌して溶液Cを得た。この溶液Cをスプレードライヤーで乾燥し、触媒顆粒を得た。
以降は上記触媒1を製造した方法と同一の方法で再生の担持触媒(触媒E1)を製造した。
10.3mlの触媒1及び触媒E1のそれぞれをそれぞれ内径18.4mmのステンレス反応管に充填した。該反応管に、原料ガス(組成(モル比);メタクロレイン:酸素:水蒸気:窒素=1:2:4:18.6)を空間速度(SV)1200h-1で通し、下記するようにメタクロレインの酸化反応を実施した。
酸化反応は、最初反応浴温度310℃で3時間反応を続け、次いで反応浴温度を350℃に上げ15時間反応を続けた(今後この処理を高温反応処理という)。次いで反応浴温度を310℃に下げて反応成績の測定を行った。
なお、高温反応処理は、過酷試験での触媒活性の劣化等を見るための加速試験である。
触媒1と触媒E1の酸化反応の結果を表1に示す。
室温の蒸留水10000mlに三酸化モリブデン1000g、85重量%燐酸水溶液88.1g、五酸化バナジウム37.9g、60重量%砒酸水溶液82.2g、酢酸第二銅55.5g、三酸化アンチモン10.2gを仕込み、攪拌しながら95℃まで昇温し、加熱還流しながら95℃で10時間かけて溶解し、赤褐色の溶液を得た。これをスプレードライヤーで乾燥し、触媒顆粒を得た。
得られた触媒顆粒500重量部に、強度向上材70重量部を混合した。これを430重量部のシリカ・アルミナ不活性担体(粒径3.5mm)に80重量%エタノール水溶液をバインダーとして担持した。
こうして得た成型物を300℃で5時間焼成しヘテロポリ酸触媒(以下触媒2という)を得た。得られた触媒の平均粒径は4.3mmであった。得られた触媒2の、酸素を除く組成比はモリブデン10に対しバナジウム0.6、リンが1.1、砒素が0.5、銅が0.4、アンチモン0.1であった。
サンプリングしたろ液(溶液A)をエバポレーターにて乾燥して得られた粉末を蛍光X線分析にて定量分析したところ、目的の使用前の触媒の理論値に戻すために追加すべき成分および重量は、三酸化モリブデン27.0g、五酸化バナジウム2.0g、酢酸第二銅2.5gであった。
溶液Aはエタノール臭がしたことから、溶液Aに純水6000gを追加した後、さらに90℃で2時間加熱攪拌した。その後攪拌を継続しながら30重量%の過酸化水素水300mlを徐々に添加したところ、溶液Aは濃い緑色から橙色の透明な溶液Bに変化した。溶液Bに、三酸化モリブデン27.0g、五酸化バナジウム2.0g、酢酸第二銅2.5gを添加して90℃にて90分間加熱攪拌して溶液Cを得た。この溶液Cをスプレードライヤーで乾燥し、触媒顆粒を得た。
以降は上記触媒2を製造した方法と同一の方法で再生の担持触媒(触媒E2)を製造した。なお、溶液Aにエタノール臭がした原因は、使用した物質Mの多くが触媒の成型工程由来であるためと推察される。
実施例1と同様に触媒2および触媒E2を用いて、メタクロレインの部分酸化反応を行った。その結果を表1に示す。
室温の蒸留水10000mlに三酸化モリブデン1000g、85重量%燐酸水溶液112.1g、五酸化バナジウム75.8g、酸化第二銅22.11gを仕込み、攪拌しながら95℃まで昇温し、加熱還流しながら95℃で10時間かけて溶解し、赤褐色の溶液を得た。これをスプレードライヤーで乾燥し、触媒顆粒を得た。
得られた触媒顆粒500重量部に、強度向上材70重量部を混合した。これを430重量部のシリカ・アルミナ不活性担体(粒径3.5mm)に80重量%エタノール水溶液をバインダーとして担持した。
こうして得た成型物を300℃で5時間焼成しヘテロポリ酸触媒2を得た。得られた触媒の平均粒径は4.3mmであった。得られたヘテロポリ酸触媒の、酸素を除く組成比はモリブデン10に対しバナジウム1.2、リンが1.4、銅が0.4であった。
サンプリングしたろ液(溶液A)をエバポレーターにて乾燥して得られた粉末を蛍光X線分析にて定量分析したところ、追加すべき成分および重量は、三酸化モリブデン27.0g、五酸化バナジウム2.0g、酢酸第二銅2.5gであった。
溶液Aはエタノール臭がしたことから、溶液Aに純水5000gを追加した後、さらに90℃で2時間加熱攪拌した。その後攪拌を継続しながら30重量%の過酸化水素水300mlを徐々に添加したところ、溶液Aは濃い緑色から橙色の透明な溶液Bに変化した。溶液Bに、三酸化モリブデン27.0g、五酸化バナジウム2.0g、酢酸第二銅2.5gを添加して90℃にて90分間加熱攪拌して溶液Cを得た。この溶液Cをスプレードライヤーで乾燥し、触媒顆粒を得た。
以降は上記触媒3を製造した方法と同一の方法で再生の担持触媒(触媒E3)を製造した。
実施例1と同様に触媒3および触媒E3を用いてメタクロレインの部分酸化反応を行った。その結果を表1に示す。
室温の蒸留水20000mlに三酸化モリブデン2000g、85重量%燐酸水溶液192.18g、五酸化バナジウム75.82g、60重量%砒酸水溶液131.46g、酸化第二銅44.2gを仕込み、攪拌しながら95度まで昇温し、加熱還流しながら95度で10時間かけて溶解し、赤褐色の溶液を得た。これをスプレードライヤーで乾燥し、触媒顆粒を得た。
得られた触媒顆粒1000重量部に、強度向上材140重量部を混合した。これを860重量部のシリカ・アルミナ不活性担体(粒径3.5mm)に80重量%エタノール水溶液をバインダーとして担持した。
こうして得た担持触媒を300℃で5時間焼成しヘテロポリ酸触媒(以下触媒4という)を得た。得られた触媒の平均粒径は4.3mmであった。得られたヘテロポリ酸触媒の、酸素を除く組成比はモリブデン10に対しバナジウム0.6、リンが1.2、砒素が0.4、銅が0.4であった。
反応を16000時間継続したところ、反応浴温度は297度、メタクロレイン転化率77%、ホットスポット温度は317度であり、メタクリル酸選択率は81.5%であった。
次いで、この使用済み触媒を反応管より抜き出して全量回収した。抜き出した触媒2000gを2000gの純水に添加し、30分間攪拌した後ろ紙を用いて吸引濾過した。ろ過残渣をヌッチェに残したまま純水1000gを添加し、再度吸引濾過する操作を都合3回行った。得られた濾液を全部一緒にして、ろ液(溶液A)を得た。最終的に残った固形分は約1000gであり、蛍光X線分析による定性分析ではシリカ、アルミナを主成分とするものであった。
サンプリングしたろ液(溶液A)をエバポレーターにて乾燥して得られた粉末を蛍光X線分析にて定量分析したところ、追加すべき成分および重量は、三酸化モリブデン174.3g、五酸化バナジウム3.86g、85重量%燐酸水溶液0.23g、酢酸第二銅0.37gであった。
該溶液Aをジャケット式の釜に再度移し、エタノールを除くため、90℃で2時間加熱攪拌した。その後攪拌を継続しながら30重量%の過酸化水素水900mlを徐々に添加したところ、溶液Aは濃い緑色から橙色の透明な溶液Bに変化した。溶液Bに、三酸化モリブデン174.3g、五酸化バナジウム3.86g、85重量%燐酸水溶液0.23g、酢酸第二銅0.37gを添加して90℃にて90分間加熱攪拌して溶液Cを得た。この溶液Cをスプレードライヤーで乾燥し、触媒顆粒を得た。
以降は上記触媒4を製造した方法と同一の方法で再生の担持触媒(触媒E4)を製造した。
実施例1と同様にE4のメタクロレインの部分酸化反応を行った。結果を表1に示す。
実施例1において、三酸化モリブデン、五酸化バナジウム、酸化銅を追加添加しなかったこと以外は実施例1と同様にして成型触媒E5を調製した。E5触媒のメタクロレインの部分酸化反応結果を表1に示す。
実施例1において、溶液Bを調製せず、かつ三酸化モリブデン、五酸化バナジウム、酸化銅を添加しなかったこと以外は実施例1と同様にして成型触媒E6を調製した。E6触媒のメタクロレインの部分酸化反応結果を表1に示す。
実施例2で得られた触媒E2(再生の担持触媒)を、ホットスポット温度の測定用に外径6mmの熱電対保護管を備えた、内径29.4mmの鋼鉄製反応管に、充填層高が350cmになるように充填した。原料ガスとしてイソブチレンをモリブデン、ビスマス、コバルト、鉄を主成分とする複合酸化物触媒の存在下で分子状酸素を使用して得られた反応生成ガスを用いた。反応生成ガスの組成(モル比)は、容積あたりメタクロレイン3.21%、酸素8.99%、窒素71.54%、水蒸気14.46%メタクリル酸0.12%、その他1.68%であった。該反応生成ガスを空間速度1000h-1となるように該反応管に供給した。反応開始後、メタクロレイン転化率が75%±2%になるように反応浴温度を調節しながらメタクロレインの部分酸化反応を継続した。反応器の出口圧力は0.5kG(50kPaG)になるように調節した。
反応開始後2000時間後のメタクロレイン酸化反応の結果は反応浴温度300℃ ホットスポット温度315℃ メタクロレイン転化率77.5%、メタクリル酸選択率83.9%であった。
Claims (10)
- 回収されたモリブデン、リン、バナジウムまたは銅を必須の成分として含有するヘテロポリ酸系触媒を原料として、再生ヘテロポリ酸系触媒を製造するにあたり、以下の工程からなることを特徴とする触媒の製造方法、
工程a) ヘテロポリ酸系触媒を水性溶媒と混合し、溶媒に不溶の成分を除去することにより溶液Aを調製する工程、
工程b) 溶液Aに含まれるモリブデン、リン、バナジウムまたは銅のうち少なくとも1つの成分の含有モル量を測定する工程、
工程c) 溶液A若しくは下記工程dで得られた溶液に過酸化水素水を添加してヘテロポリ酸を酸化する工程、
工程d) 工程bで得られた含有モル量と目的再生触媒を調製するにために必要とする元素のモル理論値との差分を求め不足している量の触媒成分を溶液A若しくは工程cで得られた溶液に添加し、追加原料成分を含む溶液を調製する工程、
工程e) 工程a~工程dを経て得られた溶液を乾燥し触媒顆粒Dを調製する工程、
工程f) 触媒顆粒Dを成型し、次いで焼成することで成型触媒Eを調製する工程。 - ヘテロポリ酸系触媒が更に下記Xから選ばれる1種以上および/またはYから選ばれる1種以上を含み、工程b)において、モリブデン、リン、バナジウム、銅、XまたはYのうち少なくとも1つの成分の含有量を測定する請求項1記載の製造方法。
X:アルカリ金属、アルカリ土類金属またはアンモニア
Y:銀、ジルコニウム、砒素、ホウ素、ゲルマニウム、錫、鉛、クロム、ビスマス、コバルト、ニッケル、セリウム、タングステン、鉄、アルミニウム、マグネシウム、アンチモン、ニオブ、マンガンまたはチタン - 前記ヘテロポリ酸系触媒が下記一般式
MoaPbVcCudXeYfOg
(式中Mo、P、V、およびCuはモリブデン、リン、バナジウム、および銅をそれぞれ表す。Xはアルカリ金属、アルカリ土類金属、アンモニアから選ばれる少なくとも1種を、Yは銀、ジルコニウム、砒素、ホウ素、ゲルマニウム、錫、鉛、クロム、ビスマス、コバルト、ニッケル、セリウム、タングステン、鉄、アルミニウム、マグネシウム、アンチモン、ニオブ、マンガンまたはチタンからなる群から選ばれる少なくとも1種の元素をそれぞれ表し、a~gの各記号は元素の原子比であり、a=10とした時、bは0.1~6、cが0.1~6、dが0.1~4.0、eが0~4、fが0~5であり、gは各々の元素の酸化状態によって定まる数値である)
で表される触媒である請求項1に記載の触媒の製造方法。 - ヘテロポリ酸系触媒がメタクロレインの気相部分酸化反応によりメタクリル酸を製造するための触媒であることを特徴とする請求項1に記載の触媒の製造方法。
- ヘテロポリ酸系触媒がメタクロレインからメタクリル酸を製造するための気相酸化触媒の製造工程で生じた廃棄触媒の回収品、又は該気相酸化触媒の仕掛品の回収品であることを特徴とする請求項1に記載の触媒の製造方法。
- Xがセシウムおよび/またはアンモニアであることを特徴とする請求項2に記載の触媒の製造方法。
- Yがアンチモンおよび/または砒素である請求項2に記載の触媒の製造方法。
- Xを含まない触媒である請求項2に記載の触媒の製造方法。
- eが0であり、Yが砒素、アンチモン及びセリウムからなる群から選ばれる少なくとも1種の元素である請求項3~8の何れか一項に記載の触媒の製造方法。
- 成型触媒Eが、不活性担体に触媒顆粒Dを、液状バインダーを用いてコーティングした成型触媒であることを特徴とする請求項1に記載の触媒の製造方法。
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US13/582,055 US20120329638A1 (en) | 2010-03-29 | 2011-03-28 | Method For Manufacturing Catalyst From Recovered Catalyst |
KR1020127022928A KR20130056208A (ko) | 2010-03-29 | 2011-03-28 | 회수촉매로부터의 촉매의 제조방법 |
JP2012508078A JP5681701B2 (ja) | 2010-03-29 | 2011-03-28 | 回収触媒からの触媒の製造方法 |
SG2012064879A SG183862A1 (en) | 2010-03-29 | 2011-03-28 | Method for manufacturing catalyst from recovered catalyst |
CN2011800175091A CN102834176A (zh) | 2010-03-29 | 2011-03-28 | 由回收催化剂制造催化剂的方法 |
EP11762225A EP2554268A1 (en) | 2010-03-29 | 2011-03-28 | Process for production of catalyst from recovered catalyst |
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CN103861640B (zh) * | 2014-03-13 | 2015-07-29 | 万华化学集团股份有限公司 | 一种杂多酸催化剂及其制备方法 |
CN104549573A (zh) * | 2014-11-05 | 2015-04-29 | 华玉叶 | 一种制备再生的环氧化催化剂的方法 |
CN109395754B (zh) * | 2018-10-29 | 2021-06-25 | 江苏扬农化工集团有限公司 | 一种从氯丙烯环氧化油层中回收杂多酸催化剂的方法 |
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JP2008000709A (ja) | 2006-06-23 | 2008-01-10 | Mitsubishi Rayon Co Ltd | メタクリル酸製造用ヘテロポリ酸系触媒の製造方法 |
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2011
- 2011-03-28 KR KR1020127022928A patent/KR20130056208A/ko not_active Application Discontinuation
- 2011-03-28 JP JP2012508078A patent/JP5681701B2/ja not_active Expired - Fee Related
- 2011-03-28 EP EP11762225A patent/EP2554268A1/en not_active Withdrawn
- 2011-03-28 CN CN2011800175091A patent/CN102834176A/zh active Pending
- 2011-03-28 SG SG2012064879A patent/SG183862A1/en unknown
- 2011-03-28 WO PCT/JP2011/001820 patent/WO2011121976A1/ja active Application Filing
- 2011-03-28 US US13/582,055 patent/US20120329638A1/en not_active Abandoned
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JPH06233938A (ja) * | 1993-02-03 | 1994-08-23 | Basf Ag | 使用ずみの多金属酸化物酸化触媒の再生方法 |
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CN112439399A (zh) * | 2019-08-29 | 2021-03-05 | 中国石油化工股份有限公司 | 一种α-氧化铝载体及制备方法和银催化剂与应用 |
CN112439399B (zh) * | 2019-08-29 | 2023-05-09 | 中国石油化工股份有限公司 | 一种α-氧化铝载体及制备方法和银催化剂与应用 |
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JPWO2011121976A1 (ja) | 2013-07-04 |
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US20120329638A1 (en) | 2012-12-27 |
EP2554268A1 (en) | 2013-02-06 |
CN102834176A (zh) | 2012-12-19 |
KR20130056208A (ko) | 2013-05-29 |
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