WO2017077969A1 - ニッケル珪藻土触媒及びその製造方法 - Google Patents
ニッケル珪藻土触媒及びその製造方法 Download PDFInfo
- Publication number
- WO2017077969A1 WO2017077969A1 PCT/JP2016/082226 JP2016082226W WO2017077969A1 WO 2017077969 A1 WO2017077969 A1 WO 2017077969A1 JP 2016082226 W JP2016082226 W JP 2016082226W WO 2017077969 A1 WO2017077969 A1 WO 2017077969A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel
- diatomaceous earth
- catalyst
- earth catalyst
- hydrogen
- Prior art date
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000005909 Kieselgur Substances 0.000 title claims abstract description 78
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000004580 weight loss Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 55
- 238000005259 measurement Methods 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 27
- 230000009467 reduction Effects 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 21
- 238000012360 testing method Methods 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000011946 reduction process Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 3
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 3
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 3
- 239000000047 product Substances 0.000 description 26
- 238000006722 reduction reaction Methods 0.000 description 23
- 230000032683 aging Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 13
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000012970 cakes Nutrition 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 3
- 235000021463 dry cake Nutrition 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 241000705939 Shortia uniflora Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite 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
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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- 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
- B01J37/08—Heat treatment
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- 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
- B01J37/16—Reducing
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- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
- C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Definitions
- the present invention relates to a nickel diatomaceous earth catalyst and a method for producing the same.
- Hydrogenation reaction using ammonia solvent is widely used, and amine synthesis from nitrile is a representative example.
- nickel, cobalt, platinum, palladium, rhodium or the like is used as a catalyst.
- Nickel is widely used from the viewpoint of price and hydrogenation ability.
- a nickel catalyst As a general method for producing a nickel catalyst, an impregnation method in which a nickel-containing solution is immersed in the pores of a molded carrier and fixed on the pore walls, dried and fired to carry an active ingredient, or a nickel component And a precipitation method in which a precipitate such as hydroxide and carbonate is produced by bringing the aqueous solution into contact with a precipitant solution, followed by filtration, washing with water, drying, molding, and firing.
- the precipitation method is a method suitable for the preparation of a multi-component catalyst or a high loading rate catalyst (20 to 40 wt%).
- the essential characteristics of the catalyst are determined at the stage of the precipitation reaction, and the subsequent activation process can be said to be a stage for effectively exhibiting the characteristics. Therefore, it is difficult to change the catalyst performance in the steps after the precipitation reaction.
- the activity and selectivity of the catalyst gradually decrease with use, and the activity of the catalyst deteriorates.
- One of the causes of the deterioration of the activity is catalyst sintering.
- the sintering speed depends on the amount of metal supported, the size of the metal particles, the type of support, the reaction conditions, etc.
- fine crystals of the catalytically active component are highly dispersed on a support with high heat resistance. It is effective to use the method supported on the surface.
- Non-Patent Document 1 discloses the heat resistance of a nickel catalyst using ⁇ -alumina as a support in a liquid ammonia and hydrogen atmosphere. Are listed. It is described that when a nickel catalyst is heat-treated at 110 ° C. to 150 ° C., sintering does not occur only in a hydrogen atmosphere or only in an ammonia atmosphere, but sintering occurs only when hydrogen and ammonia coexist.
- Patent Document 1 a precursor obtained by depositing a compound containing nickel hydroxide and nickel carbonate on the surface of a support by the precipitation method is subjected to a heat treatment step with steam, A method for obtaining a nickel catalyst which is excellent in both hydrogenation activity and heat resistance is described.
- Patent Document 1 is an effective method for suppressing a decrease in surface area when heated at 800 ° C., and is it effective in heat resistance of the catalyst in a liquid ammonia and hydrogen atmosphere? Is unknown.
- An object of the present invention is to provide a nickel diatomaceous earth catalyst having excellent heat resistance in a hydrogenation reaction using an ammonia solvent and a method for producing the same.
- the present invention is as follows. [1] A nickel diatomaceous earth catalyst having a hydrogen TG 400-600 ° C. weight loss rate of 0.05 to 2.0%. [2] The nickel diatomaceous earth catalyst according to [1] above, wherein the nickel crystallite diameter is 30 to 100 mm. [3] The nickel diatomaceous earth catalyst according to the above [1] or [2], wherein the change ⁇ of the nickel crystallite diameter before and after the heat resistance test is 210 mm or less. [4] The nickel diatomaceous earth catalyst according to any one of [1] to [3] above, having a specific surface area of 60 to 180 m 2 / g.
- a method for producing a nickel diatomaceous earth catalyst using a precipitation method Adding an alkaline solution precipitant to a dispersion of diatomaceous earth and a nickel catalyst salt; A process of sequentially performing a drying process, a baking process, and a reduction process, Including The manufacturing method of the nickel diatomaceous earth catalyst which performs the said reduction process at the peak temperature +40 degreeC or more of the hydrogen TPR measurement of the baked part obtained after the said calcination process.
- a method for producing xylylenediamine A production method comprising hydrogenating phthalonitrile in an ammonia solvent using the nickel diatomaceous earth catalyst according to the above [1] to [4] or [7].
- the nickel diatomaceous earth catalyst of the present invention exhibits excellent heat resistance in a reaction in a liquid ammonia and hydrogen atmosphere. As a result, it can be used for reactions at high temperatures, and the catalyst life can be extended.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
- each physical property can be measured by the method described in the Example mentioned later.
- the nickel diatomaceous earth catalyst in this embodiment has a hydrogen TG 400-600 ° C. weight reduction rate of 0.05 to 2.0%.
- the weight loss rate of hydrogen TG 400-600 ° C. is preferably 0.1 to 1.8%, more preferably 0.1 to 1.0%. If the weight loss rate of hydrogen TG400-600 ° C is less than 0.05%, reduction under harsh conditions is necessary, which is disadvantageous from the viewpoint of economy and safety, and if it exceeds 2.0%, heat resistance is reduced. Inferior.
- the specific surface area of the nickel diatomaceous earth catalyst in the present embodiment is preferably 50 to 180 m 2 / g, more preferably 60 to 180 m 2 / g, and still more preferably 60 to 170 m 2 / g.
- the specific surface area of the catalyst is 50 m 2 / g or more, it tends to be a catalyst excellent in hydrogenation performance, and when it is 180 m 2 / g or less, it tends to be a catalyst excellent in heat resistance.
- the nickel crystallite diameter of the nickel diatomaceous earth catalyst is preferably 20 to 250 mm, more preferably 30 to 100 mm, and further preferably 30 to 80 mm.
- the nickel crystallite diameter of the catalyst is 20 mm or more, the heat resistance in a liquid ammonia and hydrogen atmosphere tends to be improved, and when it is 250 mm or less, the hydrogenation performance tends to be improved.
- the change ⁇ of the nickel crystallite diameter before and after the heat resistance test of the nickel diatomaceous earth catalyst in the present embodiment is preferably 210 mm or less, more preferably 160 mm or less, and more preferably 100 mm or less from the viewpoint of heat resistance. More preferably it is.
- the heat resistance test refers to a heat resistance test in Examples described later.
- the nickel diatomaceous earth catalyst in this embodiment is Li, Na, K, Rb, Cs, Be, Ca, Sr, Ba, Ti, Cu, Cr, Zn, Mn, Mg, Ga, Ge, Nb, Ir, Pt, Bi.
- One or more components selected from the group consisting of Al, In, Sr, Ce, Co, and Mo may be included.
- the manufacturing method of the nickel diatomaceous earth catalyst in the present embodiment is a manufacturing method using a precipitation method, Adding an alkaline solution precipitant to a dispersion of diatomaceous earth and a nickel catalyst salt; Including a drying process, a firing process, and a reduction process.
- the reduction treatment is performed at a peak temperature of hydrogen TPR measurement of the fired portion obtained after the firing treatment + 40 ° C or higher.
- the precipitation method is not particularly limited as long as it is a method capable of depositing a compound containing nickel hydroxide and nickel carbonate on the surface of diatomaceous earth, and a conventionally known method can be applied.
- diatomaceous earth When preparing a dispersion in which diatomaceous earth and a nickel catalyst salt are mixed, diatomaceous earth may be added to the solvent, or the solvent may be added to the diatomaceous earth.
- diatomaceous earth When adding, for example, diatomaceous earth may be added to a solvent at 0 to 40 ° C. and stirred for 30 to 60 minutes, and then the temperature may be raised to a predetermined temperature, or the solvent may be kept at a predetermined temperature. Diatomaceous earth may be added.
- the salt of the nickel catalyst is not particularly limited, and examples thereof include nickel sulfate and nickel nitrate.
- the precipitating agent for the alkaline solution is not particularly limited, and examples thereof include an alkaline solution in which carbonates such as sodium carbonate and sodium bicarbonate are dissolved. You may add the precipitation agent of an alkaline solution using a tube pump etc. to the dispersion liquid obtained by adding the nickel catalyst salt solution to the solution in which diatomaceous earth is dispersed and mixing.
- the addition of the precipitant of the alkaline solution either normal injection or reverse injection may be used.
- the method of adding the alkaline solution precipitant to the salt solution of the nickel catalyst (normal Additive method) is used.
- a nickel catalyst When a nickel catalyst is used, a precursor in which a compound containing nickel hydroxide and nickel carbonate is deposited on the surface of diatomaceous earth can be obtained.
- the nickel source is nickel nitrate and the alkali source is sodium carbonate, this precipitation reaction is expressed by the following formula (1), and basic nickel carbonate is obtained.
- the molar ratio of alkali to nickel is preferably 1 to 4 times, and more preferably 1.5 to 3 times.
- the precipitation pH is about 8 to 9, and precipitation of basic nickel carbonate and deposition on diatomaceous earth tend to occur.
- the alkaline solution precipitant is added to a dispersion of a catalyst component solution in which a salt of diatomaceous earth and a nickel catalyst is dissolved (hereinafter also referred to as “mother liquor”)
- the mother liquor is preferably maintained at 50 to 90 ° C. More preferably, the temperature is maintained at 60 to 80 ° C.
- the precipitation temperature When the precipitation temperature is low, precipitated particles are generated slowly, so that highly active catalyst precipitation is easily obtained.
- the precipitation temperature When the precipitation temperature is high, the precipitate is formed in a short time, so that the process can be shortened, and it is possible to generate a precipitate having a uniform size.
- a force for aggregating particles acts on the surface of the generated precipitated particles, and it can be prevented that a large aggregate is formed by stirring the mother liquor.
- the time for pouring the precipitant is preferably 30 to 120 minutes, more preferably 60 to 90 minutes. It is preferable to continue the aging of the precipitate by heating and stirring for a while after the addition.
- the aging temperature may be higher or lower than the pouring temperature, but is preferably from 50 to 90 ° C, more preferably from 60 to 80 ° C, from the viewpoint of forming basic nickel carbonate from the produced precipitated components.
- the aging time is preferably about 0 to 3 hours, and more preferably 0.5 to 2 hours, from the viewpoint of the time for depositing and fixing basic nickel carbonate on diatomaceous earth.
- a fired product or an unfired product may be used alone or mixed so that predetermined physical properties can be obtained.
- it becomes easy to deposit basic nickel carbonate in diatomaceous earth only with an unbaked product it is easy to become a non-reducible catalyst.
- the amount of basic nickel carbonate deposited on diatomaceous earth is estimated from the amount of dissolved Si when treated with a precipitant in an alkaline solution, and the fired or unfired product is used alone, Or both may be mixed and used, and a compounding ratio may be determined suitably.
- the amount of eluted Si is preferably 0.5 to 1.5%, preferably 0.7 to 1.1%. Is more preferable.
- the diatomaceous earth may be mixed by adding a Na 2 CO 3 aqueous solution after mixing the fired product and the unfired product, or adding each of the fired product and the unfired product to the liquid.
- the mixture may be stirred in a liquid at 10 to 40 ° C. for 30 to 60 minutes and then heated to a predetermined temperature, or diatomaceous earth may be added while the liquid is kept at a predetermined temperature. May be.
- the reducibility can be controlled by changing the aging time depending on the type of diatomaceous earth. For example, when using a fired product, the aging time may be increased because it tends to be easily reducible, and when using an unfired product, it may be difficult to reduce, so the aging time may be shortened. .
- reducing properties can be similarly controlled by changing the aging temperature.
- the aging temperature when using a baked product, the aging temperature may be increased because it tends to be easily reducible, and when using an unfired product, the aging temperature may be decreased because it tends to be difficult to reduce.
- the precipitate obtained by the precipitation treatment may be washed, filtered and dried by a general method.
- the impurity ions SO 4 2 ⁇ , NO 3 ⁇ , etc.
- Nickel compounds and S, N are easy to combine and there is a danger of becoming a cause of poisoning.
- Washing is performed by suspension washing in which the filter cake obtained by filtration is suspended in water and stirred.
- the electrical conductivity of the filtrate after suspension washing is preferably 1 mS / cm or less.
- the filter cake after washing is sufficiently dried at around 100 ° C. to obtain a dry cake.
- a baking process is performed using an electric furnace.
- the firing atmosphere may be air or nitrogen.
- the firing temperature is preferably 200 to 500 ° C, more preferably 350 to 450 ° C, from the viewpoint of the temperature for decomposing nickel hydroxide and nickel carbonate.
- the firing time is preferably 3 to 10 hours, and more preferably 5 to 7 hours, from the viewpoint of the time required to sufficiently decompose nickel hydroxide and nickel carbonate.
- temperature reduction with hydrogen of the calcined powder is performed.
- the peak temperature in the hydrogen TPR measurement is preferably 200 to 500 ° C, more preferably 300 to 400 ° C, and further preferably 300 to 360 ° C.
- the nickel catalyst prepared by the above method is in an oxide state, and does not exhibit catalytic activity in this state.
- a reduction treatment is performed to activate the catalyst (see the following formula (3)).
- a general reducing agent such as hydrogen, carbon monoxide, methanol or the like may be used, and hydrogen is preferable from the viewpoint of toxicity and ease of handling.
- the reaction temperature is preferably 350 to 500 ° C, more preferably 380 to 450 ° C.
- the reduction treatment temperature is set higher than the peak temperature in the temperature-programmed reduction (hydrogen TPR measurement) of the fired powder after the firing treatment with hydrogen.
- the reduction treatment temperature is a peak temperature + 40 ° C. or higher, preferably + 50 ° C. or higher, more preferably + 60 ° C. or higher, in the hydrogen TPR measurement for the calcined portion.
- the upper limit of the reduction treatment temperature is not particularly limited, but from the viewpoint of preventing a decrease in catalyst activity, the peak temperature in the hydrogen TPR measurement for the calcined portion is preferably + 200 ° C. or less, more preferably + 150 ° C. or less, More preferably, it is + 100 ° C. or lower.
- the reduced nickel surface is partially oxidized at a low temperature or adsorbed and protected with an inert gas such as carbon dioxide or nitrogen, or dispersed in a solvent such as oil depending on the application. Protect.
- the catalyst includes Li, Na, K, Rb, Cs, Be, Ca, Sr, Ba, Ti, Cu, Cr, Zn, Mn, Mg, Ga, Ge, Nb, Ir, Pt, Bi, as necessary.
- One or more components selected from the group consisting of Al, In, Sr, Ce, Co, and Mo can be added.
- a precipitate may be formed by mixing a nickel salt solution and an aqueous solution of each component and then adding a precipitant, or the compound of each component may be added to the precipitate after washing and filtration. A fixed amount may be added.
- the shape of the catalyst is not particularly limited, and it may be molded into a necessary shape and size according to use conditions.
- the compression molding method can be used when the catalyst particles require high mechanical strength, or when other molding methods cannot obtain sufficient strength.
- graphite may be added and formed into a pellet by tableting.
- an extrusion method excellent in productivity and continuous production may be used.
- an inorganic binder may be added as a strength improver. Examples of the inorganic binder include clay minerals such as kaolin and montmorillonite, silica sol, alumina sol, and the like.
- the particle diameter of the nickel catalyst after the molding process is preferably about 0.1 mm to 10 mm.
- the nickel diatomaceous earth catalyst in this embodiment can be used for all hydrogenation reactions in an ammonia solvent.
- IPN isophthalonitrile
- TPN terephthalonitrile
- IPN / TPN diamine
- Diamine (PXDA) a mixture thereof (MXDA / PXDA) can be produced.
- the measuring method and evaluation method of each physical property in Examples and Comparative Examples are as follows.
- Physical property measurement The physical properties of the dried cake were measured. After pulverization in a mortar, dry powder obtained by a 60-80 mesh sieve was used as a measurement sample. About the specific surface area, the surface area measuring apparatus (NOVA4200e by QUANTACHROME INSTRUMENTS company) was used. As a pretreatment, the measurement sample was dried at 100 ° C. for 5 hours, and then the specific surface area was measured by nitrogen adsorption measurement (BET method).
- the specific surface area was measured by the same method as described above.
- the nickel metal surface area was calculated by measuring the hydrogen adsorption amount of the reduction catalyst by the following method.
- the apparatus used was BELCAT-B (Nippon Bell). First, about 0.4 g of fired powder was charged into a glass U-shaped tube. The temperature inside the reaction tube was set to 340 ° C., helium (50 mL / min) was introduced for 45 minutes, hydrogen (50 mL / min) was then introduced for 30 minutes, and the catalyst was hydrogen reduced. Next, helium (50 mL / min) was introduced for 10 minutes while the reduction catalyst was kept in the glass U-shaped tube, and the mixture was allowed to cool to room temperature.
- the reduction behavior was measured by hydrogen TPR.
- the apparatus used was BELCAT-A (Nippon Bell). 0.1 g of the calcined powder was charged, the temperature inside the reaction tube was set to 200 ° C., and helium (50 mL / min) was introduced for 30 minutes. Thereafter, the flow gas was switched to 10% hydrogen / 90% argon (50 mL / min), the temperature was raised to 800 ° C. at a rate of temperature rise of 2 ° C./min, and the reducibility was measured from the hydrogen consumption at that time. The TPR peak temperature was determined.
- metaxylene manufactured by Wako Pure Chemical Industries
- isophthalonitrile manufactured by Tokyo Chemical Industry
- 10 g of liquid ammonia were charged into the reactor, and hydrogen was charged to 10 MPaG.
- a hydrogenation reaction was performed by heating at 80 ° C. for 2 hours while stirring inside the reactor to obtain metaxylylenediamine (MXDA).
- Example 1 17.5 g of filter cell (unfired product, manufactured by Imeris) as diatomaceous earth and 17.5 g of Celite 503 (fired product, manufactured by Imeris), and 283.2 g of nickel sulfate hexahydrate (manufactured by Wako Pure Chemical Industries) as nickel source Then, 1000 g of water was mixed in a 3 L three-necked flask at 25 ° C. to prepare a slurry. The slurry was stirred at 300 rpm and heated to 70 ° C. Using another container, 202 g of sodium carbonate (manufactured by Wako Pure Chemical Industries) was dissolved in 1000 g of water to prepare a precipitant.
- the precipitant was poured into the slurry at 20 g / min using a tube pump. During the addition, the temperature of the slurry was kept at 70 ° C. and stirring was performed. After adding the whole amount, the temperature was raised to 80 ° C. at 2 ° C./min, and the mixture was stirred for 2 hours for aging. Thereafter, the obtained slurry was filtered under reduced pressure using Nutsche (filter paper: Advantech 4A) to obtain a filter cake. The filter cake was put into a 3 L polypropylene mug, 1000 g of pure water was added, and the mixture was slurried again with stirring at 25 ° C. to perform suspension washing and filtration.
- Nutsche filter paper: Advantech 4A
- the filter cake was dried at 110 ° C. for 12 hours using an electric dryer to obtain a dry cake.
- the dried cake was baked in a baking furnace at 380 ° C. for 5 hours to obtain a catalyst baking cake.
- the fired cake was pulverized to obtain a fired catalyst powder.
- the catalyst calcined powder was charged into a SUS reaction tube having an inner diameter of 1.4 cm, and reduced at 400 ° C. for 10 hours using 50% hydrogen / 50% nitrogen gas (60 mL / min).
- Example 2 A nickel diatomaceous earth catalyst was obtained by the same method as in Example 1 except that the reducing condition of the catalyst calcined powder was changed to 450 ° C. for 10 hours. Table 2 shows the measurement results.
- Example 3 A nickel diatomaceous earth catalyst was obtained by the same method as in Example 1 except that the reducing condition of the catalyst calcined powder was changed to 380 ° C. for 10 hours. Table 2 shows the measurement results.
- Example 1 A nickel diatomaceous earth catalyst was obtained by the same method as in Example 1 except that the reducing condition of the catalyst calcined powder was changed to 310 ° C. for 10 hours. Table 2 shows the measurement results.
- Example 2 A nickel diatomaceous earth catalyst was obtained by the same method as in Example 1 except that the ratio of diatomaceous earth was 100% by mass for the filter cell and the aging time was 180 minutes. Table 2 shows the measurement results.
- Example 6 A nickel diatomaceous earth catalyst was obtained by the same method as in Comparative Example 2 except that the aging time was 100 minutes. Table 2 shows the measurement results.
- Example 7 A nickel diatomaceous earth catalyst was obtained by the same method as in Comparative Example 2 except that the aging temperature was 70 ° C. and the aging time was 120 minutes. Table 2 shows the measurement results.
- Example 9 A nickel diatomaceous earth catalyst was obtained by the same method as in Comparative Example 2, except that the reduction temperature was 420 ° C. Table 2 shows the measurement results.
- Example 10 A nickel diatomaceous earth catalyst was obtained by the same method as in Comparative Example 3 except that the reduction temperature was 420 ° C. Table 2 shows the measurement results.
- Example 11 A nickel diatomaceous earth catalyst was obtained by the same method as in Comparative Example 2 except that the reduction temperature was 450 ° C. Table 2 shows the measurement results.
- Example 12 A nickel diatomaceous earth catalyst was obtained by the same method as in Comparative Example 3 except that the reduction temperature was 450 ° C. Table 2 shows the measurement results.
- Example 1 the crystallite diameter after the heat resistance test was able to be about 180 mm by setting the weight loss rate of TG 400-600 ° C. to 0.55%.
- Example 2 by setting the TG400-600 ° C. weight loss rate to 0.1%, the crystallite diameter after the heat resistance test could be about 100 mm, and the sintering resistance was improved.
- Example 3 the crystallite diameter after the heat resistance test could be reduced to about 250 mm by setting the TG400-600 ° C. weight loss rate to 1.8%.
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Abstract
Description
本発明の目的は、アンモニア溶媒を用いた水素化反応において、優れた耐熱性を有するニッケル珪藻土触媒およびその製造方法を提供することにある。
[1]
水素TG400-600℃重量減少率が0.05~2.0%である、ニッケル珪藻土触媒。
[2]
ニッケル結晶子径が30~100Åである、上記[1]に記載のニッケル珪藻土触媒。
[3]
耐熱性試験前後のニッケル結晶子径の変化Δが210Å以下である、上記[1]又は[2]に記載のニッケル珪藻土触媒。
[4]
比表面積が60~180m2/gである、上記[1]~[3]のいずれかに記載のニッケル珪藻土触媒。
[5]
沈殿法を用いたニッケル珪藻土触媒の製造方法であって、
珪藻土とニッケル触媒の塩を混合した分散液にアルカリ溶液の沈殿剤を入れる工程、
乾燥処理、焼成処理、還元処理を順に行う工程、
を含み、
前記焼成処理後に得られる焼成分の水素TPR測定のピーク温度+40℃以上で前記還元処理を行う、ニッケル珪藻土触媒の製造方法。
[6]
前記焼成処理後に得られる焼成分の水素TPR測定のピーク温度+200℃以下で前記還元処理を行う、上記[5]記載のニッケル珪藻土触媒の製造方法。
[7]
上記[5]又は[6]記載の製造方法によって得られるニッケル珪藻土触媒。
[8]
キシリレンジアミンの製造方法であって、
上記[1]~[4]又は[7]記載のニッケル珪藻土触媒を用いて、アンモニア溶媒中、フタロニトリルを水素化することを含む、製造方法。
なお、本実施形態中、各物性は、後述する実施例に記載された方法により測定することができる。
本実施形態におけるニッケル珪藻土触媒は、水素TG400-600℃重量減少率が0.05~2.0%である。水素TG400-600℃重量減少率は、0.1~1.8%であることが好ましく、0.1~1.0%であることがより好ましい。水素TG400-600℃重量減少率が0.05%未満であると、過酷な条件での還元が必要となるため経済性及び安全性の点から不利となり、2.0%を超えると耐熱性に劣る。
ここで、耐熱性試験とは、後述する実施例における耐熱性試験のことをいう。
本実施形態におけるニッケル珪藻土触媒の製造方法は、沈殿法を用いた製造方法であって、
珪藻土とニッケル触媒の塩を混合した分散液にアルカリ溶液の沈殿剤を入れる工程、
乾燥処理、焼成処理、還元処理を行う工程、を含み、
前記焼成処理後に得られる焼成分の水素TPR測定のピーク温度+40℃以上で還元処理を行う。
沈殿法としては、珪藻土の表面に水酸化ニッケル及び炭酸ニッケルを含む化合物を沈着させることができる方法であれば特に限定されず、従来公知の方法を適用することができる。
珪藻土とニッケル触媒の塩を混合した分散液を調製する際には、珪藻土を溶媒に添加してもよいし、珪藻土へ溶媒を添加してもよい。添加する際は、例えば、0~40℃の溶媒に珪藻土を添加して30~60分撹拌をしてから、所定の温度まで昇温してもよいし、溶媒を所定の温度にした状態で、珪藻土を添加してもよい。
Ni(NO3)2+Na2CO3→mNi(OH)2・NiCO3+NaNO3・・・(1)
沈殿処理により得られる沈殿物は、一般的な方法で洗浄、ろ過、乾燥をすればよい。例えば、ヌッチェを用いて回収し、さらに水等を用いて洗浄を行い不純物イオン(SO4 2-、NO3 -等)の除去を行うことができる。ニッケル化合物とS、Nは結合しやすく、被毒の原因物質となる危険性がある。洗浄は、一旦濾過で得た濾過ケーキを水に懸濁し、攪拌する懸濁洗浄を行う。懸濁洗浄後の濾液の電気伝導度は1mS/cm以下にすることが好ましい。洗浄終了後の濾過ケーキは100℃前後で十分乾燥を行い、乾燥ケーキを得る。
乾燥ケーキは、一般的な方法で焼成すればよい。例えば、電気炉を用いて焼成処理を行う。焼成雰囲気としては、空気でも窒素でもよい。焼成温度は、水酸化ニッケル、炭酸ニッケルを分解させる温度の観点から、200~500℃が好ましく、350~450℃がより好ましい。焼成時間は、水酸化ニッケル、炭酸ニッケルを十分に分解させるのに必要な時間の観点から、3~10時間が好ましく、5~7時間がより好ましい。塩基性炭酸ニッケルを焼成処理した場合、以下の式(2)のとおりに熱分解し、酸化ニッケル(焼成粉)となる。
mNi(OH)2+nNiCO3→(m+n)NiO+mH2O+nCO2・・・(2)
焼成処理の後、触媒を活性化させるために還元処理を行う(以下の式(3)参照)。この際用いられる還元剤としては、一般的な還元剤、例えば、水素、一酸化炭素、メタノール等を用いればよく、毒性や取り扱いやすさの観点から、水素が好ましい。例えば、焼成後の触媒を一定量SUS製反応管にとり、窒素雰囲気中で昇温し、水素ガスを導入する。反応温度は350~500℃が好ましく、380~450℃がより好ましい。
より高い温度で還元反応を行うことにより、未還元ニッケル化合物量を少なくすることができるが、温度が高過ぎると、比表面積が小さくなり、活性が下がる傾向にある。また、高温にするためには時間とエネルギーを必要とするため、経済的ではなく、危険性も増加する傾向にある。
NiO+H2→Ni+H2O・・・(3)
[物性測定]
乾燥ケーキについて物性測定を行った。乳鉢で粉砕した後、60~80メッシュの篩により得られた乾燥粉を測定試料として用いた。比表面積については、表面積測定装置(QUANTACHROME INSTRUMENTS社製 NOVA4200e)を用いた。前処理として測定試料を100℃で5時間乾燥を行った後、窒素吸着測定(BET法)によって比表面積を測定した。
ニッケル金属表面積については、以下の方法によって還元触媒の水素吸着量を測定して算出した。装置はBELCAT-B(日本ベル製)を用いた。初めに、ガラス製U字管に約0.4gの焼成粉を仕込んだ。反応管内部の温度を340℃として、ヘリウム(50mL/分)を45分導入した後、水素(50mL/分)を30分導入して、触媒を水素還元した。次に還元触媒をガラス製U字管内に保持したまま、ヘリウム(50mL/分)を10分間導入して、室温まで放冷した。次に、還元触媒をガラス製U字管内に保持したまま、水素ガス(50mL/分)を1分間導入することを繰り返し、排出されたガスの水素濃度をガスクロマトグラフィーにて測定した。U字管の入口及び出口の水素濃度増減がなくなるまでパルスを行い、その吸着量からニッケル金属表面積を算出した。
比表面積については、上記と同様の方法にて測定を行った。
還元挙動を熱天秤(TG)により測定した。装置は示差熱天秤(Rigaku製 Thermo plus evo TG8120)を用いた。還元安定化品を約10mg仕込み、3%水素/97%窒素(50mL/分)で導入した。昇温速度10℃/分にて600℃まで昇温し、この時の400-600℃の高温度域における重量減少率を測定した。該重量減少率は、未還元ニッケルから脱離した含酸素化合物と考えられ、未還元ニッケル量を示す指標になる。
液体アンモニアと水素雰囲気下における触媒の耐熱性の評価を行った。還元安定化品0.4g(60-80メッシュ)を内径6mmのSUS製反応管へ仕込んだ後、反応管内部の温度を250℃として、水素(40mL/分)を10時間導入して還元触媒を得た。その後、反応管の内部の圧力を水素10MPaG、温度を120℃として、液体アンモニア(10g/時)、水素(40mL/分)を14時間導入した。液体アンモニア導入後、常温常圧に戻した後に触媒を取りだし、XRD装置(Rigaku製 MiniFlex600)にてニッケル結晶子径の測定を行った。
焼成粉にグラファイトを3質量%添加し、打錠成形機にて6mmφ×6mmに打錠成型し、上記と同様の方法で還元安定化品を得た。この還元安定化品を用いて以下のように活性(水素化反応)試験を行った。100mLSUS製オートクレーブ反応器に還元安定化品2gを仕込んだ後、反応管内部の温度を250℃として、50%水素/50%窒素ガスを20mL/分で10時間導入した。その後、反応器にメタキシレン(和光純薬製)10g、イソフタロニトリル(東京化成工業製)6.7g、液体アンモニア10gを充填し、水素を10MPaGまで充填した。水素充填後、反応器内部の撹拌を行いながら80℃で2時間加熱して水素化反応を行い、メタキシリレンジアミン(MXDA)を得た。
珪藻土2gに10%Na2CO3水溶液80mLを加え、60℃で2時間の撹拌処理を行い、処理液中の溶出Si量をICP-AES(Varian製 Vista)にて測定した。結果を表1に示す。
なお、表2には、各実施例及び比較例で用いた珪藻土の平均の溶出Si量を示した。
珪藻土としてフィルターセル(未焼成品、イメリス社製)17.5gとセライト503(焼成品、イメリス社製)17.5g、ニッケル源として硫酸ニッケル・6水和物(和光純薬製)283.2g、水1000gを3L三口フラスコに25℃で混合し、スラリーを調製した。スラリーは300rpmで攪拌を行い、70℃まで昇温した。
別容器を用いて、炭酸ナトリウム(和光純薬製)202gを水1000gに溶解させ、沈殿剤を調製した。チューブポンプを用いて、沈殿剤をスラリーに20g/分で注加した。注加の間、スラリーの温度は70℃に保持し、撹拌を行った。全量を注加後、2℃/分で80℃に昇温し、2時間撹拌を行い、熟成を行った。その後、得られたスラリーを、ヌッチェ(ろ紙:アドバンテック 4A)を用いて減圧濾過し、濾過ケーキを得た。
濾過ケーキを3Lポリプロピレン製ジョッキに入れ、純水1000gを加え、25℃で攪拌しながら再度スラリー化して、懸濁洗浄および濾過を行った。濾液の電気伝導率が0.5mS/cm以下になるまで、懸濁洗浄と濾過を繰り返し行った。濾過ケーキは、電気乾燥機を用いて110℃で12時間乾燥を行い、乾燥ケーキを得た。
乾燥ケーキは焼成炉にて380℃で5時間焼成を行い、触媒焼成ケーキを得た。この焼成ケーキを粉砕し、触媒焼成粉を得た。
触媒焼成粉を内径1.4cmのSUS製反応管へ仕込み、50%水素/50%窒素ガス(60mL/分)を用いて400℃で10時間還元を行った。還元安定化後は窒素雰囲気にて室温まで放冷を行い、1%酸素/99%窒素ガス(60mL/分)を4時間流通させた後、続けて4%酸素/96%窒素ガス(60mL/分)を2時間流通させて安定化を行い、還元安定化品を得た。各測定結果を表2に示す。
ニッケル結晶子径は試験前後において、42Åから180Åとなった。試験後のニッケル結晶子は180Åであり、成長は小さく、耐熱性は高かった。
触媒焼成粉の還元条件を450℃で10時間に代えたこと以外は、実施例1と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
触媒焼成粉の還元条件を380℃で10時間に代えたこと以外は、実施例1と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
触媒焼成粉の還元条件を310℃で10時間に代えたこと以外は、実施例1と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
珪藻土の割合を、フィルターセル/セライト503=25質量%/75質量%に代えたこと以外は、実施例1と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
珪藻土の割合を、フィルターセル/セライト503=75質量%/25質量%に代えたこと以外は、実施例1と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
珪藻土の割合を、フィルターセル=100質量%、熟成時間を180分にしたこと以外は、実施例1と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
珪藻土の割合を、フィルターセル/Diafil♯110(未焼成品、イメリス社製)=50質量%/50質量%、熟成時間を180分に代えたこと以外は、実施例1と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
熟成時間を100分にしたこと以外は比較例2と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
熟成温度を70℃、熟成時間を120分にしたこと以外は比較例2と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
珪藻土の割合を、セライト503=100質量%にしたこと以外は、比較例2と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
還元温度を420℃にしたこと以外は、比較例2と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
還元温度を420℃にしたこと以外は、比較例3と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
還元温度を450℃にしたこと以外は、比較例2と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
還元温度を450℃にしたこと以外は、比較例3と同じ方法によりニッケル珪藻土触媒を得た。各測定結果を表2に示す。
Claims (8)
- 水素TG400-600℃重量減少率が0.05~2.0%である、ニッケル珪藻土触媒。
- ニッケル結晶子径が30~100Åである、請求項1に記載のニッケル珪藻土触媒。
- 耐熱性試験前後のニッケル結晶子径の変化Δが210Å以下である、請求項1又は2に記載のニッケル珪藻土触媒。
- 比表面積が60~180m2/gである、請求項1~3いずれか1項に記載のニッケル珪藻土触媒。
- 沈殿法を用いたニッケル珪藻土触媒の製造方法であって、
珪藻土とニッケル触媒の塩を混合した分散液にアルカリ溶液の沈殿剤を入れる工程、
乾燥処理、焼成処理、還元処理を順に行う工程、
を含み、
前記焼成処理後に得られる焼成分の水素TPR測定のピーク温度+40℃以上で前記還元処理を行う、ニッケル珪藻土触媒の製造方法。 - 前記焼成処理後に得られる焼成分の水素TPR測定のピーク温度+200℃以下で前記還元処理を行う、請求項5記載のニッケル珪藻土触媒の製造方法。
- 請求項5又は6記載の製造方法によって得られるニッケル珪藻土触媒。
- キシリレンジアミンの製造方法であって、
請求項1~4又は7記載のニッケル珪藻土触媒を用いて、アンモニア溶媒中、フタロニトリルを水素化することを含む、製造方法。
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JP2022539359A (ja) * | 2019-06-28 | 2022-09-08 | ハンファ ソルーションズ コーポレーション | 水素化反応用ニッケル触媒及びその製造方法 |
JP7352664B2 (ja) | 2019-06-28 | 2023-09-28 | ハンファ ソルーションズ コーポレーション | 水素化反応用ニッケル触媒及びその製造方法 |
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EP3372309A1 (en) | 2018-09-12 |
JP6916994B2 (ja) | 2021-08-11 |
JPWO2017077969A1 (ja) | 2018-08-23 |
US20180297932A1 (en) | 2018-10-18 |
CN108136376B (zh) | 2021-11-12 |
CN108136376A (zh) | 2018-06-08 |
KR102468578B1 (ko) | 2022-11-18 |
US20200010404A1 (en) | 2020-01-09 |
EP3372309A4 (en) | 2019-05-22 |
KR20180077178A (ko) | 2018-07-06 |
US10875824B2 (en) | 2020-12-29 |
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