CN107243342A - A kind of loaded catalyst and its preparation method and application - Google Patents
A kind of loaded catalyst and its preparation method and application Download PDFInfo
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- CN107243342A CN107243342A CN201610654478.5A CN201610654478A CN107243342A CN 107243342 A CN107243342 A CN 107243342A CN 201610654478 A CN201610654478 A CN 201610654478A CN 107243342 A CN107243342 A CN 107243342A
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- loaded catalyst
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000015556 catabolic process Effects 0.000 claims abstract description 4
- 238000006731 degradation reaction Methods 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 12
- 239000008246 gaseous mixture Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000010815 organic waste Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 238000010129 solution processing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 alkyl aromatic hydrocarbon Chemical class 0.000 description 1
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HIIGGQNLPWIVAG-UHFFFAOYSA-L nickel(2+);diacetate;hydrate Chemical compound O.[Ni+2].CC([O-])=O.CC([O-])=O HIIGGQNLPWIVAG-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Classifications
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- B01J35/615—
-
- B01J35/617—
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
Abstract
The invention discloses a kind of loaded catalyst and its preparation method and application, belong to catalyst field.The present invention is combined main catalytic active component and carrier by ion exchange, due to being combined between main catalytic active component and carrier by electrostatic force, with reference to stable, not easily runs off；Main catalytic active component is the one or more in nickel, iron, cobalt, ruthenium and its oxide；Carrier is prepared into calcium type cation adsorbent is converted into, the presence of calcium has to keep beneficial to the duct in roasting process, the not easy-sintering in high-temperature process, so that catalyst possesses higher specific surface area.The active component good dispersion of gained loaded catalyst, catalytic mechanical intensity is high, and performance is stable, can effectively improve the degradation rate and reaction efficiency of hydro-thermal method degradation of organic substances.
Description
Technical field
The invention belongs to catalyst field, more specifically to a kind of loaded catalyst and preparation method thereof and should
With.
Background technology
The aquathermolysis technology of organic waste is exactly, using sub-, supercritical water as medium, organic matter to be pyrolyzed, and makes big point
The molecular scission of sub- organic matter, hydrocarbon, is transformed into the process of small-molecule substance.Hydro-thermal gasification application more is raw
In the aspect of material, but aquathermolysis technology has many advantages in terms of organic waste is handled, and has to development distributed energy
Important function, potential Utilization prospects are wide.And important role of the catalyst in hydro-thermal gasification, it can accelerate reaction speed
Rate, improves the yield of target product, and the hydro-thermal catalyst used at present mainly divides three classes：Carbons catalyst, metal-based catalysts
And alkali catalyst.For at present, metal-based catalysts excellent catalytic effect, but there is easily poisoning mistake in monometallic class catalyst
The problems such as living, and can not reuse, and it is a kind of effective solution to prepare loaded catalyst.
Existing load type metal catalyst typically selects activated carbon, chitosan, porous ceramic grain, activated alumina, titanium dioxide
Silicon, zeolite or clay etc. are carrier, the active component of load include transition metal (such as nickel, iron, cobalt) and noble metal (such as ruthenium,
Platinum, palladium etc.).Such as, Chinese patent " a kind of preparation and its application of Ni/Ag/Cu/ tripolite composite catalysts " (notification number
CN103623841B one kind) is disclosed using copper nitrate, silver nitrate, nickel nitrate as raw material, diatomite is carrier, by dipping, do
The method that the step of dry, roasting, reduction prepares the Ni/Ag/Cu/ composite diatomite loaded catalysts of different loads amount.But leaching
Stain method is due to being mainly that non-specific adsorption is acted between active component and carrier, and adhesion is weaker, is easy to run off active component, and
And active component is difficult to be evenly distributed in carrier surface, local reunion is easily formed, catalytic activity is influenceed.
Patent " biomass gasification catalyst and production method " (notification number CN1686606A) discloses a kind of biomass
Catalyst for gasifying stove and its production method, the catalyst is by Concave-convex clay rod, alumine, iron oxide, magnesia, oxidation
Calcium and anthracite composition, finished product, wherein goudron lysis rate are detected and are packaged as through dispensing, stirring, milling, granulation, drying, screening
More than 75%.The interaction that this method is prepared between catalyst, each component using simple mechanical mixture is weaker, easily makes
The sintering of Viability metal, causes catalyst inactivation.
Patent No. CN201410768421.9 patent (notification number CN104549292A) discloses one kind with reguline metal
Nickel target is raw material；Silica solid powder is scattered in deionized water；Nickel target is placed in above-mentioned solution, stirred in magnetic force
Mix and motorized precision translation stage booster action under use ns focused pulse laser ablation target, be made nickel/silica suspension；Again
The preparation method of nickel/SiO 2 powder shape loaded catalyst will be made after the suspension suction filtration, drying.This method catalyst
Stability is higher, but there is synthesizer requirement height, is unfavorable for the shortcoming promoted.
Ion-exchanger has much been applied as the carrier of catalyst, and such as " polymetal carrying alkyl aromatic hydrocarbon is different for patent
Structure catalyst " (publication number CN1149002A), by zeolite and the first mixed-forming of aluminum oxide, is made carrier, then uses ammonium ion
By the sodium ion exchange in zeolite to certain exchange degree, then impregnated with platinum and catalyst is made, for aromatic hydrocarbons isomery
Change process produces contraposition product, with good isomerization activity, selectivity and activity stability.But ion-exchanger often exists
Easily sintered under high temperature, it is impossible to be used in the high temperature and high pressure environment of hydro-thermal method.
Prior art prepare loaded catalyst, there is its catalyst active component composition and be easy to run off, and activity into
Divide the problem of dispersiveness on carrier is difficult to regulation and control, influence the using effect and service life of catalyst.And use ion to hand over
When changing agent as catalyst carrier, although carrier and active component adhesion are relatively strong, but the catalyst being made is high in high temperature
Pressure ring is easily sintered under border, causes catalyst inactivation.
The content of the invention
1. the problem of solving
For existing loaded catalyst exist active component composition be easy to run off, the dispersiveness not easy-regulating of active component
And the problems such as easy-sintering, the present invention provides a kind of loaded catalyst and its preparation method and application, catalyst of the invention
There is high degree of dispersion, bigger serface, high intensity, high temperature high voltage resistant, available for hydro-thermal method degraded organic waste, turn
Rate is high, and service life is long.
2. technical scheme
In order to solve the above problems, the technical solution adopted in the present invention is as follows：
A kind of loaded catalyst, supported on carriers has main catalytic active component, and described carrier is handed over for calcium type cation
Change agent；Described main catalytic active component be nickel, iron, cobalt, ruthenium and its oxide in one or more, load capacity be 0.5~
20% (mass fraction).
Further, described loaded catalyst also contains CaO, CaO quality be catalyst gross mass 0.5%~
2.0%；Described main catalytic active component is combined between described carrier by electrostatic force.
Further, the specific surface area of described loaded catalyst is 300~1000m2/g。
A kind of application of the above-mentioned loaded catalyst in hydro-thermal method catalytic degradation organic waste field, reaction temperature
At 700~900 DEG C, 23~30MPa of reaction pressure, 60~90min of reaction time, conversion rate of organic matter are more than 95%.
A kind of preparation method of loaded catalyst, mainly including the steps：
(1) by cation-exchanger Ca2+Solution is processed as calcium type, forms calcium type cation-exchanger；
(2) by calcium type cation-exchanger made from step (1) with the ethanol solution of the precursor of main catalytic active component or
Ammonia spirit carries out ion exchange, and reaction temperature is 60~70 DEG C；
(3) in N after the product drying of step (2)2500~900 DEG C are warming up under protection；
(4) it is passed through activated gas and activates 2~8h；
(5) in N2Room temperature is cooled under protection；
(6) product for obtaining step (5) handles 30~90min in boiling water；
(7) dry, produce loaded catalyst.
Further, the cation-exchanger in step (1) is large hole cation exchanger resin.
Further, it is described to use Ca in step (1)2+The process of solution processing is to lead to by the order of alkali, water, acid, water, alkali
Cross the ion exchange column for being filled with carrier, wherein, the alkali is the saturated solution of calcium hydroxide or calcium carbonate, the acid for 5~
10% hydrochloric acid.
Further, the precursor of the main catalytic active component in step (2) is nickel acetate, ferric acetate, cobalt acetate, ruthenium acetate
And its one or more in hydrate, consumption is the 1~50% of the quality of cation-exchanger used.
Further, the programming rate in step (3) is 5~15 DEG C/min.
Further, the activation method in step (4) is to be passed through water vapour or air or H2/ Ar gaseous mixtures, wherein mixing
The mixed proportion of gas is H2:Ar=1:(3~5) (volume ratio).
3. beneficial effect
Compared to prior art, beneficial effects of the present invention are：
(1) main catalytic active component and carrier of the present invention is combined by ion exchange process, and main catalytic active component is with carrying
It is combined, with reference to stable, is not easily runed off by electrostatic force between body；
(2) present invention is prepared into carrier with being converted into calcium type cation-exchanger, and the presence of calcium has beneficial in roasting process
Duct keep, the not easy-sintering in high-temperature process, so that catalyst possesses higher specific surface area；
(3) present invention prepares the solution of the precursor of main catalytic active component using ammoniacal liquor or ethanol, promotes main catalytic activity
Composition is main to be existed with cation form, is associated in the formal bond of ion exchange on carrier, it is to avoid its absorption on carrier, from
And ensure the high degree of dispersion of main catalytic active component, obtain high catalytic activity；
(4) present invention use acetate for the precursor of main catalytic active component, it is to avoid generation NOx in preparation process,
SO2、H2The polluters such as S, HCl；
(5) catalyst high temperature high voltage resistant produced by the present invention, the HTHP ring of organic waste is handled in hydropyrolysis process
Performance is stable in border, and service life is long；
(6) present invention is while main catalytic active component carries out catalytic reaction, and calcium oxide component can be with absorption system
CO2, promote the generation of hydrogen.
Brief description of the drawings
Fig. 1 is the SEM sections and exterior view of the catalyst obtained in the embodiment of the present invention 6；
Fig. 2 is the SEM sections and exterior view after obtained catalyst use in the embodiment of the present invention 6；
Fig. 3 is the hydrothermal reaction process schematic diagram described in the embodiment of the present invention.
Embodiment
The present invention is further described below with reference to specific embodiment.
Embodiment 1
D001 large hole cation exchanger resins are taken, (1) is pressed with the saturated calcium hydroxide and 5% watery hydrochloric acid of 3 times of volumes
Alkali, water, acid, water, the sequential purge of alkali, (2) add the ethanol solution containing 5% ruthenium acetate at 60 DEG C and carry out ion exchange, second
The mass ratio of sour ruthenium and resin is 1:100, in N after the drying of (3) product2Under protection, with 5 DEG C/min speed liter in tube furnace
After warm to 500 DEG C, (4) are passed through steam activation 8h, and (5) are in N2Room temperature is cooled under protection, (6) product is handled in boiling water
90min, (7), in 100 DEG C of dryings, gained loaded catalyst is designated as catalyst (I).In mass, ruthenium content in catalyst (I)
For 0.5%, CaO content is 2%, and specific surface area of catalyst is 352m2/g。
Embodiment 2
Take D061 large hole cation exchanger resins, (1) with the unsaturated carbonate calcium and 5% watery hydrochloric acid of 3 times of volumes, by alkali,
Water, acid, water, the sequential purge of alkali, (2) add the ammonia solution containing 15% nickel acetate at 70 DEG C and carry out ion exchange, acetic acid
The mass ratio of nickel and resin is 1:2, in N after the drying of (3) product2Under protection, heated up in tube furnace, programming rate is 10
DEG C/min, to 900 DEG C, (4) are passed through air-activated 6h, and (5) are in N2Room temperature is cooled under protection, (6) product is handled in boiling water
30min, (7), in 110 DEG C of dryings, gained loaded catalyst is designated as catalyst (II).In mass, aoxidized in catalyst (II)
Nickel content is 18.7%, and CaO content is 0.5%, and specific surface area of catalyst is 916m2/g。
Embodiment 3
D152 large hole cation exchanger resins are taken, (1) is pressed with the saturated calcium hydroxide and 5% watery hydrochloric acid of 3 times of volumes
Alkali, water, acid, water, the sequential purge of alkali, (2) add the ethanol solution containing 10% cobalt acetate at 70 DEG C and carry out ion exchange,
The mass ratio of cobalt acetate and resin is 1:10, in N after the drying of (3) product2Under protection, heated up in tube furnace, heating speed
Spend for 8 DEG C/min, to 700 DEG C, (4) are passed through H2/ Ar gaseous mixtures activate 2h, and the wherein mixed proportion of gaseous mixture is H2:Ar=1:4
(volume), (5) are in N2Room temperature is cooled under protection, (6) product handles 60min in boiling water, (7) are born in 110 DEG C of dryings, gained
Supported catalyst is designated as catalyst (III).In mass, cobalt content is 1.6% in catalyst (III), and CaO content is 1%, catalysis
Agent specific surface area is 472m2/g。
Embodiment 4
Take D113 large hole cation exchanger resins, (1) with the unsaturated carbonate calcium and 10% watery hydrochloric acid of 3 times of volumes, by alkali,
Water, acid, water, the sequential purge of alkali, (2) are added at 60 DEG C carries out ion exchange, hydration containing 10% acetate hydrate ferrous solution
The mass ratio of ferric acetate and resin is 1:5, in N after the drying of (3) product2Under protection, heated up in tube furnace, programming rate
For 15 DEG C/min, to 600 DEG C, (4) are passed through H2/ Ar gaseous mixtures activate 5h, and the wherein mixed proportion of gaseous mixture is H2:Ar=1:5
(volume), (5) are in N2Room temperature is cooled under protection, (6) product handles 45min in boiling water, (7) are born in 110 DEG C of dryings, gained
Supported catalyst is designated as catalyst (IV).In mass, iron oxide content is 7.6% in catalyst (IV), and CaO content is
1.5%, specific surface area of catalyst is 300m2/g。
Embodiment 5
The ND-77 type large hole cation exchanger resins for taking Jiangsu NJU Environmental Technology Co., Ltd. to produce, (1) is with 3 times of bodies
Long-pending saturated calcium hydroxide and 10% watery hydrochloric acid, by alkali, water, acid, water, alkali sequential purge, (2) are added at 60 DEG C to be contained
The mass ratio of 10% acetate hydrate nickel solution progress ion exchange, hydrated Ni acetate and resin is 1:3, after (3) product is dried
In N2Under protection, heated up in tube furnace, programming rate is 15 DEG C/min, and to 600 DEG C, (4) are passed through H2/ Ar gaseous mixtures are lived
Change 5h, the wherein mixed proportion of gaseous mixture is H2:Ar=1:5 (volumes), (5) are in N2Room temperature is cooled under protection, (6) product exists
30min is handled in boiling water, (7), in 110 DEG C of dryings, gained loaded catalyst is designated as catalyst (V).In mass, catalyst
(V) nickel oxide content is 20.0% in, and CaO content is 0.5%, and specific surface area of catalyst is 1000m2/g。
Embodiment 6
The ND-77 type large hole cation exchanger resins for taking Jiangsu NJU Environmental Technology Co., Ltd. to produce, (1) is with 3 times of bodies
Long-pending saturated calcium hydroxide and 10% watery hydrochloric acid, by alkali, water, acid, water, alkali sequential purge, (2) add acetic acid at 60 DEG C
The mass ratio of the mixed solution progress ion exchange of ruthenium and nickel acetate, nickel acetate and ruthenium acetate and resin is respectively 1:5 and 1:50,
(3) in N after product is dried2Under protection, heated up in tube furnace, programming rate is 5 DEG C/min, and to 800 DEG C, (4) are passed through
H2/ Ar gaseous mixtures activate 7h, and the wherein mixed proportion of gaseous mixture is H2:Ar=1:3 (volumes), (5) are in N2Room is cooled under protection
Temperature, (6) product handles 90min in boiling water, and (7), in 100 DEG C of dryings, gained loaded catalyst is designated as catalyst (VI).With
Nickel oxide content is 8.2% in quality meter, catalyst (VI), and oxidation ruthenium content is 0.8%, and CaO content is 1%, catalyst ratio
Surface area is 580m2/g。
Comparative example 1 uses natural minerals catalyst dolomite, standby in hermetic bag in being mounted in after being calcined 4 hours at 900 DEG C,
Its component by percentage to the quality, including 29.06%CaO, 22.44%MgO, 0.38%SiO2, 0.20%Fe2O3, 0.08%
Al2O3。
Comparative example 2 is using the Cu-Zn-Al catalyst of purchase, and it is constituted by percentage to the quality, including 30%CuO, and 35%
ZnO, 20%Al2O3, 5%MnO2, 10%ZrO2。
The catalyst in above-mentioned catalyst (I)~(VI) and comparative example 1 and 2 is fitted into hydrothermal reactor respectively, with
The industrial sludge that certain chemical plant is produced is process object, and course of reaction is as shown in figure 3, reaction condition and reaction result see the table below.
Catalyst structure and similar nature that embodiment 1~6 is obtained, reaction front-end geometry and performance are said without significant changes
Bright catalyst has good stability.
The catalytic condition and Comparative result of catalyst in the embodiment 1~6 of table 1 and the catalyst in comparative example 1 and 2
Claims (10)
1. a kind of loaded catalyst, supported on carriers has main catalytic active component, it is characterised in that：Described carrier is calcium type
Cation-exchanger；Described main catalytic active component is the one or more in nickel, iron, cobalt, ruthenium and its oxide, load capacity
For 0.5~20% (mass fraction).
2. a kind of loaded catalyst according to claim 1, it is characterised in that：Described loaded catalyst also contains
CaO, CaO quality are the 0.5%~2.0% of catalyst gross mass；Described main catalytic active component and described carrier it
Between be combined by electrostatic force.
3. a kind of loaded catalyst according to claim 1, it is characterised in that：The ratio table of described loaded catalyst
Area is 300~1000m2/g。
4. a kind of loaded catalyst in claims 1 to 3 described in any one is in hydro-thermal method catalytic degradation organic waste
Application in field, it is characterised in that：Reaction temperature is at 700~900 DEG C, 23~30MPa of reaction pressure, and the reaction time 60~
90min, conversion rate of organic matter is more than 95%.
5. a kind of preparation method of loaded catalyst, mainly including the steps：
(1) by cation-exchanger Ca2+Solution is processed as calcium type, forms calcium type cation-exchanger；
(2) by the ethanol solution or ammoniacal liquor of the calcium type cation-exchanger precursor of main catalytic active component made from step (1)
Solution carries out ion exchange, and reaction temperature is 60~70 DEG C；
(3) in N after the product drying of step (2)2500~900 DEG C are warming up under protection；
(4) it is passed through activated gas and activates 2~8h；
(5) in N2Room temperature is cooled under protection；
(6) product for obtaining step (5) handles 30~90min in boiling water；
(7) dry, produce loaded catalyst.
6. a kind of preparation method of loaded catalyst according to claim 5, it is characterised in that：It is described in step (1)
Cation-exchanger be large hole cation exchanger resin.
7. a kind of preparation method of loaded catalyst according to claim 5, it is characterised in that：It is described in step (1)
Use Ca2+The process of solution processing be by alkali, water, acid, water, alkali order by being filled with the ion exchange column of carrier, wherein, institute
It is calcium hydroxide or the saturated solution of calcium carbonate, the hydrochloric acid that the acid is 5~10% to state alkali.
8. a kind of preparation method of loaded catalyst according to claim 5, it is characterised in that：It is described in step (2)
Main catalytic active component precursor be nickel acetate, ferric acetate, cobalt acetate, ruthenium acetate and its hydrate in one or more,
Consumption is the 1~50% of the quality of cation-exchanger used.
9. a kind of preparation method of loaded catalyst according to claim 5, it is characterised in that：It is described in step (3)
Programming rate be 5~15 DEG C/min.
10. a kind of preparation method of loaded catalyst according to claim 5, it is characterised in that：In step (4), institute
The activation method stated is to be passed through water vapour or air or H2The mixed proportion of/Ar gaseous mixtures, wherein gaseous mixture is H2:Ar=1:(3
~5) (volume ratio).
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| CN109908919A (en) * | 2019-03-11 | 2019-06-21 | 华侨大学 | A kind of monatomic Ag1/Co of thermoplastic polymer3O4The preparation method of catalyst |
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