CN107243342B - Supported catalyst and preparation method and application thereof - Google Patents
Supported catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN107243342B CN107243342B CN201610654478.5A CN201610654478A CN107243342B CN 107243342 B CN107243342 B CN 107243342B CN 201610654478 A CN201610654478 A CN 201610654478A CN 107243342 B CN107243342 B CN 107243342B
- Authority
- CN
- China
- Prior art keywords
- supported catalyst
- catalyst
- active component
- carrier
- catalytic active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims abstract description 3
- 238000006731 degradation reaction Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 239000000292 calcium oxide Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003729 cation exchange resin Substances 0.000 claims description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229940078494 nickel acetate Drugs 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 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 compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000010815 organic waste Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 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 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 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
- 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 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000011068 loading method Methods 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
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000004480 active ingredient Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 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
- 150000002500 ions Chemical class 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910021543 Nickel dioxide Inorganic materials 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 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
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 ammonium ions Chemical class 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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 supported catalyst and a preparation method and application thereof, belonging to the field of catalysts. The main catalytic active component is combined with the carrier through ion exchange, and the main catalytic active component is combined with the carrier through electrostatic acting force, so that the combination is stable and is not easy to lose; the main catalytic active component is one or more of nickel, iron, cobalt, ruthenium and oxides thereof; the carrier is prepared by the cation adsorbent converted into calcium, the existence of calcium is beneficial to maintaining pore channels in the roasting process, and the catalyst is not easy to sinter during high-temperature treatment, so that the catalyst has higher specific surface area. The obtained supported catalyst has good active component dispersibility, high mechanical strength and stable performance, and can effectively improve the degradation rate and the reaction efficiency of organic matters degraded by a hydrothermal method.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a supported catalyst and a preparation method and application thereof.
Background
The water pyrolysis technology of organic waste is a process of pyrolyzing organic matters by using subcritical and supercritical water as a medium to break molecular bonds of macromolecular organic matters and hydrocarbons and convert the macromolecular organic matters and the hydrocarbons into micromolecular substances. The hydrothermal gasification is mostly applied to biomass, but the hydrothermal technology has many advantages in the aspect of treating organic waste, plays an important role in developing distributed energy and has a wide potential utilization prospect. The catalyst plays an important role in hydrothermal gasification, can accelerate the reaction rate and improve the yield of a target product, and the currently used hydrothermal catalysts are mainly classified into three types: carbon-based catalysts, metal-based catalysts and base-based catalysts. At present, the metal catalyst has good catalytic effect, but the problems of easy poisoning and inactivation, incapability of recycling and the like exist in the single metal catalyst, and the preparation of the supported catalyst is an effective solution.
The existing supported metal catalyst generally adopts activated carbon, chitosan, porous ceramsite, activated alumina, silica, zeolite or clay and the like as carriers, and the supported active components comprise transition metals (such as nickel, iron, cobalt and the like) and noble metals (such as ruthenium, platinum, palladium and the like). For example, the chinese patent "preparation of a Ni/Ag/Cu/diatomite composite catalyst and its application" (publication No. CN103623841B) discloses a method for preparing Ni/Ag/Cu/diatomite composite supported catalysts with different loading amounts by using copper nitrate, silver nitrate, and nickel nitrate as raw materials and diatomite as a carrier through the steps of impregnation, drying, calcination, and reduction. However, in the impregnation method, due to the fact that the active components and the carrier are mainly subjected to nonspecific adsorption, the binding force is weak, the active components are easy to run off, the active components are difficult to distribute uniformly on the surface of the carrier, local agglomeration is easy to form, and catalytic activity is affected.
The patent 'biomass gasification furnace catalyst and production method' (publication No. CN1686606A) discloses a biomass gasification furnace catalyst and a production method thereof, wherein the catalyst is composed of attapulgite clay, high alumina bauxite, iron oxide, magnesium oxide, calcium oxide and anthracite, and is prepared into a finished product by proportioning, stirring, grinding, granulating, drying, screening, detecting and packaging, wherein the cracking rate of tar is more than 75%. The method adopts simple mechanical mixing to prepare the catalyst, the interaction among the components is weak, and the sintering of active metal is easily caused to cause the inactivation of the catalyst.
Patent No. CN201410768421.9 (publication No. CN104549292A) discloses a method of using a bulk metallic nickel target as a raw material; dispersing silicon dioxide solid powder in deionized water; placing a nickel target material into the solution, and ablating the target material by nanosecond focused pulse laser under the auxiliary action of magnetic stirring and an electric translation table to prepare a nickel/silicon dioxide suspension; and then the suspension is filtered and dried to prepare the nickel/silicon dioxide powdery supported catalyst. The catalyst has high stability, but has the defects of high requirement on a synthesis device and inconvenience for popularization.
The ion exchanger has been widely used as a carrier of a catalyst, for example, in a patent "noble metal supported alkyl aromatic isomerization catalyst" (publication number CN1149002A), zeolite and alumina are mixed and molded to prepare a carrier, then sodium ions in the zeolite are exchanged to a certain exchange degree by ammonium ions, and then platinum metal is impregnated to prepare the catalyst, so that the catalyst is used for preparing a para-product in an aromatic isomerization process, and has good isomerization activity, selectivity and activity stability. However, the ion exchanger is often very easy to sinter at high temperature and cannot be used in the high-temperature and high-pressure environment of a hydrothermal method.
The problems that active ingredients of the catalyst prepared by the prior art are easy to lose and the dispersibility of the active ingredients on the carrier is difficult to regulate and control exist in the supported catalyst prepared by the prior art, so that the using effect and the service life of the catalyst are influenced. When the ion exchanger is used as a catalyst carrier, although the binding force between the carrier and active ingredients is relatively strong, the prepared catalyst is easy to sinter under the high-temperature and high-pressure environment, so that the catalyst is inactivated.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that the active ingredients of the existing supported catalyst are easy to lose, the dispersibility of the active ingredients is difficult to regulate and control, the existing supported catalyst is easy to sinter and the like, the supported catalyst provided by the invention has the advantages of high dispersity, large specific surface area, high strength, high temperature and high pressure resistance and the like, can be used for degrading organic wastes by a hydrothermal method, and is high in conversion rate and long in service life.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a load type catalyst, load the active ingredient of main catalysis on the carrier, the said carrier is a calcium type cation exchanger; the main catalytic active component is one or more of nickel, iron, cobalt, ruthenium and oxides thereof, and the loading amount is 0.5-20% (mass fraction).
Furthermore, the supported catalyst also contains CaO, and the mass of the CaO is 0.5-2.0% of the total mass of the catalyst; the main catalytic active component is combined with the carrier through electrostatic acting force.
Further, the specific surface area of the supported catalyst is 300-1000 m2/g。
The application of the supported catalyst in the field of catalytic degradation of organic wastes by a hydrothermal method has the advantages that the reaction temperature is 700-900 ℃, the reaction pressure is 23-30 MPa, the reaction time is 60-90 min, and the conversion rate of organic matters is more than 95%.
A preparation method of a supported catalyst mainly comprises the following steps:
(1) using Ca as cation exchanger2+Treating the solution into calcium type to form calcium type cation exchanger;
(2) carrying out ion exchange on the calcium type cation exchanger prepared in the step (1) by using an ethanol solution or an ammonia water solution of a precursor of a main catalytic active component, wherein the reaction temperature is 60-70 ℃;
(3) drying the product of the step (2) and then adding the dried product into N2Heating to 500-900 ℃ under protection;
(4) activating for 2-8 h by introducing activating gas;
(5) in N2Cooling to room temperature under protection;
(6) treating the product obtained in the step (5) in boiling water for 30-90 min;
(7) and drying to obtain the supported catalyst.
Further, the cation exchanger in the step (1) is macroporous cation exchange resin.
Further, in the step (1), Ca is used2+The solution treatment process comprises the step of passing through an ion exchange column filled with a carrier in the order of alkali, water, acid, water and alkali, wherein the alkali is a saturated solution of calcium hydroxide or calcium carbonate, and the acid is 5-10% hydrochloric acid.
Further, the precursor of the main catalytic active component in the step (2) is one or more of nickel acetate, iron acetate, cobalt acetate, ruthenium acetate and hydrates thereof, and the dosage of the precursor is 1-50% of the mass of the used cation exchanger.
Further, the temperature rise speed in the step (3) is 5-15 ℃/min.
Further, the activation method in the step (4) is to inject water vapor or air or H2The mixed gas of/Ar, wherein the mixing ratio of the mixed gas is H2Ar is 1 (3-5) (volume ratio).
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the main catalytic active component and the carrier are combined through an ion exchange process, and the main catalytic active component and the carrier are combined through electrostatic acting force, so that the combination is stable and is not easy to lose;
(2) the carrier is prepared by the cation exchanger converted into calcium, the existence of calcium is beneficial to maintaining pore channels in the roasting process, and the catalyst is not easy to sinter during high-temperature treatment, so that the catalyst has higher specific surface area;
(3) the invention adopts ammonia water or ethanol to prepare the solution of the precursor of the main catalytic active component, so that the main catalytic active component mainly exists in a cation form and is bonded on the carrier in an ion exchange form to avoid the adsorption of the main catalytic active component on the carrier, thereby ensuring the high dispersion degree of the main catalytic active component and obtaining high catalytic activity;
(4) the invention adopts acetate as the precursor of the main catalytic active component, thereby avoiding generating NOx and SO in the preparation process2、H2S, HCl and the like;
(5) the catalyst prepared by the invention is resistant to high temperature and high pressure, stable in performance and long in service life in a high-temperature and high-pressure environment for treating organic wastes by a hydrothermal method;
(6) the invention can absorb CO in the system by the calcium oxide component while the main catalytic active component carries out catalytic reaction2And the generation of hydrogen is promoted.
Drawings
FIG. 1 is an SEM cross-section and surface view of a catalyst obtained in example 6 of the present invention;
FIG. 2 is a SEM cross-section and surface view of the catalyst obtained in example 6 of the present invention after use;
FIG. 3 is a schematic diagram of a hydrothermal reaction process according to an embodiment of the present invention.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
Taking D001 macroporous cation exchange resin, (1) washing with 3 times volume of saturated calcium hydroxide and 5% of dilute hydrochloric acid in sequence of alkali, water, acid, water and alkali, (2) adding an ethanol solution containing 5% of ruthenium acetate at 60 ℃ for ion exchange, wherein the mass ratio of the ruthenium acetate to the resin is 1:100, and (3) drying the product, and then carrying out N-phase ion exchange on the dried product2Under protection, heating to 500 ℃ in a tube furnace at the speed of 5 ℃/min, (4) introducing water vapor for activation for 8h, and (5) activating in N2Cooling to room temperature under protection, (6) treating the product in boiling water for 90min, and (7) drying at 100 ℃, wherein the obtained supported catalyst is marked as catalyst (I). By mass, the ruthenium content in the catalyst (I) was 0.5%, the CaO content was 2%, and the specific surface area of the catalyst was 352m2/g。
Example 2
Taking D061 macroporous cation exchange resin, (1) washing with 3 times volume of saturated calcium carbonate and 5% of dilute hydrochloric acid in sequence of alkali, water, acid, water and alkali, (2) adding an ammonia solution containing 15% of nickel acetate at 70 ℃ for ion exchange, wherein the mass ratio of nickel acetate to resin is 1:2, and (3) drying the product, and then carrying out N-phase ion exchange2Under protection, heating in a tube furnace at a heating rate of 10 ℃/min to 900 ℃, (4) activating for 6h by introducing air, and (5) activating in N2Cooling to room temperature under protection, (6) treating the product in boiling water for 30min, (7) drying at 110 ℃, and recording the obtained supported catalyst as catalystAn agent (II). The content of nickel oxide in the catalyst (II) was 18.7% by mass, the content of CaO was 0.5% by mass, and the specific surface area of the catalyst was 916m2/g。
Example 3
Taking D152 macroporous cation exchange resin, (1) washing with 3 times volume of saturated calcium hydroxide and 5% of dilute hydrochloric acid in sequence of alkali, water, acid, water and alkali, (2) adding ethanol solution containing 10% of cobalt acetate at 70 ℃ for ion exchange, wherein the mass ratio of the cobalt acetate to the resin is 1:10, and (3) drying the product, and then carrying out N-phase ion exchange2Under protection, heating in a tube furnace at a heating rate of 8 ℃/min to 700 ℃, (4) introducing H2Activating for 2H by using/Ar mixed gas, wherein the mixing ratio of the mixed gas is H2Ar is 1:4 (volume), (5) is N2Cooling to room temperature under protection, (6) treating the product in boiling water for 60min, (7) drying at 110 ℃, and recording the obtained supported catalyst as catalyst (III). By mass, the cobalt content in the catalyst (III) was 1.6%, the CaO content was 1%, and the specific surface area of the catalyst was 472m2/g。
Example 4
Taking D113 macroporous cation exchange resin, (1) washing with 3 times volume of saturated calcium carbonate and 10% of dilute hydrochloric acid in sequence of alkali, water, acid, water and alkali, (2) adding a solution containing 10% of hydrated iron acetate at 60 ℃ for ion exchange, wherein the mass ratio of the hydrated iron acetate to the resin is 1:5, and (3) drying the product, and then carrying out N-phase ion exchange on the dried product2Under protection, heating in a tubular furnace at a heating rate of 15 ℃/min to 600 ℃, (4) introducing H2Activating for 5H by using/Ar mixed gas, wherein the mixing ratio of the mixed gas is H2Ar is 1:5 (volume) and (5) is N2Cooling to room temperature under protection, (6) treating the product in boiling water for 45min, and (7) drying at 110 ℃, wherein the obtained supported catalyst is marked as catalyst (IV). The catalyst (IV) contained 7.6% by mass of iron oxide, 1.5% by mass of CaO and a specific surface area of 300m2/g。
Example 5
Taking ND-77 type macroporous cation exchange resin produced by Jiangsu south environmental protection science and technology Limited company, (1) using 3 times volume of saturated calcium hydroxide and 10% of dilute hydrochloric acid according to alkaliSequentially washing with water, acid, water and alkali, (2) adding a solution containing 10% of hydrated nickel acetate at 60 ℃ for ion exchange, wherein the mass ratio of the hydrated nickel acetate to the resin is 1:3, and (3) drying the product and then carrying out N2Under protection, heating in a tubular furnace at a heating rate of 15 ℃/min to 600 ℃, (4) introducing H2Activating for 5H by using/Ar mixed gas, wherein the mixing ratio of the mixed gas is H2Ar is 1:5 (volume) and (5) is N2Cooling to room temperature under protection, (6) treating the product in boiling water for 30min, (7) drying at 110 ℃, and recording the obtained supported catalyst as catalyst (V). The catalyst (V) had a nickel oxide content of 20.0% by mass, a CaO content of 0.5% by mass, and a specific surface area of 1000m2/g。
Example 6
Taking ND-77 type macroporous cation exchange resin produced by Jiangsu south environmental protection science and technology limited company, (1) washing with 3 times volume of saturated calcium hydroxide and 10% of dilute hydrochloric acid according to the sequence of alkali, water, acid, water and alkali, (2) adding mixed solution of ruthenium acetate and nickel acetate at 60 ℃ for ion exchange, wherein the mass ratio of the nickel acetate to the resin is 1:5 and 1:50 respectively, and (3) drying the product, and then carrying out N-phase ion exchange2Under protection, heating in a tubular furnace at a heating rate of 5 deg.C/min to 800 deg.C, and (4) introducing H2Activating for 7H by using/Ar mixed gas, wherein the mixing ratio of the mixed gas is H2Ar is 1:3 (volume), (5) is N2Cooling to room temperature under protection, (6) treating the product in boiling water for 90min, and (7) drying at 100 ℃, wherein the obtained supported catalyst is marked as a catalyst (VI). By mass, the content of nickel oxide in the catalyst (VI) was 8.2%, the content of ruthenium oxide was 0.8%, the content of CaO was 1%, and the specific surface area of the catalyst was 580m2/g。
Comparative example 1A natural mineral catalyst dolomite, which was calcined at 900 ℃ for 4 hours and packed in a sealed bag for later use, was composed of, by mass, 29.06% CaO, 22.44% MgO, and 0.38% SiO2，0.20％Fe2O3，0.08％Al2O3。
Comparative example 2A Cu-Zn-Al catalyst was purchased and composed of 30% CuO and 35% ZnO by mass，20％Al2O3，5％MnO2，10％ZrO2。
The catalysts (I) to (VI) and the catalysts of comparative examples 1 and 2 were charged into a hydrothermal reactor, respectively, and the reaction process was as shown in FIG. 3, taking industrial sludge from a chemical plant as a treatment object, and the reaction conditions and the reaction results are shown in the following tables.
The catalyst obtained in the embodiments 1 to 6 has similar structure and performance, and the structure and performance before and after the reaction have no significant change, which shows that the catalyst has good stability.
TABLE 1 comparison of catalytic conditions and results for catalysts in examples 1-6 and catalysts in comparative examples 1 and 2
Claims (8)
1. A supported catalyst, a carrier is loaded with a main catalytic active component, and the supported catalyst is characterized in that: the carrier is a calcium type cation exchanger which is macroporous cation exchange resin; the main catalytic active component is one or more of nickel, iron, cobalt, ruthenium and oxides thereof, and the loading amount is 0.5-20% in terms of mass fraction; the supported catalyst also contains CaO, and the mass of the CaO is 0.5-2.0% of the total mass of the catalyst; the main catalytic active component is combined with the carrier through electrostatic acting force.
2. A supported catalyst according to claim 1, wherein: the specific surface area of the supported catalyst is 300-1000 m2/g。
3. The application of the supported catalyst of any one of claims 1-2 in the field of catalytic degradation of organic waste by a hydrothermal method is characterized in that: the reaction temperature is 700-900 ℃, the reaction pressure is 23-30 MPa, the reaction time is 60-90 min, and the conversion rate of organic matters is more than 95%.
4. A preparation method of a supported catalyst mainly comprises the following steps:
(1) using Ca as cation exchanger2+Treating the solution into a calcium type to form a calcium type cation exchanger, wherein the cation exchanger is macroporous cation exchange resin;
(2) carrying out ion exchange on the calcium type cation exchanger prepared in the step (1) by using an ethanol solution or an ammonia water solution of a precursor of a main catalytic active component, wherein the reaction temperature is 60-70 ℃;
(3) drying the product of the step (2) and then adding the dried product into N2Heating to 500-900 ℃ under protection;
(4) activating for 2-8 h by introducing activating gas;
(5) in N2Cooling to room temperature under protection;
(6) treating the product obtained in the step (5) in boiling water for 30-90 min;
(7) and drying to obtain the supported catalyst.
5. The process for preparing a supported catalyst according to claim 4, wherein: in the step (1), the Ca is used2+The solution treatment process comprises the step of passing through an ion exchange column filled with a carrier in the order of alkali, water, acid, water and alkali, wherein the alkali is a saturated solution of calcium hydroxide or calcium carbonate, and the acid is 5-10% hydrochloric acid.
6. The process for preparing a supported catalyst according to claim 4, wherein: in the step (2), the precursor of the main catalytic active component is one or more of nickel acetate, iron acetate, cobalt acetate, ruthenium acetate and hydrates thereof, and the dosage of the precursor is 1-50% of the mass of the cation exchanger.
7. The process for preparing a supported catalyst according to claim 4, wherein: in the step (3), the temperature rise speed is 5-15 ℃/min.
8. According to the claimsThe preparation method of the supported catalyst according to claim 4 is characterized in that: in the step (4), the activation method is to introduce water vapor or air or H2The mixed gas of/Ar, wherein the mixing ratio of the mixed gas is H2Ar is 1, (3-5) in volume ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610654478.5A CN107243342B (en) | 2016-08-11 | 2016-08-11 | Supported catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610654478.5A CN107243342B (en) | 2016-08-11 | 2016-08-11 | Supported catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107243342A CN107243342A (en) | 2017-10-13 |
| CN107243342B true CN107243342B (en) | 2020-04-24 |
Family
ID=60016178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610654478.5A Active CN107243342B (en) | 2016-08-11 | 2016-08-11 | Supported catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107243342B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983407A (en) * | 2017-12-18 | 2018-05-04 | 深圳市固废环保科技有限公司 | A kind of hydrocarbon cracks agent and its application in gasification of biomass |
| CN109908919B (en) * | 2019-03-11 | 2021-08-31 | 华侨大学 | Spontaneous dispersion monoatomic Ag1/Co3O4Process for preparing catalyst |
| CN110508306A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol LaNiO3/SiC-SiO2- Foam and preparation method thereof |
| CN111203184B (en) * | 2020-02-24 | 2022-06-17 | 成都信息工程大学 | Fe-Al-Zr anthracite modified material and preparation method and application thereof |
| CN111592903B (en) * | 2020-04-29 | 2021-10-19 | 中国科学院广州能源研究所 | Method for removing tar by using municipal sludge |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559365A (en) * | 2009-05-21 | 2009-10-21 | 中国矿业大学(北京) | Preparation and application of supported silver catalyst |
| CN103394354A (en) * | 2013-08-22 | 2013-11-20 | 神华集团有限责任公司 | Catalyst loaded on carbon sphere and preparation method of catalyst |
| CN104986742A (en) * | 2015-06-29 | 2015-10-21 | 济南大学 | Bead-chain-like graphitized carbon nitride nano material and preparation method thereof |
-
2016
- 2016-08-11 CN CN201610654478.5A patent/CN107243342B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559365A (en) * | 2009-05-21 | 2009-10-21 | 中国矿业大学(北京) | Preparation and application of supported silver catalyst |
| CN103394354A (en) * | 2013-08-22 | 2013-11-20 | 神华集团有限责任公司 | Catalyst loaded on carbon sphere and preparation method of catalyst |
| CN104986742A (en) * | 2015-06-29 | 2015-10-21 | 济南大学 | Bead-chain-like graphitized carbon nitride nano material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107243342A (en) | 2017-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107243342B (en) | Supported catalyst and preparation method and application thereof | |
| CN103394356B (en) | Biomass pyrolysis gasification multifunctional iron-based catalyst and preparation method thereof | |
| CN108355668B (en) | Methanation catalyst and preparation method and application thereof | |
| CN110327933B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN101518728B (en) | Integral type high specific surface area porous sorption agent and preparation method thereof | |
| CN103394367A (en) | Preparation method of ZSM-5 molecular sieve core shell double-layer catalyst by utilizing fly ash | |
| CN110152663A (en) | It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application | |
| CN107890870A (en) | A kind of carbon dioxide and water methanation catalyst and its preparation method and application | |
| CN111250092B (en) | Preparation method and application of biomass honeycomb-shaped semicoke-loaded nickel-iron nanoparticle catalyst | |
| CN109908931B (en) | Catalyst with Al modified activated carbon as carrier and preparation method thereof | |
| CN103408032B (en) | Method for supercritical hydrothermal synthesis of flyash zeolite | |
| CN107233888A (en) | Biomass prepares gas combustion multifunction catalyst and preparation method | |
| CN109261183B (en) | Cobalt-based catalyst for methanation of carbon dioxide and application thereof | |
| CN103183319B (en) | A kind of method of lighter hydrocarbons producing hydrogen from steam conversion, device and reactive system | |
| KR101614031B1 (en) | Methanation catalyst of carbon dioxide, preparation method and usage of same | |
| CN111804300A (en) | Ozone oxidation catalyst for advanced treatment of organic wastewater and preparation method thereof | |
| CN103480368B (en) | A kind of low-carbon (LC) gaseous mixture catalytic combustion deoxygenation catalyst and preparation method thereof | |
| CN107638883B (en) | Catalyst for directly synthesizing low-carbon olefin by Fischer-Tropsch synthesis, preparation and application | |
| CN103736524A (en) | Preparation method of hydrocarbon conversion catalyst carrier | |
| CN109701556B (en) | Method for removing trace carbon oxides in methanol-containing hydrogen at low temperature | |
| CN109701557B (en) | Composite catalyst, activated composite catalyst, and preparation method and application thereof | |
| CN110092702B (en) | Method for preparing methane by catalytic hydrogenation of biological coke | |
| CN107376915B (en) | Carbon dioxide methanation catalyst and preparation method thereof | |
| CN113426448A (en) | Preparation method and application of novel biochar-based tar cracking catalyst | |
| CN113731422A (en) | Preparation method of slurry bed methane synthesis catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |