CN102527394B - Nickel-based catalyst and preparation method thereof - Google Patents
Nickel-based catalyst and preparation method thereof Download PDFInfo
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- CN102527394B CN102527394B CN201110420366.0A CN201110420366A CN102527394B CN 102527394 B CN102527394 B CN 102527394B CN 201110420366 A CN201110420366 A CN 201110420366A CN 102527394 B CN102527394 B CN 102527394B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 title abstract description 21
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 12
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000005554 pickling Methods 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims description 25
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000011265 semifinished product Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000001413 cellular effect Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000010306 acid treatment Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000003303 reheating Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 6
- 241000264877 Hippospongia communis Species 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate 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
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a nickel-based catalyst and a preparation method thereof. The catalyst takes cordierite or mullite subjected to high-temperature acid treatment as a carrier, nickel as an active component as well as one or more of Cu, Co, Mg, La, Ce, Ba, Al, Zr or Ca oxide or composite oxide as assistants, wherein the content of the active component is 5-25 percent, the content of the assistants is 1-10 percent and the balance of the carrier. The preparation method of the nickel-based catalyst comprises the steps of high-temperature pickling of the carrier, impregnating of the assistants, heating and decomposing, impregnating and reheating of the active components and part of assistants and the like. The nickel-bases catalyst disclosed by the invention has the advantages of high strength, favorable thermal stability, small resistance and suitability for high airspeed operation.
Description
Technical field
The invention belongs to catalyst field, relate in particular to a kind of nickel catalyst and preparation method thereof.
Background technology
World's natural gas resource reserves reach 3.5 × 10
14cubic meter, compares rich in petroleum resources.From world energy sources development trend, natural gas shared ratio in energy resource structure increases just year by year.In addition,, for opening up the requirement of new forms of energy and environmental protection, some are rich in CH
4gas also day by day come into one's own as the utilization of coal bed gas, oven gas etc.Therefore,, the in the situation that of petroleum resources growing tension, be rich in CH
4effective utilization of gas has very wide prospect.In order to adapt to future source of energy and industrial chemicals route shifts this inexorable trend, research and development utilization is rich in CH
4self-heating recapitalization technique and the catalyst of gas become focus.H in this reaction institute production of synthetic gas
2/ CO=2/1, is suitable for the building-up processes such as oil, methyl alcohol and methyl ether, receives the concern of academia and industrial quarters, becomes producing synthesis gas from natural gas and manufactures one, field new growth point.Need reaction system unstripped gas and oxygen to carry out premixed, so there is the possibility of blast in reaction system, particularly under high temperature and pressurized conditions, the security of reaction system is difficult to ensure card, and reaction needed is being carried out (air speed can reach tens times of Steam Reforming) under air speed greatly;
Cellular integer catalyst carrier is a kind of porous industrial ceramic, and its internal styling is the honeycomb shape parallel channels of many perforations, and these honeycomb ceramics unit are split to form by cancellate thin partition.Compared with the epigraph of general bulk, the feature such as ceramic honey comb has low heat expansion, and thermal insulation is better, and external surface area reaches, and weight is lighter, is therefore specially adapted to the catalyst carrier of various uses.In addition, because fluid is by the cavity of running through upper and lower surface on the partition of ceramic honey comb, so can utilize the partition of ceramic honey comb to carry out heat exchange and chemical reaction.At present, the chemical reaction carrier of ceramic honey comb extensive use and automobile exhaust purifier, ozone inhibition catalyst carrier, the heat exchange of metallurgical industry and the filtration of molten metal, chemical industry and catalyst, mining industry obtain the heat-barrier material of purified treatment, the spraying of light industry and the deadener of building materials industry and the kiln of toxic gas and liquid.
Therefore can find out, the feature that cellular integer catalyst carrier has can make reaction bed resistance reduce, and improves the effect of air speed, solves with this problem that autothermal reforming reaction system exists.Develop cellular integer catalyst carrier and become the needs of new application at present.
Summary of the invention
For solving above technical problem, the object of the invention provides a kind of novel nickel catalyst and preparation method.
A kind of nickel catalyst that the present invention solves the problems of the technologies described above, comprise carrier, active component and auxiliary agent, it is characterized in that: carrier is cordierite or mullite, active component is nickel, and auxiliary agent is one or more in Cu, Co, Mg, La, Ce, Ba, Al, Zr or Ca oxide or composite oxides;
In above-mentioned nickel catalyst, cordierite or mullite content are 74%～94%, and nickel content is that one or more content in 5%～25%, Cu, Co, Mg, La, Ce, Ba, Al, Zr or Ca oxide or composite oxides are 1～10%.
Above-mentioned nickel catalyst is that integer is cellular, and hole density is 7～62 hole/square centimeters.
Cordierite or mullite are through high temperature 1000-1400 ℃ of sintering processes mistake in the present invention.
It is high that catalyst has intensity, Heat stability is good, and resistance drop is little, is suitable for the running of large air speed.
A preparation method for nickel catalyst, comprises the following steps:
(1) high temperature pickling carrier: one or more in cordierite or mullite process 3-10% hydrochloric acid, sulfuric acid, nitric acid, at temperature 80-100 ℃, wash 2-5h, then wash with distilled water, until washing distilled water pH value=6.5-7.5, in 80 ℃ of baking ovens, dry 1-10h obtains semi-finished product A;
(2) dipping of auxiliary agent: one or more make solution B by the nitrate of 2-4%Cu, Co, Mg, La, Ce, Ba, Al, Zr or Ca, sulfate, acetate or chloride, semi-finished product A is placed in solution B and is flooded, temperature is 30～100 ℃, and 1～4h obtains semi-finished product C;
(3) add thermal decomposition: at 60～150 ℃ of temperature, dry 1～10h, is heated to afterwards 300～560 ℃ again and decomposes 4～8h and obtain semi-finished product D by semi-finished product C;
(4) dipping of active component and part of auxiliary: the nitrate of 45-60% nickel or 1-5%Cu, Co, Mg, La, Ce, Ba, Al, Zr or Ca, sulfate, acetate or muriatic form are made to solution E, D is placed in solution E and is flooded, temperature is 30～100 ℃, 1～8h, drier 1-10h obtains F in 80 ℃ of baking ovens; ;
(5) again add thermal decomposition: F repeating step (3) is made to nickel catalyst.
As improvement of the present invention, by the prepared nickel catalyst of step (5) carry out auxiliary agent for the second time dipping, add the dipping of thermal decomposition, active component and part of auxiliary and again add thermal decomposition, method is same step (2), (3), (4), (5) respectively, make required nickel catalyst.
The present invention adopts the method for high temperature pickling farthest to enrich the pore structure of cellular integer carrier and increased specific area, pressure drop while making reaction mass pass through catalyst bed reduces greatly, thereby can make system operate under very low pressure, thereby can make material away from explosion limit, react safer carrying out; At the catalyst of same volume, the external surface area of integer honeycombed catalyst is larger, by the dipping of auxiliary agent, has further improved external surface area.In application, methane catalytic combustion and methyl hydride catalyzed conversion are external diffusion control simultaneously, and therefore this catalyst can use very high dry gas air speed, has reduced instrument size, has saved investment.In addition, entrance oxygen content can be at larger scope modulation, has reduced the tolerance of circulation, has reduced energy consumption.The heat that auto-thermal produces, is consumed by the endothermic reaction of methane reforming, makes to react latent heat and is kept in gas, has reduced the temperature rise of beds, and what the gross calorific value of gas retained simultaneously is more.And improve the anti-carbon performance of catalyst by the adjustment of auxiliary agent.
the specific embodiment
Below in conjunction with the specific embodiment, the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
By cordierite carrier, at 80 ℃, dipping washing 3 hours in the dilute nitric acid solution that mass fraction is 10% then with distilled water washing, until washing distilled water pH value is 6.5, is dried 10h and obtains A in 80 ℃ of baking ovens;
In the mixed solution B that the mass fraction that A is immersed in to zirconium nitrate is 2%, the mass fraction of aluminum nitrate is 4%, dipping temperature is 90 ℃, and dip time is 1h, and then in 60 ℃ of baking ovens, dry 10h obtains C;
C is added at 300 ℃ to thermal decomposition 8h and obtain D;
D is immersed in to 60% nickel nitrate, in the mixed solution E of 5% cobalt nitrate, at 90 ℃ of temperature, dipping 1h, the then dry F that obtains for 10 hours in 80 ℃ of baking ovens;
F is added at 350 ℃ to thermal decomposition 8 hours, make nickel catalyst.
Embodiment 2
By cordierite carrier, at 80 ℃, dipping washing 5 hours in the dilute hydrochloric acid solution that mass fraction is 10% then with distilled water washing, until washing distilled water pH value is 7.5, is dried 10h and obtains A in 80 ℃ of baking ovens;
A is immersed in the mixed solution B of 2% cerous nitrate, 2% aluminum nitrate, dipping temperature is 30 ℃, and dip time is 4 hours, then within dry 10 hours in 80 ℃ of baking ovens, obtains C;
C is added at 450 ℃ to thermal decomposition and within 4 hours, obtain D;
D is immersed in the mixed solution E of 2% cerous nitrate, 2% aluminum nitrate, at 90 ℃ of temperature, dipping 1h, the then dry F that obtains for 10 hours in 80 ℃ of baking ovens;
F is added at 450 ℃ to thermal decomposition and within 4 hours, obtain G.
G being immersed in to 60% nickel nitrate, in the mixed solution of 4.5% copper nitrate, is at 90 ℃ in temperature again, dipping 1h, the then dry H that obtains for 10 hours in 80 ℃ of baking ovens;
H is added at 450 ℃ to thermal decomposition 4 hours, make nickel catalyst.
Embodiment 3
By cordierite carrier, at 80 ℃, dipping washing 4 hours in the solution of 9% hydrochloric acid, 3% nitric acid then with distilled water washing, until washing distilled water pH value is 7, is dried 10h and obtains A in 80 ℃ of baking ovens;
A is immersed in the mixed solution B of 2% cerous nitrate, 2% zirconium nitrate and 4% aluminum nitrate, at 100 ℃ of temperature, dipping 3h, then obtains C for dry 10 hours in 80 ℃ of baking ovens;
C is added at 500 ℃ to thermal decomposition and within 6 hours, obtain D;
D is immersed in 45% nickel nitrate, 1% lanthanum nitrate mixed solution E, and at 90 ℃ of temperature, dipping 3h, then obtains F for dry 10 hours in 80 ℃ of baking ovens;
F is added at 500 ℃ to thermal decomposition and within 6 hours, obtain G;
G is immersed in to 45% nickel nitrate, in the mixed solution of 1% lanthanum nitrate, is 90 ℃ in temperature, and then dipping 3h obtains H for dry 10 hours in 80 ℃ of baking ovens;
H is added at 500 ℃ to thermal decomposition 6 hours, make nickel catalyst.Wherein nickel oxide content is 5.8%, and cerium oxide content is 0.11%, and zirconia content is 0.1%, and lanthana content is 0.1%, and alumina content is 0.1%.
Embodiment 4
By mullite carrier, at 100 ℃, dipping washing 2 hours in the solution of 9% hydrochloric acid, 3% nitric acid then with distilled water washing, until washing distilled water pH value is 6.5, is dried 10h and obtains A in 100 ℃ of baking ovens;
A is immersed in mixed solution B 1% lanthanum nitrate, 2% aluminum nitrate, is 100 ℃ in temperature, dipping 3h, and then in 80 ℃ of baking ovens, dry 10h obtains C;
C is added at 560 ℃ to thermal decomposition and within 4 hours, obtain D;
D being immersed in the mixed solution E of 1% lanthanum nitrate, 2% aluminum nitrate, is at 100 ℃ in temperature, dipping 3h, the then dry F that obtains for 8 hours in 80 ℃ of baking ovens;
F is added at 560 ℃ to thermal decomposition and within 4 hours, obtain G;
G is immersed in the solution of 45% nickel nitrate, at 100 ℃ of temperature, dipping 3h, then obtains H for dry 10 hours in 80 ℃ of baking ovens;
H is added at 560 ℃ to thermal decomposition and within 4 hours, obtain I;
I being immersed in the solution of 45% nickel nitrate, is 100 ℃ in temperature, dipping 3h, and then in 80 ℃ of baking ovens, dry 10h obtains J.
J is added at 560 ℃ to thermal decomposition 4 hours, make nickel catalyst.
Determination of activity.
With N in gas chromatographic analysis gas
2, H
2, CH
4, CO, CO
2.
The following table 1 of unstripped gas component parts.
The composition of table 1 determination of activity raw material unstripped gas
| Title | CH 4 | N 2 | O 2 | CO 2 |
| Composition (V/V) | 45.63% | 44.18% | 9.51% | 0.68% |
, under 0.2MPa, reduce 5 hours at 350 ℃ with hydrogen, reduction air speed 4000h
-1.Reduction finishes rear disconnection hydrogen, adds methane, nitrogen, oxygen and water vapour, 700 ℃ of inlet temperatures, and pressure 0.3MPa, dry gas air speed is 8000 h
-1, steam/hydrocarbons ratio gets 1, carries out the active testing of methane self-heating recapitalization, records reaction result as described in Table 2.
The active testing result of four example catalyst samples of table 2
Can find out from the data of table 2, four kinds of methane self-heating recapitalization nickel in example are that integer catalyst all has good catalytic performance.
Claims (4)
1. a nickel catalyst, comprise carrier, active component and auxiliary agent, it is characterized in that: carrier is cordierite or mullite, active component is nickel, and auxiliary agent is one or more in Cu, Co, Mg, La, Ce, Ba, Al, Zr or Ca oxide or composite oxides; In above-mentioned nickel catalyst, cordierite or mullite content are 74%～94%, and nickel content is that one or more content in 5%～25%, Cu, Co, Mg, La, Ce, Ba, Al, Zr or Ca oxide or composite oxides are 1～10%; Above-mentioned nickel catalyst is that integer is cellular, and wherein, the preparation method of nickel catalyst, comprises the following steps:
(1) high temperature pickling carrier: one or more in cordierite or mullite process 3-10% hydrochloric acid, sulfuric acid, nitric acid, at temperature 80-100 ℃, wash 2-5h, then wash with distilled water, until washing distilled water pH value=6.5-7.5, in 80 ℃ of baking ovens, dry 1-10h obtains semi-finished product A;
(2) dipping of auxiliary agent: one or more make solution B by the Cu of 2-4%, Co, Mg, La, Ce, Ba, Al, Zr or Ca nitrate, acetate or chloride, semi-finished product A is placed in solution B and is flooded, temperature is 30～100 ℃, and 1～4h obtains semi-finished product C;
(3) add thermal decomposition: at 60～150 ℃ of temperature, dry 1～10h, is heated to afterwards 300～560 ℃ again and decomposes 4～8h and obtain semi-finished product D by semi-finished product C;
(4) dipping of active component and part of auxiliary: the Cu of the nickel of 45-60% and 1-5%, Co, Mg, La, Ce, Ba, Al, Zr or Ca nitrate, acetate or muriatic form are made to solution E, D is placed in solution E and is flooded, temperature is 30～100 ℃, 1～8h, drier 1-10h obtains F in 80 ℃ of baking ovens;
(5) again add thermal decomposition: F repeating step (3) is made to nickel catalyst.
2. a kind of nickel catalyst according to claim 1, is characterized in that: the hole density of above-mentioned nickel catalyst is 7～62 hole/square centimeters.
3. a kind of nickel catalyst according to claim 1, is characterized in that: cordierite or mullite are through high temperature 1000-1400 ℃ of sintering processes mistake.
4. a kind of nickel catalyst according to claim 1, it is characterized in that: by the prepared nickel catalyst of step (5) carry out auxiliary agent for the second time dipping, add the dipping of thermal decomposition, active component and part of auxiliary and again add thermal decomposition, method is same step (2), (3), (4), (5) respectively, make required nickel catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110420366.0A CN102527394B (en) | 2011-12-15 | 2011-12-15 | Nickel-based catalyst and preparation method thereof |
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|---|---|---|---|
| CN201110420366.0A CN102527394B (en) | 2011-12-15 | 2011-12-15 | Nickel-based catalyst and preparation method thereof |
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| CN102527394B true CN102527394B (en) | 2014-06-25 |
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|---|---|---|---|---|
| CN106311250A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Nickel-based catalyst, preparation method of nickel-based catalyst, reduction state nickel-based catalyst and method for preparing synthesis gas through methane auto-thermal reforming |
| CN105413734B (en) * | 2015-12-07 | 2020-05-26 | 西南化工研究设计院有限公司 | Nickel-based catalyst for preparing reducing gas by reforming methane-carbon dioxide and preparation method thereof |
| CN112742412B (en) * | 2021-01-20 | 2022-11-08 | 成都理工大学 | Mullite loaded W-promoted Co-based catalyst for autothermal reforming of acetic acid |
| CN116393137A (en) * | 2023-03-28 | 2023-07-07 | 德龙钢铁有限公司 | Catalyst for high-humidity sintering flue gas and preparation method and application thereof |
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| CN101560413A (en) * | 2009-05-15 | 2009-10-21 | 中国科学院广州能源研究所 | Method for automatic thermocatalytic reforming and purification of biomass fuel gas and device |
| CN102000570A (en) * | 2010-10-11 | 2011-04-06 | 广东工业大学 | Pd/Ce0.8Zr0.2O2/cordierite honeycomb ceramic monolithic catalyst, preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560413A (en) * | 2009-05-15 | 2009-10-21 | 中国科学院广州能源研究所 | Method for automatic thermocatalytic reforming and purification of biomass fuel gas and device |
| CN102000570A (en) * | 2010-10-11 | 2011-04-06 | 广东工业大学 | Pd/Ce0.8Zr0.2O2/cordierite honeycomb ceramic monolithic catalyst, preparation method and application thereof |
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