CN1093433C - Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process - Google Patents
Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process Download PDFInfo
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- CN1093433C CN1093433C CN99100701A CN99100701A CN1093433C CN 1093433 C CN1093433 C CN 1093433C CN 99100701 A CN99100701 A CN 99100701A CN 99100701 A CN99100701 A CN 99100701A CN 1093433 C CN1093433 C CN 1093433C
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Abstract
The present invention relates to a catalyst which uses nickel as the active component of the catalyst and is used for producing synthetic gases by the natural oxidation and the reformation of auxiliary agents. The catalyst comprises nickel oxide, alkaline earth oxide or rare earth oxide, wherein the catalyst has the component of Ln<x>O<y>-Ni /MAl2O4; the carrying capacity corresponding to a carrier is 1.0 to 20% of Ni, 1 to 20% of Ln, and 1 to 15% of M; the Ln is La, Ce, Mg, Ca, Ba, Co and Pd; the M is Ni, Co, Mg, Ca and Ba. The carrier or the surface of the carrier is formed into a spinel structure. The present invention has the advantages of rich sources of the catalyst carrier, simple preparation, industrial production, low reaction temperature for the oxidation production of the synthetic gases, high stability, high selectivity, high activity, sintering resistance, loss resistance and good reproducibility. The present invention overcomes the defect of catalyst deactivation generated by the irreversible solid phase reaction between the Ni and the catalyst carrier.
Description
The natural gas auto-thermal oxidation and reformation catalyst for preparing synthetic gas and the manufacture method thereof of the present invention relates to a kind of nickel and be the activity of such catalysts component, adding auxiliary agent and carrier surface is modified.
Natural gas catalyzing part oxidation preparing synthetic gas is a kind of gas utilization method that great industrial applications prospect is arranged, have following problem but existing Ni is catalyst based: (1) is under the high temperature of reaction, serious irreversible solid phase reaction takes place between Ni and catalyst carrier, promptly
(2) catalyst surface carbon distribution inactivation; (3) sintering of active component and inactivation; (4) the slow catalysqt deactivation that causes of factor such as losss and be difficult to satisfy the requirement that industrialization is turned round of Ni.
The characteristics of catalyst are that carbon accumulation resisting ability is stronger among the patent application CN1157256 of Xiamen University, but need evaporated under reduced pressure in its preparation process and utilize citric acid to prepare the organic precursor of catalyst.Preparation of catalysts has been introduced heavy rare earth metal oxide Re among the patent application CN1156641 of Chengdu organic chemistry institute of the Chinese Academy of Sciences
2O
3, the oxide of roasting or employing fusion prepares catalyst under 1300～1600 ℃ of high temperature.Chinese Academy of Sciences Chengdu has introduces precious metals pt as auxiliary agent in the Preparation of catalysts among the chemical patent application CN1131638 of institute.The used carrier material of the patent application CN1120469 of South China Science ﹠ Engineering University is ZrO
2, TiO
2, ZSM molecular sieve and their composition.Catalyst among the patent application CN1154944 of the Dalian Chemistry and Physics Institute is in α-Al with alkaline earth, rare earth and active constituent loading
2O
3On.Prepared catalyst then is as auxiliary agent with alkali metal oxide among the patent application CN1130150 of the Dalian Chemistry and Physics Institute.
It is low that the object of the invention provides a kind of oxidation and reformation preparing synthetic gas reaction temperature, high stability, high selectivity, high activity, anti-sintering, anti-current mistake, good reproducibility and anti-carbon ability, low-cost natural gas auto-thermal oxidation and reformation catalyst for preparing synthetic gas and preparation method thereof.
Technical scheme provided by the invention is:
A kind of nickel oxide, alkaline earth or rare earth oxide catalyst of containing, the component formula is: LnxOy-Ni base/M Al
2O
4Wherein each component with respect to the loading (weight) of carrier is: Ni1.0～20%, Ln1～20%, M1～15%.
Ln can be element La, Ce, Mg, Ca, Ba, Co, Pd in the component, and M can be element Ni, Co, Mg, Ca, Ba, and carrier or carrier surface are spinel structures.
Above-mentioned Preparation of catalysts method comprises the steps:
A. get an amount of Al (NO
3)
3With second component (M) Ni, Co, Mg, Ca, Ba solution, with NH
3H
2O, NH
4HCO
3Or (NH
4)
2CO
3Solution is precipitating reagent, precipitates ageing, washing and oven dry preparation precursor carrier fully;
B. sell γ-Al with the merchant
2O
3To be dipped into just wet being immersed in the second an amount of component Ni, Co, Mg, Ca, the Ba solution, dry, stand-by;
C. the precursor roasting of step a or b preparation is 5-24 hour, makes carrier or carrier surface form spinel structure;
D. the carrier that contains spinel structure of above-mentioned steps c preparation is immersed in the mixed solution of the active component (Ni) of suitable composition and auxiliary agent (Ln), be as the criterion to be dipped into just to wet;
E. the catalyst precarsor that above-mentioned steps d is made is placed, and oven dry activates 5-15 hour and makes.
Preferably 700～1200 ℃ of temperature, preferably 550～650 ℃ of activation temperatures are watered in above-mentioned preparation roasting.
The catalyst carrier source of the present invention's preparation is abundant, preparation process is simple, be suitable for industrialized large-scale production, the methane portion oxidation synthesis gas reaction temperature is low, the result is near calculation of thermodynamic equilibrium, and catalyst also has high stability, high selectivity, high activity, anti-sintering, anti-current mistake, good reproducibility and anti-carbon ability.Catalyst has overcome under the high temperature of reaction, and the serious catalysqt deactivation that irreversible solid phase reaction caused takes place between Ni and catalyst carrier.
For example: at 700 ℃, under the 0.1MPa, unstripped gas air speed GHSV=200000/h, reaction 100h, methane conversion＞92%, H
2Be respectively 100% more than 93% with the selectivity of CO.Unstripped gas air speed GHSV=520000/h, reaction 300h, methane conversion＞90%, the selectivity of H2 and CO is respectively more than 96% and 91%, and catalyst reaction finishes all not have sintering and deactivation phenomenom.With the catalyzer temperature-elevating to 800 ℃ of reaction 300h, methane conversion＞95%, the selectivity of H2 and CO is respectively more than 98.2% and 98.8%.Unstripped gas air speed GHSV=120000/h reacted 24 hours under 0.5MPa pressure, and catalyst keeps the yield of CH_4_ conversion ratio, CO and H2 can reach 90-92%, 83-84% and 89-90% respectively.At 700 ℃, under the 0.1MPa, unstripped gas air speed GHSV=200000/h, the catalyst of reaction 100h contains 33%O through 850 ℃
2He atmosphere handle after, after 30 minutes, its catalytic reaction activity slightly descends 700 ℃ of in-situ reducing, but reaction temperature is elevated to 727 ℃ by 700 ℃, catalyst reaches original activity.
Below be the embodiment of the invention: Preparation of Catalyst example one:
Get 0.5 gram merchant and sell γ-Al
2O
3, be immersed in 0.09ml2M Mg (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 900 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 0.10ml 1M Ni (NO
3)
2With 0.76ml 0.1M La (NO
3)
3Solution, dipping 24h, 80 ℃ of oven dry down were 630 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 1%, and Ln=La 2%, and M=Mg 1%.Preparation of Catalyst example two:
Get 0.5 gram merchant and sell γ-Al
2O
3, be immersed in 0.59ml 1M Co (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 1100 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 0.60ml 1M Ni (NO
3)
2With 0.63ml 1M Mg (NO
3)
2Solution, dipping 24h, 80 ℃ of oven dry down were 630 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 8%, and Ln=Mg 3%, and M=Co 5%.Preparation of Catalyst example three:
Get 1 gram merchant and sell γ-Al
2O
3, be immersed in 0.72ml 2M Mg (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 1100 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 0.60ml 1M Ni (NO
3)
2With 3.16ml 0.1M Ba (NO
3)
2Solution, dipping 24h, 80 ℃ of oven dry down were 550 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 3.5%, and Ln=Ba 12%, and M=Mg 3.5%.Preparation of Catalyst example four:
Get 200ml 1M Al (NO
3)
3With 14.69ml 2M Mg (NO
3)
2Solution is with dense NH
4OH solution splashes into slowly that the PH to solution is 14 in the solution, and solution temperature maintains 40 ℃ in the precipitation process, and mixing speed is followed solution viscosity to increase and slowly is increased to 1800 rev/mins by 1200 rev/mins of beginning.Kept same temperature and mixing speed after reaction finishes two hours, and stopped to stir and heating, precipitation battle arrayization 100 hours, suction filtration, washing is spent the night.In 80 ℃ of 12h and 120 ℃ of 12h oven dry, at 900 ℃ of following roasting 10h, naturally cool to room temperature, make carrier or carrier surface form spinel structure.Prepared carrier immerses 12.16ml 1M Ni (NO
3)
2With 2.68ml1M Ca (NO
3)
2Solution, dipping 24h, 80 ℃ of oven dry down were 500 ℃ of following roastings 6 hours.Each component with respect to the loading of carrier is: Ni 71%, and Ln=Ca 9%, and M=Mg 7%.Preparation of Catalyst example five:
Get 2 gram merchants 4 and sell γ-Al
2O
3, be immersed in 5ml 1M Mg (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 900 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 5ml 1M Ni (NO
3)
2With 30ml 1M Ba (NO
3)
2Solution, dipping 24h, 80 ℃ of oven dry down were 600 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 15%, and Ln=Co 20%, and M=Mg 15%.Preparation of Catalyst example six:
Get 100ml 2M Al (NO
3)
3With 7.5ml 2M Mg (NO
3)
2Solution is with 320ml 1M (NH
4)
2CO
3Solution splashes in the solution slowly, and solution temperature maintains 40 ℃ in the precipitation process, and mixing speed is followed solution viscosity to increase and slowly is increased to 2000 rev/mins by 1200 rev/mins of beginning.Kept same temperature and mixing speed after reaction finishes two hours, and stopped to stir and heating, precipitation battle arrayization 100 hours, suction filtration, washing is spent the night.In 80 ℃ of 12h and 120 ℃ of 12h oven dry, at 1100 ℃ of following roasting 10h, naturally cool to room temperature, make carrier or carrier surface form spinel structure.Prepared carrier immerses 12.16ml 1MNi (NO
3)
2With 14.65ml 1M La (NO
3)
3Solution, dipping 24h, 80 ℃ of oven dry down were 500 ℃ of following roastings 6 hours.Each component with respect to the loading of carrier is: Ni 7%, and Ln=La 20%, and M=Mg 3%.Preparation of Catalyst example seven:
Get 2 gram merchants and sell γ-Al
2O
3, be immersed in 0.5ml 1M Ca (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 900 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 5ml 1M Ni (NO
3)
2With 2ml 0.5M Ce (NO
3)
2Solution, dipping 24h, 80 ℃ of oven dry down were 600 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 15%, and Ln=Ce 2%, and M=Ca 1%.Preparation of Catalyst example eight:
Get 1 gram merchant and sell γ-Al
2O
3, be immersed in 1.44ml 2M Mg (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 1100 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 2ml 1M Ni (NO
3)
2With 0.15g 0.88wt%PdCl
2Solution, dipping 24h, 80 ℃ of oven dry down were 600 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 12%, and Ln=Pd 1%, and M=Mg 7%.Preparation of Catalyst example nine:
Get 1 gram merchant and sell γ-Al
2O
3, be immersed in 0.165ml 0.5M Mg (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 1100 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 0.5ml 1M Ni (NO
3)
2With 0.72ml 0.1M La (NO
3)
3Solution, dipping 24h, 80 ℃ of oven dry down were 600 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 3%, and Ln=La 1%, and M=Mg 1%.Preparation of Catalyst example ten:
Get 1 gram merchant and sell γ-Al
2O
3, be immersed in 3.09ml 2M Mg (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 1100 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 2.9ml 1M Ni (NO
3)
2With 10.8ml 0.1M La (NO
3)
3Solution, dipping 24h, 80 ℃ of oven dry down were 600 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 17%, and Ln=La 15%, and M=Mg 15%.Preparation of Catalyst example 11:
Get 2 gram merchants and sell γ-Al
2O
3, be immersed in 0.5ml 1M Ba (NO
3)
2Solution spends the night.80 ℃ of 12h oven dry, 900 ℃ of following roasting 10h naturally cool to room temperature, make carrier or carrier surface form spinel structure, and the carrier of preparation immerses 5ml 1M Ni (NO
3)
2With 2ml 0.5M Ce (NO
3)
2Solution, dipping 24h, 80 ℃ of oven dry down were 600 ℃ of roastings 6 hours.Each component with respect to the loading of carrier is: Ni 15%, and Ln=Ce 2%, and M=Ba 1%.
The method that catalyst of the present invention is produced synthesis gas from gas material is: premixed natural gas, oxygen or oxygen-containing gas, and the steam of different proportion feeds the reactor that catalyst is housed, 600～1000 ℃ of reaction temperatures, reactor can be normal pressure or pressurization static bed or fluidized-bed reactor, be reflected at normal pressure or add to depress and carry out, the reaction gas air speed can change in 7-120 * 104/h scope and not influence reaction result.Catalyst is at partial oxidation reaction of methane, 500～900 ℃ of reaction temperatures, comprehensive energy consumption and reaction result, 700～800 ℃ of suitable reaction temperatures;
Catalytic reaction effect example of the present invention is as follows:
Example one:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with catalyst among the preparation embodiment one.Catalyst amount 0.4g, particle diameter 40-60mesh, the reaction procatalyst is at 30ml/min H
2Middle original position prereduction 30min.With premixed 2/1CH
4/ O
2Gaseous mixture switches into reactor.700 ℃ of reaction temperatures, unstripped gas air speed GHSV=170000/h.Reaction result sees Table one: table one: a pair of partial oxidation reaction of methane result of catalyst embodiment (700 ℃)
11 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 92.37 | 82.43 | 8.93 | 90.33 | 91.47 | 99.03 |
Example two:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with catalyst among the preparation embodiment six.Catalyst amount 0.06g, unstripped gas air speed GHSV=520000/h, all the other conditions are the same, and reaction result sees Table two: table two: six couples of partial oxidation reaction of methane results of catalyst embodiment (700 ℃)
7 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 92.03 | 90.00 | 2.02 | 97.79 | 88.30 | 95.95 |
Example three:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with embodiment two catalyst in the preparation.Catalyst amount 0.1g, unstripped gas air speed GHSV=300000/h, all the other conditions are the same, and reaction result sees Table three: table three: two couples of partial oxidation reaction of methane results of catalyst embodiment (700 ℃)
7 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 91.33 | 87.04 | 4.28 | 95.31 | 87.58 | 95.90 |
Example four:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with embodiment eight catalyst in the preparation.Catalyst amount 0.06g, unstripped gas air speed GHSV=170000/h, all the other conditions are the same, and reaction result sees Table four: table four: eight couples of partial oxidation reaction of methane results of catalyst embodiment (700 ℃)
11 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 92.25 | 88.19 | 4.06 | 95.59 | 89.13 | 96.62 |
Example five:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with embodiment one catalyst in the preparation, catalyst amount 1g, 800 ℃ of reaction temperatures, unstripped gas air speed GHSV=115000/h, all the other conditions are the same, and reaction result sees Table five: table five: a pair of partial oxidation reaction of methane result of catalyst embodiment (800 ℃)
11 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 98.44 | 93.46 | 3.79 | 94.95 | 99.02 | 100 |
Example six:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with embodiment one catalyst in the preparation, catalyst amount 1g, 700 ℃ of reaction temperatures, unstripped gas air speed GHSV=170000/h, all the other conditions are the same, and reaction result sees Table six: table six: a pair of partial oxidation reaction of methane result of catalyst embodiment (700 ℃)
100 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 92.37 | 82.43 | 8.93 | 90.33 | 91.47 | 99.03 |
Example seven:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with embodiment five catalyst in the preparation, catalyst amount 0.06g, 800 ℃ of reaction temperatures, unstripped gas air speed GHSV=520000/h, all the other conditions are the same, and reaction result sees Table seven: table seven: five couples of partial oxidation reaction of methane results of catalyst embodiment (800 ℃)
10 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 95.04 | 93.9 | 1.14 | 98.80 | 93.13 | 97.99 |
Example eight:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with embodiment five catalyst in the preparation, 700 ℃ of reaction temperatures, all the other conditions are the same, and reaction result sees Table eight: table eight: five couples of partial oxidation reaction of methane results of catalyst embodiment (700 ℃)
300 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 88.96 | 85.85 | 3.76 | 96.51 | 84.99 | 95.5 |
Example nine:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with embodiment seven catalyst in the preparation, 700 ℃ of reaction temperatures, unstripped gas air speed GHSV=300000/h, all the other conditions are the same, and reaction result sees Table nine: table nine: seven couples of partial oxidation reaction of methane results of catalyst embodiment (700 ℃)
24 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 91.34 | 88.57 | 5.23 | 96.97 | 90.25 | 98.81 |
Example ten:
Adopt atmospheric fixed bed reaction unit, carry out partial oxidation reaction of methane with catalyst among the preparation embodiment one.Catalyst amount 0.1g, unstripped gas air speed GHSV=170000/h, all the other conditions are the same.React after 100 hours, adopt 27 ℃/min speed that this catalyst is being contained 33%O
2Helium-atmosphere under, carry out the temperature programming reaction of making charcoal, the regenerability of post catalyst reaction the results are shown in Table ten: table ten: the catalyst regeneration performance is investigated
Note: X: conversion ratio, Y: yield, S: selectivity
| Temperature (℃) | XCH 4 | YCO | YCO 2 | SCO | YH 2 | SH 2 |
| 700 (fresh) | 91.71％ | 83.14％ | 8.57％ | 90.66％ | 90.03％ | 98.17％ |
| 700 (100 hours reaction backs) | 85.82％ | 76.89％ | 8.93％ | 89.59％ | 81.37％ | 94.82％ |
| 727 (regeneration backs) | 92.05％ | 83.64％ | 8.40％ | 90.87％ | 90.46％ | 98.28％ |
Example 11:
Adopt pressurization static bed reaction unit, carry out partial oxidation reaction of methane with catalyst among the preparation embodiment seven.Catalyst amount 0.02g, 700 ℃ of reaction temperatures, reaction pressure 0.5MPa, unstripped gas air speed GHSV=700000/h.Reaction result sees Table 11: table ten one: seven couples of partial oxidation reaction of methane results of catalyst embodiment (700 ℃)
24 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 91 | 83.5 | 8.5 | 91.76 | 89.5 | 98.35 |
Example 12:
Adopt atmospheric fixed bed reaction unit, catalyst amount 0.06g, particle diameter 40-60mesh is increased to 800 ℃ with reaction temperature, raw material air speed GHSV=520000/h with catalyst E in the preparation enforcement five after carrying out partial oxidation reaction of methane 300h.Reaction result sees Table 12: table ten two: catalyst E is to partial oxidation reaction of methane result (800 ℃)
15 hours reaction time
| CH 4Conversion ratio (%) | CO yield (%) | CO 2Yield (%) | CO selectivity (%) | H 2Yield (%) | H 2Selectivity (%) |
| 95.04 | 93.90 | 1.14 | 98.80 | 93.13 | 97.99 |
Claims (6)
1. the catalyst of a natural gas auto-thermal oxidation and reformation preparing synthetic gas is characterized in that containing nickel oxide, alkaline earth or rare earth oxide, and the component formula is: LnxOy-Ni base/M Al
2O
4Wherein each component with respect to the loading (weight) of carrier is: Ni1.0～20%, Ln1～20%, M1～15%; Ln can be element La, Ce, Mg, Ca, Ba, Co, Pd in the above each component, and M can be element Ni, Co, Mg, Ca, Ba.
2. natural gas auto-thermal oxidation and reformation catalyst for preparing synthetic gas according to claim 1 is characterized in that catalyst carrier or carrier surface are spinel structures.
3. the preparation method of a natural gas auto-thermal oxidation and reformation catalyst for preparing synthetic gas comprises the steps:
A. get an amount of Al (NO
3)
3With second component (M) Ni, Co, Mg, Ca, Ba solution, with NH
3H
2O, NH
4HCO
3Or (NH
4)
2CO
3Solution is precipitating reagent, precipitates ageing, washing and oven dry preparation precursor carrier fully;
B. the precursor roasting of step a preparation is 5-24 hour, and carrier or carrier surface form spinel structure;
C. the carrier that contains spinel structure of above-mentioned steps b preparation is immersed in the mixed solution of the active component (Ni) of suitable composition and auxiliary agent (Ln), wet to be dipped into just;
D. the catalyst precarsor that above-mentioned steps c is made is placed, and oven dry activates 5-15 hour and makes.
4. the preparation method of natural gas auto-thermal oxidation and reformation catalyst for preparing synthetic gas according to claim 4 is characterized in that it is 700～1200 ℃ that temperature is watered in roasting;
5. the preparation method of natural gas auto-thermal oxidation and reformation catalyst for preparing synthetic gas according to claim 4 is characterized in that activation temperature is 550～650 ℃;
6. the preparation method of natural gas auto-thermal oxidation and reformation catalyst for preparing synthetic gas according to claim 4 is characterized in that step a also can adopt γ-Al
2O
3Be dipped into just and wet, be immersed in an amount of second component Ni, Co, Mg, Ca, the Ba solution, oven dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99100701A CN1093433C (en) | 1999-02-10 | 1999-02-10 | Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99100701A CN1093433C (en) | 1999-02-10 | 1999-02-10 | Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process |
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| CN1093433C true CN1093433C (en) | 2002-10-30 |
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| US3929431A (en) * | 1972-09-08 | 1975-12-30 | Exxon Research Engineering Co | Catalytic reforming process |
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| CN1154944A (en) * | 1996-01-17 | 1997-07-23 | 中国科学院大连化学物理研究所 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
| CN1156641A (en) * | 1996-12-30 | 1997-08-13 | 中国科学院成都有机化学研究所 | Process for preparing catalyst for producing synthetic gas from hydrocarbons |
| US5753143A (en) * | 1996-03-25 | 1998-05-19 | Northwestern University | Process for the CO2 reforming of methane in the presence of rhodium zeolites |
-
1999
- 1999-02-10 CN CN99100701A patent/CN1093433C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3929431A (en) * | 1972-09-08 | 1975-12-30 | Exxon Research Engineering Co | Catalytic reforming process |
| CN1120469A (en) * | 1995-06-15 | 1996-04-17 | 华南理工大学 | Catalyst for producing synthetic gas by methane selectively oxidizing |
| CN1154944A (en) * | 1996-01-17 | 1997-07-23 | 中国科学院大连化学物理研究所 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
| US5753143A (en) * | 1996-03-25 | 1998-05-19 | Northwestern University | Process for the CO2 reforming of methane in the presence of rhodium zeolites |
| CN1156641A (en) * | 1996-12-30 | 1997-08-13 | 中国科学院成都有机化学研究所 | Process for preparing catalyst for producing synthetic gas from hydrocarbons |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102949997A (en) * | 2012-09-18 | 2013-03-06 | 华东理工大学 | Catalyst-absorbent complex for absorbing and strengthening low-carbon hydrocarbon steam reforming hydrogen and preparing method of complex |
| CN102949997B (en) * | 2012-09-18 | 2015-01-07 | 华东理工大学 | Catalyst-absorbent complex for absorbing and strengthening low-carbon hydrocarbon steam reforming hydrogen and preparing method of complex |
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|---|---|
| CN1232720A (en) | 1999-10-27 |
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