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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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 39
- 239000007789 gas Substances 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 239000003345 natural gas Substances 0.000 title claims abstract description 13
- 238000002407 reforming Methods 0.000 title claims abstract 8
- 238000010438 heat treatment Methods 0.000 title description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 18
- 239000011029 spinel Substances 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 241000143437 Aciculosporium take Species 0.000 claims 1
- 239000012018 catalyst precursor Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 70
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 5
- 230000009849 deactivation Effects 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010671 solid-state reaction Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明涉及镍为催化剂的活性组分、添加助剂天然气自热氧化重整制合成气催化剂及其制造方法，催化剂含有氧化镍、碱土或稀土氧化物，组份为：LnxOy-Ni基/M Al2O4，其中相对于载体的担载量为：Ni1.0～20%，Ln1～20%，M1～15%，Ln为La、Ce、Mg、Ca、Ba、Co、Pd，M为Ni、Co、Mg、Ca、Ba，载体或载体表面是尖晶石结构，本发明催化剂载体来源丰富，制备简单，适于工业化生产，氧化制合成气反应温度低，还具有高稳定性、高选择性、高活性、抗烧结、抗流失、良好再生性，克服了Ni与催化剂载体间发生不可逆固相反应导致的催化剂失活。The present invention relates to nickel as the active component of the catalyst, adding additives, natural gas autothermal oxidation reforming synthesis gas catalyst and its manufacturing method. The catalyst contains nickel oxide, alkaline earth or rare earth oxide, and the components are: LnxOy-Ni base/M Al 2 O 4 , where the loading amount relative to the carrier is: Ni1.0-20%, Ln1-20%, M1-15%, Ln is La, Ce, Mg, Ca, Ba, Co, Pd, M is Ni, Co, Mg, Ca, Ba, the carrier or the surface of the carrier is a spinel structure, the source of the catalyst carrier of the present invention is rich, the preparation is simple, it is suitable for industrial production, the reaction temperature of oxidation to synthesis gas is low, and it also has high stability and high Selectivity, high activity, anti-sintering, anti-loss, good regeneration, overcome the catalyst deactivation caused by the irreversible solid-state reaction between 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 |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2857003B1 (en) * | 2003-07-02 | 2006-08-11 | Inst Francais Du Petrole | NEW CATALYST FOR VAPOREFORMING ETHANOL |
| US7449167B2 (en) * | 2004-07-08 | 2008-11-11 | Air Products And Chemicals, Inc. | Catalyst and process for improving the adiabatic steam-reforming of natural gas |
| EP2076331A4 (en) * | 2006-10-23 | 2012-02-08 | Bp Plc | METHOD AND CATALYST FOR THE CONVERSION OF HYDROCARBONS |
| KR100991263B1 (en) * | 2008-08-01 | 2010-11-01 | 현대중공업 주식회사 | Nickel-based catalyst for mixed reforming to reform natural gas into steam and carbon dioxide simultaneously |
| JP4897112B2 (en) | 2009-05-19 | 2012-03-14 | 新日本製鐵株式会社 | Tar-containing gas reforming catalyst, method for producing tar-containing gas reforming catalyst, tar-containing gas reforming method using tar-containing gas reforming catalyst, and method for regenerating tar-containing gas reforming catalyst |
| CN103447045B (en) * | 2012-05-28 | 2015-07-29 | 中国石油天然气股份有限公司 | Preparation method of pre-conversion catalyst for hydrogen production from dry gas |
| FR3013609B1 (en) * | 2013-11-27 | 2017-08-11 | Ifp Energies Now | PROCESS FOR THE CONVERSION OF CARBONYLIC ORGANIC COMPOUNDS AND / OR ALCOHOLS IN THE PRESENCE OF AN ALUMINATE COPPER CATALYST |
| PL3129142T3 (en) * | 2014-04-07 | 2021-05-31 | Haldor Topsøe A/S | Shell impregnated catalyst and process for producing a shell impregnated catalyst body |
| CN104399471A (en) * | 2014-09-29 | 2015-03-11 | 中国科学院上海高等研究院 | Nickel-based catalyst and moulding method and application thereof |
| CN112892542B (en) * | 2021-01-20 | 2022-10-14 | 成都理工大学 | Barium-aluminum spinel composite oxide cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
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| CN1120469A (en) * | 1995-06-15 | 1996-04-17 | 华南理工大学 | Catalyst for producing synthetic gas by methane selectively oxidizing |
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| 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 |
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| 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 |
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| 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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