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Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry

A carbon dioxide and catalyst technology, applied in the field of industrial catalysts, can solve the problems of catalyst carbon deposition and inability to industrialize, and achieve the effects of stable catalyst performance, strong anti-carbon deposition and high catalytic activity

Active Publication Date: 2009-06-24
SHANGHAI HUAYI ENERGY CHEM +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] The technical problem to be solved by the present invention is to provide an industrial catalyst for reforming natural gas-carbon dioxide to produce synthesis gas, its preparation method and its application in industrial scale-up, so as to overcome the shortcomings of existing catalysts that are seriously carbon-deposited and cannot be industrialized

Method used

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  • Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry
  • Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Raw material: nickel nitrate: Ni(NO 3 ) 2· 6H 2 o

[0037] Lanthanum nitrate: La(NO 3 ) 3· 6H 2 o

[0038] Citric acid: HO 2 CCH 2 (OH)(CO 2 H)CH 2 CO 2 h

[0039] Ethylene glycol: HOCH 2 CH 2 Oh

[0040] Aluminum glue: AlOOH

[0041] Prepare a certain concentration of Ni(NO 3 ) 2 and La(NO 3 ) 3 The mixed aqueous solution, and then add citric acid and ethylene glycol solution of 1.5 times the concentration of metal ions. Stir for 20 hours under the condition of 50-60 degrees Celsius to obtain a green transparent gel. The gel is aged at a constant temperature for 2-3 days, and then foamed and dried in an oven at 70-80° C. for 20 hours under normal pressure. That is, the precursor of a porous Ni-based catalyst is obtained. The precursor is calcined in the air at 500° C. for 6 hours to prepare the nano-particle Ni-La powder catalyst. The catalyst is ground, mixed with 10% aluminum glue, and then processed into In the catalyst for industrial use, t...

Embodiment 2

[0047] According to the same method as in Example 1, mix La(NO 3 ) 3 and Ni(NO 3 ) 2 solution, adding a small amount of RuCl 3 or RhCl 3 Dissolve in the mixed solution, and then add organic reagents such as citric acid with 1.5 times the concentration of metal ions.

[0048] Stir at 60°C for more than 10 hours to form a uniform transparent Ni-M-La sol (M=Ru and / or Rh). Aging at room temperature for 4-5 days, foaming and drying in an oven at 110-120°C for 10 hours under normal pressure. Then bake in a muffle furnace at 800 DEG C for 6 hours to prepare a nickel-based nano-catalyst containing noble metal Ru or Rh (0.01-2%). Then prepare according to the same method as in Example 1 The cylindrical industrial catalyst has the weight percentage of each component: 9-15% of Ni, 17-35% of La and 0.4% of Ru.

[0049] In the evaluation of catalyst activity, the commercially scaled-up catalyst was crushed into granular catalysts with a diameter of about 1-2 mm. Before the reacti...

Embodiment 3

[0054] According to the same method as in Example 1, La(NO 3 ) 3 and Ni(NO 3 ) 2 Inject the mixed solution of 200g of commercially available ZSM-5 molecular sieves (purchased from Nankai University Catalyst Factory), impregnate for 5 hours under constant stirring, then add citric acid and ethylene glycol with 1.5 times the metal ion concentration, and stir at 60°C Make a gel containing ZSM-5 carrier. Then aging according to the method of Example 1, foaming and drying in an oven, and finally calcining at 550° C. for 6 hours in a muffle furnace to obtain a supported catalyst containing 9% (weight ratio) of nickel. Then prepare 9%Ni-La / ZSM-5 industrial catalyst according to the method of embodiment 1 The weight percent content of each component is: Ni9%, La40-46%, and the rest are carrier, adhesive and auxiliary agent.

[0055] Pack 0.3 kg of industrial catalyst in the industrial scale-up reactor. The catalyst was heated at 850°C in 20% H 2 / N 2 Reduction in the mixed ga...

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Abstract

The invention provides an industrial catalyst for producing synthesis gas by natural gas-carbon dioxide reforming. The catalyst comprises the following components in percentage by weight: 5 to 19 percent of Ni, 20 to 70 percent of La, and 0 to 2 percent of precious metal; and the catalyst is prepared by powder molding or the impregnation of a carrier by an active constituent, and the carrier is amolecular sieve and a molding additive. The catalyst has high catalytic activity through a micro-reactor and pilot magnification activity evaluation; and compared with other catalysts, the catalyst has strong carbon deposition resistance and steady performance. The catalyst is suitable to produce the synthesis gas by reforming natural gas and carbon dioxide, and also is suitable to produce the synthesis gas by reforming combined raw materials such as flue gas, coke-oven gas and coal bed gas of fuel electric plants, dry gas of oil refineries and the like.

Description

Technical field: [0001] The invention belongs to the field of chemical industry, and in particular relates to an industrial catalyst for producing synthesis gas by reforming natural gas-carbon dioxide. Background technique: [0002] With the gradual increase in energy demand, the comprehensive utilization of natural gas and the reduction of "greenhouse effect" gas emissions have attracted widespread attention. China is rich in natural gas resources, but there are still gas associated with oil exploitation and coal seam mine gas that are not fully utilized. And found that there are a large number of natural gas resources (methane hydrate) in the seabed. In addition, a large amount of CO 2 The gas has constituted global warming and poses a serious threat to the future ecological balance. The main component of natural gas is methane (accounting for about 75-95%), and steam reforming of methane to produce synthesis gas or hydrogen has been industrialized for many years. Part...

Claims

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Application Information

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IPC IPC(8): B01J23/83B01J29/46C01B3/40
CPCY02P20/52
Inventor 刘炳泗王群赖春波唐大川张万东廖爱民田玲
Owner SHANGHAI HUAYI ENERGY CHEM
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