CN1061320C - Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation - Google Patents
Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation Download PDFInfo
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- CN1061320C CN1061320C CN96115030A CN96115030A CN1061320C CN 1061320 C CN1061320 C CN 1061320C CN 96115030 A CN96115030 A CN 96115030A CN 96115030 A CN96115030 A CN 96115030A CN 1061320 C CN1061320 C CN 1061320C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a multi-component non-precious metal catalyst for preparing synthetic gas by directly oxidizing methane. Ni Rare earth and alkaline earth metal oxide are carried on alpha-Al2O3, and prepared in a dipping method. The active compositions of the catalyst comprise 5 to 12 wt% of Ni, 1.5 to 5 wt% of rare earth and 0.5 to 2 wt% of alkaline earth metal. The catalyst has the advantages of high activity and high selectivity. When air speed is higher than 10<5>h<-1> and the temperature of a bed layer is higher than 750 DEG C, the conversion rate of methane is more than 87%, the selectivity of H2 is more than 95%, and the activity of the catalyst approaches to that of a precious Rh catalyst. The catalyst o has constant activity after continuously reacting for 100 hours and good carbon deposit resistant performance, and is suitable for industrial production.
Description
The invention provides a cheap catalyst for preparing synthesis gas by directly oxidizing methane. The catalyst is under the condition of large space velocity (>10)5h-1) Has the advantages of high activity, high selectivity and good anti-carbon deposition performance.
The reaction for preparing the synthesis gas by directly oxidizing the methane comprises the following steps:
there have been reports since the beginning of the nineties abroad. The reaction has a light exotherm, a reaction product H2CO =2.0 (suitable for subsequent methanol and fischer-tropsch synthesis) and can be operated at high space velocity. Therefore, there is a high possibility of replacing the conventional steam reforming of methane to produce synthesis gas. At present, from the results reported in the literature, supported group VIII metals such as Rh, Pt, Ir and Ru are generally used as the catalyst. Wherein Rh has high activity and good carbon deposition resistance. And carbon deposition is easily generated on Ni, and Ni is easily lost in the operation process. There are few patents working in this regard and the active components of the catalysts used in the patent reports are mainly concentrated on the noble metals. For example, European patent 640559 uses Pt group elements (the content is 0.1-20%); european patent 640561 mainly uses Rh/La2Zr2O7. Because the main components are noble metals, the catalyst is expensive in cost and not very practical when used in industrial processes. Therefore, the development of a novel catalyst which is expected to become industrial production is the key point forthe popularization and application of the technology.
The invention aims to prepare a catalyst with high activity, good stability and strong anti-carbon deposition capability on a non-noble metal Ni-based catalyst through the modulation effect of adding an auxiliary agent. The catalyst is used for directly oxidizing methane to prepare synthesis gas under the condition of large space velocity, and the activity of the catalyst is close to that of a noble metal catalyst under the same condition.
The catalyst of the invention has Ni as the main active component and is loaded on α -Al with good thermal stability2O3The catalyst is characterized in that the catalyst is added with auxiliary agents of rare earth and alkaline earth metal elements for modulation, active components and the auxiliary agents are supported on a carrier by oxides, the weight percentage of the catalyst is 5-12 percent of Ni, the weight percentage of the rare earth and the alkaline earth metal are 1.5-5 percent and 0.5-2 percent respectively, and the rest is α -Al2O3. The rare earth can be one or a mixture of La, Ce or Pr.
The preparation process of the catalyst adopts a step impregnation method of nitrate solution of Ni, rare earth and alkaline earth metal to load active components and auxiliary components on a carrier. And drying, and roasting at 750-900 ℃ for 2-10 hours to obtain a finished product. The dipping sequence is carried out by using alkaline earth, rare earth and Ni nitrate.
The catalyst of the invention is used for preparing synthesis gas by directly oxidizing methane, and the operation conditions are as follows: space velocity: 1 to 7 x 105h-1,CH4/O2= 1.75-2.3, reaction temperature: 600-1000 ℃.
The technique of the present invention is described in one step below by way of examples and comparative examples.
Example 1 preparation of catalyst 1
0.191 g Ca (NO) is weighed out3)2·4H2O,0.136 g La (NO)3)3·4H2O,1.245 g Ni (NO)3)2·6H2Dissolving O in deionized water to obtain solutions, and mixing with 3 g of α -Al2O3(30 meshes to 40 meshes) sequentially dipping the solution for 18 hours respectively step by step, evaporating the dipped sample to dryness at 50 ℃ to 60 ℃, drying for 8 hours at 110 ℃ to 120 ℃, and then roasting for 6 hours in air at 800 ℃.
Example 2 preparation of catalyst 2
Weigh 0.316 g Mg (NO)3)2·6H2O,0.156 g Ce (NO)3)3·4H2O,1.314 g Ni (NO)3)2·6H2Dissolving O in deionized water to obtain solutions, and mixing with 3 g of α -Al2O3The solution was sequentially immersed in the solution (30 to 40 mesh) for 18 hours in steps, and the treatment conditions after immersion were the same as in example 1.
EXAMPLE 3 Performance of the catalyst 1
Determination of catalyst Activity: using the catalyst of example 1, 0.03ml of the catalyst (40mg of particles of 30 to 40 mesh) was charged in a quartz reaction tube having a diameter of 4mm by using a fixed bed flow reactor. Feed gas CH4And O2(CH4/O2=2.0, molar ratio) was fed into the reaction tube at a flow rate of 250 ml/min.A temperature thermocouple was inserted into the catalyst bed to measure the bed temperature. The product was detected by gas chromatography.
TABLE 1Ni-La-Ca/α -Al2O3Investigation of catalyst Performance
Catalyst methane conversion CO selectivity H2Selectivity H2Ratio 72081.787.895.02.1676085.390.296.42.1480088.492.797.22.1084091.394.798.02.0790094.496.598.92.05 of/CO bed temperature (. degree. C.) (%) (%) in terms of 72081.787.895.02.1676085.390.296.42.1480088.492.797.22.1084091.394.798.02.0790094.496.598.92.05
EXAMPLE 4 Performance 2 of the catalyst
Using the catalysts of examples 1 and 2 and the apparatus and conditions of example 3, the influence of the auxiliary on the catalytic performance and the carbon deposition resistance was examined, and the results and reaction conditions thereof are shown in tables 2 and 3
EXAMPLE 5 Properties of the catalyst 3
Catalyst chop stability studies were performed using the catalyst of example 2 and the apparatus and conditions of example 3, with the reaction conditions: space velocity =5 × 105h-1,CH4/O2=2.0, catalyst layer temperature: 780 ℃. The reaction is continued for 100 hours, and the activity of the catalyst is not Changed (CH)4Conversion 87%), H2And selectivity to CO and H2The ratio/CO also remains stable (H)2Selectivity 96%, CO selectivity 94%, H2The ratio of/CO is 2).
Comparative example 1 comparison of catalyst Activity
Catalysts containing Ni and the same amount of rare earth or alkaline earth metal component were prepared according to the methods for preparing the catalysts of examples 1 to 2, and the results of the tests were shown in tables 2 and 3, respectively, by using the apparatus and conditions of example 3.
TABLE 2 Effect of the promoters on catalyst ActivityCatalyst reaction temperature methane conversion COSelectivity H2Selectivity H2/CO Carrier α -Al2O3(%) (%) Ni 91092.794.898.822.08 Ni-Mg 89094.196.299.32.07 Ni-La 90094.596.298.82.05 Ni-Ce 89093.895.698.92.07 Ni-Mg 91095.696.099.82.08 Ni-La-Ca 90094.496.598.92.05 reaction conditions: space velocity: 5X 105h-1,CH4/O2=2.0。
TABLE 3 investigation of anti-carbon deposition Performance on different catalysts Ni Rh Ni-La Ni-Ce Ni-Mg Ni-La-Ca Ni-Ce-Mg Carrier α -Al2O3Amount of carbon deposition 6.370.46.765.924.692.101.0
Reaction conditions are as follows: space velocity: 5X 105h-1,CH4/O2Reaction time of = 2.10: for 1.5 hours.
The results of the above examples and comparative examples show that the catalyst of the present invention is used for preparing synthesis gas by direct oxidation of methane, and the catalyst has the advantages of high activity, high selectivity, carbon deposition resistance, etc. under the condition of large space velocity. Meanwhile, the catalyst has simple preparation process and low cost and is suitable for application in industrial production.
Claims (2)
1. The Ni-base catalyst for preparing synthetic gas by direct oxidation of methane features that rare-earth and alkaline-earth metal elements as assistant are added and the oxide of Ni, rare-earth and alkaline-earth metal is carried on α -Al2O3The alloy comprises 5-12 wt% of Ni, 1.5-5 wt% of rare earth metal, 0.5-2 wt% of alkaline earth metal and the balance α -Al2O3。
2. A method for preparing the catalyst of claim 1, wherein the catalyst is prepared by loading the components in α -Al of 30-40 meshes by using nitrate through a step-by-step impregnation method2O3And (2) sequentially carrying out impregnation on the carrier by using alkaline earth metal, rare earth metal and nitrate of Ni, wherein the impregnation time is 18 hours each time, evaporating the impregnated sample to dryness at 50-60 ℃, drying at 110-120 ℃ for 8 hours, and roasting the impregnated sample at 750-900 ℃ for 2-10 hours after drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115030A CN1061320C (en) | 1996-01-17 | 1996-01-17 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115030A CN1061320C (en) | 1996-01-17 | 1996-01-17 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
Publications (2)
| Publication Number | Publication Date |
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| CN1154944A CN1154944A (en) | 1997-07-23 |
| CN1061320C true CN1061320C (en) | 2001-01-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN96115030A Expired - Fee Related CN1061320C (en) | 1996-01-17 | 1996-01-17 | Nickel based catalyst for prepn. of synthetic gas by methane direct oxidation |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093433C (en) * | 1999-02-10 | 2002-10-30 | 石油大学(北京) | Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process |
| CN103752315B (en) * | 2014-01-15 | 2016-08-10 | 易高环保能源研究院有限公司 | A kind of metal phase carrier load type catalyst and its production and use |
| CN104084211B (en) * | 2014-07-10 | 2017-01-11 | 山西潞安矿业(集团)有限责任公司 | Catalyst for preparing synthesis gas or hydrogen and preparation method and application thereof |
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1996
- 1996-01-17 CN CN96115030A patent/CN1061320C/en not_active Expired - Fee Related
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