CN1247447C - Catalyzer for preparing synthetic gas from natural gas partial oxidation and its preparation method - Google Patents
Catalyzer for preparing synthetic gas from natural gas partial oxidation and its preparation method Download PDFInfo
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- CN1247447C CN1247447C CNB2003101096588A CN200310109658A CN1247447C CN 1247447 C CN1247447 C CN 1247447C CN B2003101096588 A CNB2003101096588 A CN B2003101096588A CN 200310109658 A CN200310109658 A CN 200310109658A CN 1247447 C CN1247447 C CN 1247447C
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- natural gas
- partial oxidation
- nickel
- preparing synthetic
- rare earth
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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
Abstract
The present invention relates to a catalyst for preparing synthetic gas by oxidizing partial natural gas, which comprises the compositions of 6 to 25 wt% of nickel oxide, 0 to 6 wt% of rare earth oxide and 69 to 94 wt% of silicon carbide. Soluble metal nickel salt or the mixture of the soluble metal nickel salt and rare earth metal salt is dissolved in distilled water or alcohol solvent; then, silicon carbide with high specific surface area is soaked in the solution; under certain conditions, metal salt is deposited on the surface of the silicon carbide to be dried and roasted; finally, the catalyst is prepared. The catalyst has the advantages of high methane conversion rate, high carbon monoxide and hydrogen selectivity, long catalyst life, simple regeneration, good performance for a regenerated catalyst, etc.
Description
Technical field:
The invention belongs to a kind of Catalysts and its preparation method, relate in particular to a kind of Catalysts and its preparation method of preparing synthetic gas by partial oxidation of natural gas.
Background technology:
The natural gas source of China is very abundant, mainly concentrates on the west area that economy falls behind relatively.Sweet natural gas is as a kind of important energy, and it has cleaning and eco-friendly characteristics, but Sweet natural gas use and transportation aspect have inconvenience, thereby limited Sweet natural gas in the energy and other Application for Field.Therefore, development and utilization natural gas source how effectively, convert it into and be easy to the high added value liquid chemical that transports and use, the strategical reajustment of China's energy structure and development of the West Regions and whole western economic Sustainable development are had very important realistic meaning.Preparing synthetic gas by partial oxidation of natural gas be an important middle-chain that realizes natural its conversion, and the research and development of high-performance catalyst is its key.Change into the existing lot of documents report of Catalysts and its preparation method of synthetic gas at present about gas by partial oxidation of natural, as Chinese patent (application number: 95111279) disclose a kind of Catalysts and its preparation method of preparing synthetic gas by partial oxidation of natural gas, it is characterized by and use precious metal as promotor, (with the carrier is benchmark to bullion content 0.1～5%, weight percent), specific surface is 5～20m
2/ g.The Preparation of catalysts method: (1) stirs the soluble nickel salts solution of carrier and metering under 10～80 ℃.(2) leave standstill more than 1 hour, 50～200 ℃ of oven dry down.(3), get nickel catalyst carried 500～700 ℃ of following roastings.(4) noble metal compound solution with supported nickel catalyst and metering mixes, and leaves standstill, dries, and promptly gets to add the nickel catalyst carried of precious metal; (application number: 99111080) also disclose the Catalysts and its preparation method that a kind of two-stage reaction prepares synthetic gas, its catalyst characteristics is to contain nickel oxide, alkaline earth or rare earth oxide in the catalyzer to Chinese patent, consists of: LnxOy-Ni base/MAl
2O
4, the relative carrier of component is: Ni1.0～20%, Ln1～20%.M1～15％。But in the preparing synthetic gas by partial oxidation of natural gas process, the present catalyzer of exploitation, the catalyzer of the preparing synthetic gas by partial oxidation of natural gas that provides as above-mentioned two patents is all made support of the catalyst with oxide material.
As everyone knows, preparing synthetic gas by partial oxidation of natural gas is a heat release and the favourable chemical reaction of high temperature, and both reaction needed was carried out under very high temperature (usually greater than 700 ℃) condition, and followed a large amount of exothermic phenomenon.We know that oxide carrier exists the defective of heat conductivity and poor heat stability, therefore in reaction process because timely hot form " focus " of diffusion reaction, it can cause catalyzer generation sintering and " inactivation " phenomenon.
Summary of the invention:
The objective of the invention is to solve the thermally-stabilised difference and the easy-sintering inactivation problem that exist in the preparing synthetic gas by partial oxidation of natural gas catalyzer, develop a kind of high temperature resistant, anti-sintering and the high preparing synthetic gas by partial oxidation of natural gas catalyzer of catalytic activity.
The present invention realizes like this, soluble metal nickel salt or soluble metal nickel salt and rare earth metal salt mixture are dissolved in distilled water or the alcohol solvent, then high-specific surface area carbonization silicon is immersed in the above-mentioned solution, under certain condition metal-salt is deposited on the silicon carbide, after the oven dry roasting, can obtain the preparing synthetic gas by partial oxidation of natural gas catalyzer.
The weight percent of catalyzer of the present invention consists of:
Nickel oxide 6～25%
Rare earth oxide 0～6%
Silicon carbide 69～94%
The surface-area of long-pending silicon carbide is 20～200m as mentioned above
2/ g.
Aforesaid method for preparing catalyst is:
1. compound concentration is that the aqueous solution of soluble nickel salt of 1～20Wt% or alcoholic solution and concentration are the rare earth metal salt solutions of 1～20Wt%;
2. the mixing solutions with nickel salt solution or nickel salt solution and rare earth metal salt is heated to 20～60 ℃, under agitation condition, Carboround is immersed in the mixing solutions of nickel salt solution or nickel salt solution and rare earth metal salt, stirring is 1～12 hour, treat solvent evaporates or the pH value of solution is adjusted to 6-10, active ingredient is deposited on the carrier surface, and wherein each weight percent add-on of forming is: nickel oxide 6～25%, rare earth oxide 0～6%, silicon carbide 69～94%;
3. under 80～150 ℃ of conditions, in air, dry,, can obtain the loaded catalyst of preparing synthetic gas by natural gas partial oxidation 600 ℃～750 ℃ roastings 1～6 hour.
Aforesaid soluble nickel salt is nickelous nitrate, nickel acetate or single nickel salt.
Aforesaid soluble ree metal-salt is nitrate or hydrochloride.
Comprise lanthanum nitrate, cerous nitrate, cerous nitrate, hydrochloric acid lanthanum, hydrochloric acid cerium, lanthanum acetate or cerous acetate as above-mentioned rare earth metal salt.
The evaluation test of catalyzer is carried out in fixed-bed reactor, and the mol ratio of methane and oxygen is 2: 1, and air speed is 40000.Wherein, under 700 ℃ of conditions, methane conversion is greater than 80%, and the selectivity of carbon monoxide and hydrogen is greater than 90%.
The high-specific surface area carbonization silicon materials that principal feature of the present invention is high with thermostability and heat-conductive characteristic is good are as the carrier of the catalyzer of preparing synthetic gas by partial oxidation of natural gas, method by pickling process or co-precipitation loads on active component nickel and coagent rare earth oxide on the silicon carbide, prepares the catalyzer of preparing synthetic gas by partial oxidation of natural gas.Preparing synthetic gas by partial oxidation of natural gas catalyzer of the present invention has the methane conversion height, the long and advantages such as simple and regenerated catalyst excellent property of regenerating of carbon monoxide and hydrogen selective height, catalyst life.
Embodiment:
Embodiment 1:
Get 1 gram nickelous nitrate and be dissolved in 10 milliliters of dehydrated alcohols, be mixed with 10% nickelous nitrate alcoholic solution.Getting 3 gram specific surfaces then is 20m
2The silicon carbide powder of/g is dispersed in silicon carbide powder in the nickelous nitrate alcoholic solution under 20 ℃ and agitation condition, stirs 3 hours.600 ℃ of roastings 3 hours in muffle furnace again after 80 ℃ of oven dry can obtain nickel oxide loaded amount and be 8.5% preparing synthetic gas by partial oxidation of natural gas catalyzer.
The evaluation test of this catalyzer is carried out in fixed-bed reactor, and the mol ratio of methane and oxygen is 2: 1, and air speed is 40000.Wherein, under 700 ℃ of conditions, methane conversion is 80%, and the selectivity of carbon monoxide and hydrogen is respectively 93% and 91%.
Embodiment 2:
Get 0.1 gram nickel acetate and be dissolved in 10 ml distilled waters, be mixed with 1% nickel acetate aqueous solution; Get cerous nitrate 0.02 gram again, be dissolved in 2 ml waters, be made into 1% the cerous nitrate aqueous solution; Then with the two mixing.Getting 0.2 gram specific surface is 40m
2The silicon carbide powder of/g is dispersed in silicon carbide powder in the mixing solutions under 40 ℃ and agitation condition, stirs 6 hours.With the Ph value of ammoniacal liquor regulator solution, make nickel and cerium in the solution form co-precipitation, be deposited on the silicon carbide.Under 100 ℃ of conditions, sample is dried then.Put into 700 ℃ of roastings of muffle furnace 2 hours again, can obtain nickel oxide loaded amount is 12.7%, and the cerium oxide charge capacity is 3.3% preparing synthetic gas by partial oxidation of natural gas catalyzer.The evaluation test of this catalyzer is carried out in fixed-bed reactor, and the mol ratio of methane and oxygen is 2: 1, and air speed is 40000.Wherein, under 700 ℃ of conditions, methane conversion is 83%, and the selectivity of carbon monoxide and hydrogen is respectively 95% and 93%.
Embodiment 3:
Get 0.1 gram nickel acetate and be dissolved in 10 ml distilled waters, be mixed with 1% nickel acetate aqueous solution; Get cerous acetate 0.02 gram again, be dissolved in 2 ml waters, be made into 1% the cerous nitrate aqueous solution.Getting 0.2 gram specific surface is 60m
2The silicon carbide powder of/g is dispersed in silicon carbide powder in the nickel acetate solution under 60 ℃ and agitation condition, stirs 6 hours.Under 100 ℃ of conditions, sample is dried then.Sample after will drying again joins under agitation condition in the cerous nitrate solution for preparing, and stirs 1 hour.Put into 700 ℃ of roastings of muffle furnace 1 hour after 140 ℃ of oven dry again, can obtain nickel oxide loaded amount is 12.7%, and the cerium oxide charge capacity is 3.3% preparing synthetic gas by partial oxidation of natural gas catalyzer.The evaluation test of this catalyzer is carried out in fixed-bed reactor, and the mol ratio of methane and oxygen is 2: 1, and air speed is 40000.Wherein, under 700 ℃ of conditions, methane conversion is 82%, and the selectivity of carbon monoxide and hydrogen is respectively 94% and 92%.
Embodiment 4:
Get 2 gram single nickel salt (NiSO
46H
2O) be dissolved in 10 ml distilled waters, be mixed with 20% nickel sulfate solution.Getting 2 gram specific surfaces then is 120m
2The silicon carbide powder of/g is dispersed in silicon carbide powder in the single nickel salt alcoholic solution under 60 ℃ and agitation condition, stirs 5 hours.With the Ph value of ammoniacal liquor regulator solution, make the nickel in the solution form precipitation again, be deposited on the silicon carbide.Sample after 100 ℃ of oven dry again in muffle furnace 700 ℃ burnt 5 hours, can obtain nickel oxide loaded amount and be 25% preparing synthetic gas by partial oxidation of natural gas catalyzer.The evaluation test of this catalyzer is carried out in fixed-bed reactor, and the mol ratio of methane and oxygen is 2: 1, and air speed is 40000.Wherein, under 750 ℃ of conditions, methane conversion is 80%, and the selectivity of carbon monoxide and hydrogen is respectively 94% and 91%.
Embodiment 5:
Get 0.8 gram nickelous nitrate and be dissolved in 10 ml distilled waters, be mixed with 8% nickel nitrate aqueous solution; Get lanthanum nitrate 0.3 gram again, be dissolved in 2 ml waters, then with the two mixing.Getting 1.5 gram specific surfaces is 40m
2The silicon carbide powder of/g is dispersed in silicon carbide powder in the mixing solutions under 20 ℃ and agitation condition, stirs 6 hours.Under 100 ℃ of conditions, sample is dried then.Put into 750 ℃ of roastings of muffle furnace 4 hours again, can obtain nickel oxide loaded amount is 12.7%, and the lanthanum trioxide charge capacity is 6% preparing synthetic gas by partial oxidation of natural gas catalyzer.The evaluation test of this catalyzer is carried out in fixed-bed reactor, and the mol ratio of methane and oxygen is 2: 1, and air speed is 40000.Wherein, under 700 ℃ of conditions, methane conversion is 83%, and the selectivity of carbon monoxide and hydrogen is respectively 95% and 93%.
Embodiment 6:
Get 0.5 gram nickelous nitrate and be dissolved in 10 milliliters of dehydrated alcohols, be mixed with 10% nickelous nitrate alcoholic solution; Get lanthanum nitrate 0.02 gram again, be dissolved in 2 ml waters, be made into 15% lanthanum nitrate aqueous solution; Then with the two mixing.Getting 1.5 gram specific surfaces is 200m
2The silicon carbide powder of/g is dispersed in silicon carbide powder in the mixing solutions under 20 ℃ and agitation condition, stirs 3 hours.120 ℃ of oven dry, 700 ℃ of roastings 3 hours in muffle furnace again, can obtain nickel oxide loaded amount is 7.6%, the lanthanum trioxide charge capacity is 0.4% preparing synthetic gas by partial oxidation of natural gas catalyzer.The evaluation test of this catalyzer is carried out in fixed-bed reactor, and the mol ratio of methane and oxygen is 2: 1, and air speed is 40000.Wherein, under 700 ℃ of conditions, methane conversion is 80%, and the selectivity of carbon monoxide and hydrogen is respectively 93% and 91%.
Claims (5)
1. the catalyzer of a preparing synthetic gas by partial oxidation of natural gas is characterized in that the weight percent of catalyzer consists of:
Nickel oxide 6～25%
Rare earth oxide 0～6%
Silicon carbide 69～94%
The surface-area of described silicon carbide is 20～200m
2/ g.
2. the Preparation of catalysts method of a kind of preparing synthetic gas by partial oxidation of natural gas as claimed in claim 1 is characterized in that comprising the steps:
(1) compound concentration is that the aqueous solution of soluble nickel salt of 1～20Wt% or alcoholic solution and concentration are the rare earth metal salt solutions of 1～20Wt%;
(2) mixing solutions with nickel salt solution or nickel salt solution and rare earth metal salt is heated to 20～60 ℃, under agitation condition, Carboround is immersed in the mixing solutions of nickel salt solution or nickel salt solution and rare earth metal salt, stirring is 1～12 hour, treat solvent evaporates or the pH value of solution is adjusted to 6-10, active ingredient is deposited on the carrier surface, and wherein each weight percent add-on of forming is: nickel oxide 6～25%, rare earth oxide 0～6%, silicon carbide 69～94%;
(3) under 80～150 ℃ of conditions, in air, dry,, can obtain the loaded catalyst of preparing synthetic gas by natural gas partial oxidation 600 ℃～750 ℃ roastings 1～6 hour.
3. the Preparation of catalysts method of a kind of preparing synthetic gas by partial oxidation of natural gas as claimed in claim 2 is characterized in that described soluble nickel salt is nickelous nitrate, nickel acetate or single nickel salt.
4. the Preparation of catalysts method of a kind of preparing synthetic gas by partial oxidation of natural gas as claimed in claim 2 is characterized in that described soluble ree metal-salt is nitrate or hydrochloride.
5. the Preparation of catalysts method of a kind of preparing synthetic gas by partial oxidation of natural gas as claimed in claim 4 is characterized in that described rare earth metal salt comprises lanthanum nitrate, cerous nitrate, cerous nitrate, hydrochloric acid lanthanum, hydrochloric acid cerium, lanthanum acetate or cerous acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101096588A CN1247447C (en) | 2003-11-11 | 2003-11-11 | Catalyzer for preparing synthetic gas from natural gas partial oxidation and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101096588A CN1247447C (en) | 2003-11-11 | 2003-11-11 | Catalyzer for preparing synthetic gas from natural gas partial oxidation and its preparation method |
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|---|---|
| CN1544311A CN1544311A (en) | 2004-11-10 |
| CN1247447C true CN1247447C (en) | 2006-03-29 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438978C (en) * | 2006-12-20 | 2008-12-03 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing synthetic gas by partial oxidation of natural gas and preparation method thereof |
| RU2446879C1 (en) * | 2010-10-07 | 2012-04-10 | Министерство Промышленности И Торговли Российской Федерации | Catalyst for steam reforming hydrocarbons and method of producing said catalyst |
| CN102614903A (en) * | 2011-01-28 | 2012-08-01 | 中国科学院大连化学物理研究所 | Monolithic catalyst and use of the monolithic catalyst in natural gas reforming for synthesis gas preparation |
| CN102504760B (en) * | 2011-11-05 | 2014-04-16 | 中国科学院山西煤炭化学研究所 | Preparation method of silicon carbide and carbon nano tube composite wave-absorbing material |
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