CN101108353A - Improved catalyzer of methyl hydride catalyzed partially oxidized synthesis gas and method of manufacturing the same - Google Patents
Improved catalyzer of methyl hydride catalyzed partially oxidized synthesis gas and method of manufacturing the same Download PDFInfo
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- CN101108353A CN101108353A CNA2007100924442A CN200710092444A CN101108353A CN 101108353 A CN101108353 A CN 101108353A CN A2007100924442 A CNA2007100924442 A CN A2007100924442A CN 200710092444 A CN200710092444 A CN 200710092444A CN 101108353 A CN101108353 A CN 101108353A
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- methyl hydride
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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
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- 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 invention relates to an improved catalyst for partial oxidation of methane to prepare synthetic gas, which comprises ABCDOx/Gamma-Al2O3, A is one of Rh, Pd, Pt and Ir, which accounts for 0.1-1.0wt% taking a blank carrier as a reference; B is equal to Ni and/ or Co, which accounts for 4.0-15.0wt% taking a blank carrier as a reference; C is one of La, Ce, Sm and Th, which accounts for 2.0-8.0wt% taking a blank carrier as a reference; D is one of or a mixture of two or more from W, V, Mn or Cr, which accounts for 30-60wt% taking a blank carrier as a reference. The preparation method comprises dipping the properly-dosed salt solution of D on the blank carrier, drying, incinerating at high temperature to obtain an improved carrier; then dipping step by step or co-dipping the properly-dosed nitrate of A,B,C on the improved carrier, drying, incinerating at the high temperature to obtain improved catalyst. When the invention is used for preparing synthetic gas, the transforming rate of CH4 is up to 96-98%, the selectivity of H2 and CO is above 96.0%, H2/CO=1.9-2.2. Under a reaction pressure of 0.1-2.0 MPa, the invention has good catalytic activity, selectivity and heat stability.
Description
One, technical field
The invention belongs to what and comprise the catalyst of metal or metal oxide or hydroxide, be specifically related to catalyst of using from producing synthetic gas from hydrocarbons that includes nickel and noble metal and the method for preparing catalyst.
Two, background technology
Methane is the main component of natural gas, many in the world in recent years countries methane is carried out rationally and effectively processing and utilization given attention more and more widely, methane has become the emphasis that research and develop countries in the world via the indirect reformer utilization of synthesis gas.
At present, the method for methane preparing synthetic gas mainly contains three kinds of steam reforming process (SR), self-heating recapitalization method (ATR) and catalyzing part oxidation methods (CPOX).Steam reforming process (SR) is a strong endothermic reaction, require to carry out (reaction condition is generally 15-30atm, 850-900 ℃) under high-temperature and high-pressure conditions, so this process energy consumption is than higher, especially in order to prevent employed catalyst n i/Al
2O
3Carbon distribution and need high liquid to steam ratio (3.5: 1) makes that undoubtedly energy consumption is higher, and conversion per pass is also lower, makes this technology that the equipment complexity be arranged, and investment is big, high temperature, shortcoming such as high pressure and corrosivity are big.Self-heating recapitalization method (ATR) is a non-selective oxidation reaction, has carried out water vapour and CO subsequently
2To the reforming reaction of methane, H in the product
2/ CO=2.6-3: 1, shortcoming is CO in the product
2Content is higher, and the utilization rate of carbon is low in the natural gas, with " atom economy " require inconsistent; Catalyzing part oxidation method (CPOX) is at high CO and H
2A low exothermic reaction under the selectivity situation, H in the synthesis gas of being produced
2/ CO is 2: 1, this H
2/ CO value, process and many subsequent machining technologies for Fischer-Tropsch synthetic system artificial oil and synthesizing methanol and other hydro carbons are very desirable, enter nineteen nineties, it becomes the novel path for transformation that the countries in the world industrial circle is extensively paid attention to, and is considered to be hopeful in the recent period to realize industrialized method; Selecting the economical and practical again catalyst of a kind of function admirable for use is that catalyzing part oxidation method (CPOX) realizes industrialized key.
Methane takes catalyzing part oxidation method preparing synthetic gas to be low exothermic reaction, under condition of high voltage, reactant density increases with the raising of pressure in the reactor, the exothermic heat of reaction amount significantly increases thereupon on the Reactor inlet place per volume of catalyst, makes catalyst be easy to the sintering inactivation under condition of high voltage.Take all factors into consideration from the operating cost equal angles, in actual industrial production, should directly utilize pipeline transport gas with certain pressure, and in most prior aries, catalyst application response operating pressure is a normal pressure, if directly utilize the pipeline transport gas, will the service life and the mechanical strength of catalyst be impacted, finally influence the overall performance and the operating cost of catalyst.
What methyl hydride catalyzed partial oxidation process was carried out in adiabatic reactor is a fast reaction.Claim in the document that it is the reaction of microsecond level.This fast response generally is to be under the mass transfer limited condition to carry out.Reactant reacts when reaching the catalyst outer surface promptly to be finished, thereby the inner surface of catalyst does not have much contributions to goal response.Excessive inner surface causes the decline of polyphone side reaction and bed thermal conductivity on the contrary, experiment shows: come the micropore of blocking catalyst to arrive suitable scope with the specific surface that reduces catalyst by adding high-melting point metal, can reduce side reaction, the thermal conductivity that increases bed simultaneously is to prolong life of catalyst.
In the prior art, it is open that the Chinese invention patent that we have a name to be called " methyl hydride catalyzed portion oxidation synthesis gas Catalysts and its preparation method " applies on June 14th, 2006, publication number CN1785516A.This catalyst consist of ABCO
X/ γ-Al
2O
3., be that the loading of benchmark is 16.0-60.0wt% with the carrier; A is selected from Ru, Rh, and a kind of among Pd and the Pt is 0.1-1.0wt% with the content of the benchmark of carrier; B=Ni is that the content of benchmark is 8.0-30.0wt% with the carrier; C is selected from a kind of among La, Ce, Sm and the Th, is that the content of benchmark is 8.0-30.0wt% with the carrier.Owing to added the metal that is up to 60wt%, the micropore of catalyst is blocked basically, makes the thermal conductivity of beds increase, thereby has reduced side reaction, has prolonged life of catalyst.Its defective is do not have concrete requirement for the catalyst specific surface of making, thereby the catalyst performance of making repeatability does not guarantee; Simultaneously, because the fusing point of rare earth is not high enough, the rare earth of part in micropore can leave micropore in reaction, can not reach the purpose that reduces specific surface.
Three, summary of the invention
The objective of the invention is to carry out technological improvement, a kind of cheap function admirable again is provided, have the improved catalysts and preparation method thereof of the methyl hydride catalyzed portion oxidation synthesis gas of prospects for commercial application at the defective that above-mentioned prior art exists.
For realizing purpose of the present invention, the technical scheme of being taked is as follows.
A kind of improved catalysts of methyl hydride catalyzed portion oxidation synthesis gas, catalyst consists of ABCDO
X/ γ-Al
2O
3, it is characterized in that:
1) A is selected from a kind of among Ru, Rh, Pd, Pt or the Ir, is that the content of benchmark is 0.1-1.0wt% with blank carrier;
2) B=Ni and/or Co are that the content of benchmark is 4.0-15.0wt% with blank carrier;
3) C is selected from a kind of among La, Ce, Sm or the Th, is that the content of benchmark is 2.0 with blank carrier.-8.0wt％；
4) D is selected from one or more the mixture among W, V, Mn or the Cr, is that the content of benchmark is 30-60wt% with blank carrier;
5) specific area≤3.0m of catalyst
2/ g.
Above-mentioned catalyst of the present invention, its preparation method is: 1.) salt solution impregnation of the D of usefulness corresponding measurement is to blank carrier, and successively through 100-120 ℃ of drying, 800-1200 ℃ of high-temperature roasting handled, and making specific area earlier is 5-20m
2The improved carrier of/g; 2) adopt the nitrate step impregnation or be immersed in altogether on the improved carrier that makes successively of A, B, the C of corresponding measurement again, successively through 100-120 ℃ of drying, 800-1200 ℃ of high-temperature roasting handled, and makes specific area≤3.0m
2Purpose product-improved catalysts of/g.
Above-mentioned catalyst of the present invention, the reaction temperature when being used for methyl hydride catalyzed partial oxidation and producing synthesis gas is: 800-1000 ℃, reaction pressure is: 0.1-2.0MPa, air speed is: 3.6 * 10
4-1.5 * 106hr
-1, material molar ratio is: CH
4: O
2=2: 1; It goes for the reaction under high pressure condition, is under the 0.1-2.0Mpa situation in reaction pressure, and catalyst has good catalytic activity, selectivity and heat endurance.
The catalyst of methyl hydride catalyzed portion oxidation synthesis gas of the present invention detects with XRD, does not find the active component crystalline phase, illustrates that active component is disperseed well at carrier surface.In catalyst of the present invention, Ni and/or Co and noble metal (Pt, Rh, Ru, Pd) all are the good main active component that is used for methyl hydride catalyzed portion oxidation synthesis gas catalyst, the present invention effectively makes up the metal of two kinds of systems, make full use of the advantage of two kinds of catalyst systems, bring into play their synergy, and the content of suitably controlling noble metal has carried out catalyst design.
The present invention improves catalyst carrier, before declines to a great extent through its specific area of carrier that improves, by original 100-200m
2/ g is reduced to 5-20m
2/ g, improved carrier has improved catalytic active component and catalyst promoter in the dispersion of carrier surface, has increased the catalytic active center number, shows good heat endurance in the catalysis experiment, has strengthened the heat conductivility of beds.
The present invention adopts and adds small amount of precious metals the mode in catalyst based is increased catalytic activity to Ni and/or Co, and has improved methane conversion, has strengthened catalyst activity stability.
The present invention adopts rare earth oxide that active component Ni and/or Co are evenly disperseed on the low surface area carrier surface of improvement, increased the position, activated centre, strengthened the thermal conductivity of beds, prevented active component Ni and/or Co loss and the sintering in pyroreaction, make catalyst have high activity, high selectivity, high-temperature stability.
The present invention adopts noble metal, and the reasonable assembly that rare earth metal and Ni and/or Co are catalyst based makes it can produce the catalyzing cooperation effect in the course of reaction of preparing synthetic gas, has reached good reaction result: CH
4Conversion ratio reaches 96-98%, H
2With the CO selectivity more than 96.0%, H
2/ CO=1.9-2.2.
That the present invention has developed that a kind of methyl hydride catalyzed portion oxidation synthesis gas uses is stable, novel Ni and/or Co are catalyst based efficiently, the high activity and the high stability characteristics that not only have noble metal catalyst, and catalyst preparation process is simple, have cheap, the advantage of small investment is produced the catalyst system that synthesis gas provides a good efficient stable for utilizing natural gas (methane).
Four, the specific embodiment
Enumerate the specific embodiment that a plurality of embodiment further specify catalyst of the present invention below, and the embodiment catalyst is used for the good result of methyl hydride catalyzed portion oxidation synthesis gas.But catalyst of the present invention never is confined to illustrated embodiment.
Embodiment 1
(1) takes by weighing the 100 γ-Al that restrain
2O
3, add 150 gram chromium nitrate solutions, through 100-120 ℃ of drying, through 800-1200 ℃ of roasting, make γ-Al again
2O
3Improved carrier is standby, after tested,
3The specific area of improved carrier is 15.0m
2/ g.
(2) take by weighing 14 gram γ-Al
2O
3Improved carrier adds 7.2 gram Ni (NO successively
3)
26H
2O, 5 gram Ce (NO
3)
36H
2O, 0.9 gram PtCl
4The aqueous solution of configuration through 100-120 ℃ of drying, again through 800-1200 ℃ of roasting, makes about 5 grams of catalyst granules, and after tested, the specific area of this catalyst is 1.2m
2/ g.。
(3) place methyl hydride catalyzed partial oxidation to produce the synthesis gas fixed bed reactors catalyst granules that makes, reaction condition is: temperature is 800 ℃, and reaction pressure is: 0.2MPa, air speed is: 3.6 * 10
5Hr
-1, material molar ratio is: CH
4: O
2=2: 1.Reaction result is CH
4Conversion ratio is 95%, CO and H
2Selectivity is being more than 95.0%, H
2/ CO=1.95.
Embodiment 2
(1) takes by weighing the 100 γ-Al that restrain
2O
3, add 125 gram wolframic acid solution, through 100-120 ℃ of drying, through 800-1200 ℃ of roasting, make γ-Al again
2O
3Improved carrier is standby, after tested,
3The specific area of improved carrier is 17.0m
2/ g.
(2) take by weighing 14 gram γ-Al
2O
33Improved carrier adds 5.2 gram Ni (NO successively
3)
26H
2O, 2.6 gram Co (NO
3)
2, 5.4 gram Ce (NO
3)
36H
2O, 0.7 gram Rh (NO
3)
3The aqueous solution of configuration through 100-120 ℃ of drying, again through 800-1200 ℃ of roasting, makes about 5 grams of catalyst granules, and after tested, the specific area of this catalyst is 2.1m
2/ g.
(3) place methyl hydride catalyzed partial oxidation to produce the synthesis gas fixed bed reactors catalyst granules that makes, reaction condition is: temperature is 800 ℃, and reaction pressure is: 0.2MPa, air speed is: 3.6 * 10
5Hr
-1, material molar ratio is: CH
4: O
2=2: 1.Reaction result is CH
4Conversion ratio is 95%, CO and H
2Selectivity is being more than 95.0%, H
2/ CO=1.97.
Embodiment 3
1) takes by weighing the 100 γ-Al that restrain
2O
3, add 137 gram vanadic sulfate solution, through 100-120 ℃ of drying, through 800-1200 ℃ of roasting, make γ-Al again
2O
33Improved carrier is standby, and after tested, the specific area of improved carrier is 20.0m
2/ g.
2) use the step impregnation method controlling catalyst:
(1) takes by weighing 14 gram γ-Al
2O
3Improved carrier adds 7.5 gram Ni (NO
3)
26H
2The aqueous solution of O configuration is through 100-120 ℃ of drying, again through 800-1200 ℃ of calcination process.
(2) carrier that step (1) is handled adds 5.7 gram Ce (NO
3)
36H
2The aqueous solution of O configuration is through 100-120 ℃ of drying, again through 800-1200 ℃ of calcination process.
(3) catalyst that step (2) is made adds 0.5 gram Ru (NO
3)
3The aqueous solution of configuration through 100-120 ℃ of drying, makes the improved catalysts that methyl hydride catalyzed partial oxidation is produced synthesis gas through 800-1200 ℃ of calcination process again.
(4) the methyl hydride catalyzed partial oxidation that will the make improved catalysts particle (about 5 gram) of producing synthesis gas places methyl hydride catalyzed partial oxidation to produce the synthesis gas fixed bed reactors, reaction condition is: temperature is 800 ℃, reaction pressure is: 0.2MPa, air speed is: 3.6 * 10
5Hr
-1, material molar ratio is: CH
4: O
2=2: 1.Reaction result is CH
4Conversion ratio is 95%, CO and H
2Selectivity is being more than 95.0%, H
2/ CO=1.95.
Embodiment 4
(1) takes by weighing the 100 γ-Al that restrain
2O
3, add 142 gram vanadic sulfate solution, through 100-120 ℃ of drying, through 800-1200 ℃ of roasting, make γ-Al again
2O
3Improved carrier is standby, and after tested, the specific area of preliminary treatment carrier is 19.0m
2/ g.
(2) take by weighing 14 gram γ-Al
2O
3Improved carrier adds 8 gram Ni (NO successively
3)
26H
2O, 5.5 gram Ce (NO
3)
36H
2O, 0.8 gram Rh (NO
3)
3The aqueous solution of configuration through 100-120 ℃ of drying, again through 800-1200 ℃ of roasting, makes about 5 grams of catalyst granules, and after tested, the specific area of this catalyst is 1.3m
2/ g.。
(3) place methyl hydride catalyzed partial oxidation to produce the synthesis gas fixed bed reactors catalyst granules that makes, reaction condition is: temperature is 800 ℃, and reaction pressure is: 0.2MPa, air speed is: 3.6 * 10
5Hr
-1, material molar ratio is: CH
4: O
2=2: 1.Reaction result is CH
4Conversion ratio is 96%, CO and H
2Selectivity is being more than 96.0%, H
2/ CO=1.99.
Embodiment 5
The reaction stability experiment:
Catalyst is the catalyst of 5 gram embodiment, 4 preparations, and reaction temperature is 850 ℃, and reaction pressure is: 1.0MPa, air speed is: 1.0 * 10
6Hr
-1, material molar ratio is: CH
4: O
2=2: 1.
The data list of course of reaction is as follows:
| Reaction time | 20min | 60min | 5hr | 10hr | 20hr | 40hr | 60hr |
| CH 4conv.(％) | 92.0 | 94.0 | 95.0 | 95.0 | 94.5 | 94.5 | 94.0 |
| H 2 selectivity(％) | 92.0 | 96.5 | 99.0 | 99.8 | 99.0 | 99.3 | 99.0 |
| CO selectivity(％) | 91.3 | 93.2 | 95.8 | 94.5 | 95.6 | 96.2 | 96.8 |
Claims (2)
1. the improved catalysts of a methyl hydride catalyzed portion oxidation synthesis gas, catalyst consists of ABCDOx/ γ-Al
2O
3, it is characterized in that:
1) A is selected from a kind of among Ru, Rh, Pd, Pt or the Ir, is that the content of benchmark is 0.1-1.0wt% with blank carrier;
2) B=Ni and/or Co are that the content of benchmark is 4.0-15.0wt% with blank carrier;
3) C is selected from a kind of among La, Ce, Sm or the Th, is that the content of benchmark is 2.0-8.0wt% with blank carrier;
4) D is selected from one or more the mixture among W, V, Mn or the Cr, is that the content of benchmark is 30-60wt% with blank carrier;
5) specific area≤3.0m of catalyst
2/ g.
2. the preparation method of a methyl hydride catalyzed portion oxidation synthesis gas improved catalysts as claimed in claim 1 is characterized in that:
1) salt solution impregnation of the D of usefulness corresponding measurement is to blank carrier, and successively through 100-120 ℃ of drying, 800-1200 ℃ of high-temperature roasting handled, and making specific area earlier is 5-20m
2The improved carrier of/g;
2) adopt the nitrate step impregnation or be immersed in altogether on the improved carrier that makes successively of A, B, the C of corresponding measurement again, successively through 100-120 ℃ of drying, 800-1200 ℃ of high-temperature roasting handled, and makes specific area≤3.0m
2Purpose product-improved catalysts of/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100924442A CN100488628C (en) | 2007-07-18 | 2007-07-18 | Improved catalyzer of methane catalysis and partial oxidation for synthesizing gas and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100924442A CN100488628C (en) | 2007-07-18 | 2007-07-18 | Improved catalyzer of methane catalysis and partial oxidation for synthesizing gas and method of manufacturing the same |
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| Publication Number | Publication Date |
|---|---|
| CN101108353A true CN101108353A (en) | 2008-01-23 |
| CN100488628C CN100488628C (en) | 2009-05-20 |
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ID=39040729
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728341A (en) * | 2012-07-12 | 2012-10-17 | 中国石油大学(华东) | Supported perovskite catalyst and preparation technique thereof |
| CN103785395A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for preparation of synthetic gas through partial oxidation of methane, and preparation method and application thereof |
| CN106944068A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method for methane portion oxidation synthesis gas catalyst |
| CN112449615A (en) * | 2018-08-03 | 2021-03-05 | 株式会社新生能源研究 | Steam reforming catalyst |
-
2007
- 2007-07-18 CN CNB2007100924442A patent/CN100488628C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728341A (en) * | 2012-07-12 | 2012-10-17 | 中国石油大学(华东) | Supported perovskite catalyst and preparation technique thereof |
| CN103785395A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Catalyst for preparation of synthetic gas through partial oxidation of methane, and preparation method and application thereof |
| CN103785395B (en) * | 2012-11-01 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of methane portion oxidation synthesis gas Catalysts and its preparation method and application |
| CN106944068A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method for methane portion oxidation synthesis gas catalyst |
| CN106944068B (en) * | 2016-01-07 | 2019-07-12 | 中国石油化工股份有限公司 | A kind of preparation method for methane portion oxidation synthesis gas catalyst |
| CN112449615A (en) * | 2018-08-03 | 2021-03-05 | 株式会社新生能源研究 | Steam reforming catalyst |
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| Publication number | Publication date |
|---|---|
| CN100488628C (en) | 2009-05-20 |
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