CN100478071C - Catalyst for making synthetic gas from methane by catalyzing partly oxidation and its preparation method - Google Patents
Catalyst for making synthetic gas from methane by catalyzing partly oxidation and its preparation method Download PDFInfo
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- CN100478071C CN100478071C CNB2005100573803A CN200510057380A CN100478071C CN 100478071 C CN100478071 C CN 100478071C CN B2005100573803 A CNB2005100573803 A CN B2005100573803A CN 200510057380 A CN200510057380 A CN 200510057380A CN 100478071 C CN100478071 C CN 100478071C
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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
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- 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
A catalyst for preparing the synthetic gas from methane by partial catalytic oxidizing has a formula ABCOx/Al2O3, where A is chosen from Ru, Rh, Pd and Pt, B=Ni and C is chosen from La, Ce, Sm and Th. Its advantages are high conversion rate of CH4, and high selectivity to CO and H2.
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, very desirable for fischer-tropsch process system methyl alcohol and many subsequent machining technologies such as higher alcohol and hydro carbons, 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.
The catalyst that methane takes catalyzing part oxidation legal system synthesis gas to use, there is a Granted publication number to announce on November 3rd, 1999 in the prior art for the Chinese invention patent of CN1046099C, it is characterised in that it consists of: ABCOX/Al2O3, loading are 5.0-20.0wt%, wherein, A is selected among Li, Na or the K a kind of, content is 0.1-10wt%, and B is selected among Ni, Fe or the Co a kind of, and content is 2-10wt%, C is selected among La, Sm, Y or the Ce a kind of, and content is 0-10wt%.Its preparation method must carry out the preparation of catalyst carrier colloidal sol, the supercritical drying and the roasting of complex catalyst precursor thing; And its suitable reaction pressure condition is a normal pressure, reacting gas air speed (1.2 * 10
4-3.6 * 10
4) excursion is narrower and small, if be used for industrialization, its catalyst preparation process is comparatively complicated, and operating flexibility changes little, and technological equipment investment and operating cost are bigger.Also having a name to be called " catalyst of producing synthetic gas by methane selectively oxidizing " Granted publication number in the prior art announces on November 17th, 1999 for the Chinese invention patent of CN1046435C, its active component is Ni, the consumption that it is characterized in that Ni is a 5-20% weight, carrier is ZrO2, TiO2, molecular sieve (ZSM) or its composition of 75-95% weight, and co-catalyst is the rare earth oxide of 0-5% weight.This Preparation of catalysts process must be carried out 24 hours dippings to active component having under the situation of continuous stirring, then macerate is heated into sticky matter, heat treatment step such as drying, roasting again, Preparation of Catalyst length consuming time, it is normal pressure that this catalyst system is suitable for reaction pressure, and the reacting gas air speed is 2.5 * 10
5Mlg
-1H
-1About, operating flexibility is still less.As being used for industrialization, its equipment investment and operating cost are still higher.
Methyl hydride catalyzed partial oxidation process preparing synthetic gas is low exothermic reaction, under high pressure, high-speed condition, 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 operating cost, equipment investment, catalyst overall performance equal angles, in actual industrial production, should directly utilize pipeline transport gas with certain pressure.And synthesis gas downstream processing technology, as reactions such as synthesizing methanol, artificial oil, synthetic ammonia all is to carry out under condition of high voltage, natural gas prepared synthesis gas and the synthesis gas downstream process is integrated takes all factors into consideration, utilizing original pressure of pipeline transport gas that synthesis gas preparation is reflected under the certain pressure condition carries out, reactor volume will reduce greatly, simultaneously, reactor outlet supercharging expense also greatly reduces.Even under the lower situation of pipeline gas pressure, pressurization is also than good in the reactor outlet pressurization, because the system molecular amounts doubles to make the pressurization difficulty to increase before and after the synthesis gas reaction before reactor.If use the high pressure synthesis gas process, will reduce the investment of equipment investment and operating cost greatly.Therefore, the synthesis gas preparation reaction should be carried out under condition of high voltage.And in the above-mentioned existing patented technology, catalyst application response operating pressure is a normal pressure, it is little that catalyst is suitable for the air speed excursion, make that technological operation elasticity is little, if directly utilize the pipeline transport gas, will the service life and the mechanical strength of catalyst be impacted, finally influence the overall performance of catalyst, increase reaction process operating cost and equipment investment expense, also uneconomical to the synthesis gas downstream process.
Three, summary of the invention
The objective of the invention is to deficiency, a kind of cheap function admirable again is provided, have the Catalysts and its preparation method of the methyl hydride catalyzed part oxygen preparing synthetic gas of prospects for commercial application at the prior art existence.
For realizing purpose of the present invention, the technical scheme of being taked is as follows.
The catalyst that a kind of methyl hydride catalyzed part oxygen preparing synthetic gas is used, catalyst consists of ABCO
x/ Al
2O
3, it is characterized in that: the loading that 1) with the carrier is benchmark is 16.0-60.0wt%; 2) A is selected from a kind of among Ru, Rh, Pd or the Pt, is that the content of benchmark is 0.1-1.0wt% with the carrier; 3) B=Ni is that the content of benchmark is 8.0-30.0wt% with the carrier; 4) C is selected from a kind of among La, Ce, Sm or the Th, is that the content of benchmark is 8.0-30.0wt% with the carrier.
Above-mentioned catalyst of the present invention, its preparation method is: the nitrate step impregnation or be immersed in carrier γ-Al altogether successively that adopts B, C, the A of corresponding measurement
2O
3On, successively through 100-120 ℃ of drying, the 800-1000 ℃ of catalyst that the high-temperature roasting Processing of Preparation is required.
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 * 10
6Hr
-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, the Al that only disperses
2O
3Diffraction maximum illustrates that active component is disperseed well at carrier surface.In catalyst of the present invention, Ni 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 catalyst system and catalyzings, make full use of the advantage of two kinds of catalyst systems, bring into play their synergy, and the content (cost control) of suitably controlling noble metal has carried out catalyst design.
The present invention adopts and adds small amount of precious metals the mode in catalyst based is increased catalytic activity to Ni, and has improved methane conversion, has strengthened catalyst activity stability.
The present invention adopts the rare earth oxide that is higher than the typical catalyst load capacity to make active component Ni at carrier A l
2O
3The even dispersion on surface has increased the position, activated centre, has reduced catalyst internal voids rate, strengthen the thermal conductivity of beds, prevented loss and the sintering of active component Ni in pyroreaction, made catalyst have high activity, high selectivity, high thermal stability.
The present invention adopts noble metal, rare earth metal and Ni/Al
2O
3Reasonable assembly, make it in the course of reaction of preparing synthetic gas, can produce the catalyzing cooperation effect, reached good reaction result: CH
4Conversion ratio is greater than 95%, H
2With the CO selectivity at 95 above .0%, H
2/ CO=1.9-2.0, the CO yield is more than 94%.
Catalyst of the present invention is compared with CN1046435C with prior art CN1046099C, reaction pressure when producing synthesis gas (0.1-2.0) and gas space velocity (3.6 * 10
4-1.5 * 10
6Hr
-1) the equal broad of excursion, it is big that operating flexibility is wanted relatively.
That the present invention has developed that a kind of methyl hydride catalyzed portion oxidation synthesis gas uses is stable, novel Ni is catalyst based efficiently, the high activity and the high stability characteristics that not only have noble metal catalyst, and catalyst preparation process is simple, has cheap, the advantage of small investment is for utilizing natural gas (CH
4) produce the catalyst system that synthesis gas provides a good efficient stable.
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 be confined to for embodiment.
Embodiment 1
Use the co-impregnation controlling catalyst:
(1) takes by weighing 10 gram γ-Al
2O
3, add 5 gram Ni (NO successively
3)
26H
2O, 5 gram Ce (NO
3)
36H
2O, 0.1 gram Ru (NO
3)
3The aqueous solution of configuration through 100-120 ℃ of drying, again through 800-1000 ℃ of roasting, makes about 5 grams of catalyst granules.
(2) 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, CO yield are more than 94.0%.
Embodiment 2
Use the step impregnation method controlling catalyst:
(1) takes by weighing 10 gram γ-Al
2O
3, add 5 gram Ni (NO
3)
26H
2The aqueous solution of O configuration is through 100-120 ℃ of drying, again through 800-1000 ℃ of calcination process.
(2) catalyst that step (1) is handled adds 5 gram Ce (NO
3)
36H
2The aqueous solution of O configuration is through 100-120 ℃ of drying, again through 800-1000 ℃ of calcination process.
(3) catalyst that step (2) is made adds 0.1 gram Ru (NO
3)
3The aqueous solution of configuration through 100-120 ℃ of drying, makes methyl hydride catalyzed partial oxidation through 800-1000 ℃ of calcination process again and produces synthetic gas catalyst.
(4) the methyl hydride catalyzed partial oxidation that will make is produced synthetic gas catalyst particle (about 5 gram) and is placed methyl hydride catalyzed partial oxidation to produce the synthesis gas fixed bed reactors, and 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, CO yield are more than 94.0%.
Embodiment 3
(1) takes by weighing 10 gram γ-Al
2O
3, add 6 gram Ni (NO successively
3)
26H
2O, 5 gram Ce (NO
3)
36H
2O, 0.1 gram Rh (NO
3)
3The aqueous solution of configuration through 100-120 ℃ of drying, again through 800-1000 ℃ of roasting, makes about 5 grams of catalyst granules.
(2) 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 95.0%, H
2/ CO=1.98, CO yield are more than 94.0%.
Embodiment 4
(1) takes by weighing 10 gram γ-Al
2O
3, add 8 gram Ni (NO successively
3)
26H
2O, 5 gram La (NO
3)
36H
2O, 0.1 gram Rh (NO
3)
3The aqueous solution of configuration through 100-120 ℃ of drying, again through 800-1000 ℃ of roasting, makes about 5 grams of catalyst granules.
(2) place methyl hydride catalyzed partial oxidation to produce the synthesis gas fixed bed reactors catalyst granules that makes, reaction condition is: temperature is 900 ℃, and reaction pressure is: 0.5MPa, air speed is: 4.0 * 10
5Hr
-1, material molar ratio is: CH
4: O
2=2: 1.Reaction result is CH
4Conversion ratio is 95.5.0%, CO and H
2Selectivity is being more than 95.0%, H
2/ CO=2.0, CO yield are more than 94.0%.
Embodiment 5
(1) takes by weighing 10 gram γ-Al
2O
3, add 8 gram Ni (NO successively
3)
26H
2O, 6 gram La (NO
3)
36H
2O, 0.1 gram Rh (NO
3)
3The aqueous solution of configuration through 100-120 ℃ of drying, again through 800-1000 ℃ of roasting, makes about 5 grams of catalyst granules.
(2) place methyl hydride catalyzed partial oxidation to produce the synthesis gas fixed bed reactors catalyst granules that makes, reaction condition is: temperature is 930 ℃, and reaction pressure is: 0.5MPa, air speed is: 4.5 * 10
5Hr
-1, material molar ratio is: CH
4: O
2=2: 1.Reaction result is CH
4Conversion ratio is 95.5.0%, CO and H
2Selectivity is being more than 95.0%, H
2/ CO=2.0, CO yield are more than 94.0%.
Embodiment 6
The reaction stability experiment:
Catalyst is the catalyst of 5 gram embodiment, 5 preparations, and reaction temperature is 950 ℃, 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.(％) | 93.0 | 94.5 | 95.0 | 94.9 | 94.5 | 94.6 | 94.6 |
| CO selectivity(％) | 92.0 | 97.7 | 97.5 | 97.8 | 97.5 | 97.6 | 97.6 |
| H 2/CO | 1.95 | 1.98 | 1.99 | 1.99 | 1.96 | 1.95 | 1.96 |
Claims (2)
1, the catalyst used of a kind of methyl hydride catalyzed portion oxidation synthesis gas, catalyst consists of ABCO
X/ γ-Al
2O
3, it is characterized in that:
1) be that the loading of benchmark is 16.0-60.0wt% with the carrier;
2) A is selected from a kind of among Ru, Rh, Pd or the Pt, is that the content of benchmark is 0.1-1.0wt% with the carrier;
3) B=Ni is that the content of benchmark is 8.0-30.0wt% with the carrier;
4) C is selected from a kind of among La, Ce, Sm or the Th, is 8.0-30.0% with the carrier for benchmark content;
This catalyst makes like this: the nitrate step impregnation or be immersed in carrier γ-Al altogether successively that adopts B, C, the A of corresponding measurement
2O
3On, successively through 100-120 ℃ of drying, 800-1000 ℃ of high-temperature roasting handled and made.
2, adopt catalyst as claimed in claim 1 to produce the method for synthesis gas, it is characterized in that: the reaction temperature when producing synthesis gas is 800-1000 ℃, and reaction pressure is: 0.1-2.0MPa, air speed is: 3.6 * 10
4-1.5 * 10
6Hr
-1, material molar ratio is CH
4: O
2=2: 1.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279271B (en) * | 2007-04-06 | 2010-09-29 | 中国石油天然气股份有限公司 | Catalyst for producing synthesis gas by catalytic partial oxidation of methane and preparation thereof |
| 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 |
| CN104492456A (en) * | 2014-11-26 | 2015-04-08 | 南京大学 | Ru-based core-shell catalyst and its preparation method and use in methane oxidation reforming preparation of synthetic gas |
| CN106944071B (en) * | 2016-01-07 | 2019-07-12 | 中国石油化工股份有限公司 | The preparation method of methane portion oxidation synthesis gas catalyst |
| CN111282573A (en) * | 2018-12-10 | 2020-06-16 | 中国石油化工股份有限公司 | Iron-based catalyst and preparation method and application thereof |
| CN115739143A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院大连化学物理研究所 | Pt/alpha-MoC-CeO 2 Catalyst, preparation method thereof and application thereof in hydrogen production from methanol steam |
| CN116651460A (en) * | 2023-05-31 | 2023-08-29 | 中国矿业大学 | Preparation method and application of low-load Ni-Mo-based catalyst |
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