CN102614903A - Monolithic catalyst and use of the monolithic catalyst in natural gas reforming for synthesis gas preparation - Google Patents
Monolithic catalyst and use of the monolithic catalyst in natural gas reforming for synthesis gas preparation Download PDFInfo
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- CN102614903A CN102614903A CN2011100308697A CN201110030869A CN102614903A CN 102614903 A CN102614903 A CN 102614903A CN 2011100308697 A CN2011100308697 A CN 2011100308697A CN 201110030869 A CN201110030869 A CN 201110030869A CN 102614903 A CN102614903 A CN 102614903A
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- integral foam
- natural gas
- monolithic catalyst
- catalyst
- gas
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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 invention discloses a monolithic catalyst for natural gas catalytic conversion for synthesis gas preparation. The monolithic catalyst is characterized in that whole foam silicon carbide is utilized as a carrier; the carrier has a three-dimensional communicated-aperture channel structure having open aperture sizes of 0.1 to 6mm and carries at least one of Ni and Rh; and the content of an active metal component is in a range of 0.1 to 25wt%. The monolithic catalyst can convert natural gas, steam and oxygen into synthesis gas so that the temperature distribution of catalyst bed layers is more uniform.
Description
Technical field
The present invention relates to a kind of integer catalyzer of natural gas catalyzed conversion preparing synthetic gas.This catalyst is suitable for needs and strengthens the course of reaction that heat transmits.
Background technology
In natural gas oxygen catalyzing part oxidation preparing synthetic gas reaction,, cause regional area easily if particularly the heat transfer of catalyst carrier is relatively poor for reaction system; Too much heat radiation is too slow and local temperature is high to produce heat such as oxygen and methane gas stream haptoreaction zone; Form focus, same, the but heat undersupply formation cold spot in natural gas and steam reaction zone; Focus causes catalysqt deactivation easily, and cold spot descends reactivity.Traditional packed bed beaded catalyst is because therefore its poor-performing aspect heat transfer and mass transfer is necessary to develop new catalyst.The overall structure catalyst is a carrier with a beautiful gem green stone ceramic honey comb mainly for a long time.This kind material is a basic composition with oxides such as inorganic silicon-aluminums; Exist under the metal cation situation, be prone to generate salt in the high temperature and crystalline phase is changed and cause fragmentation, the poor-performing that shakes of its heat resistanceheat resistant simultaneously; Be difficult to stand violent thermal cycle, its relatively poor capacity of heat transmission has also limited the application of this material.Compare honeycomb structure carrier, the foaming structure carrier is owing to having three-dimensional open-framework, and is therefore more excellent than honeycomb aspect reinforcing mass transfer and heat transfer.General foamed material, such as foam metal, its high-temperature stability and poor chemical stability, foamed alumina is also damaged easily except the heat conductivility difference, and other foam carriers are the problem of ubiquity above-mentioned material all.Carborundum is a kind of excellent high-temperature carrier material, and at high temperature physico-chemical property is stable, good heat-conductive characteristic is arranged, higher antioxygenic property.
Summary of the invention
The purpose of this invention is to provide a kind of integral foam carborundum catalyst, can be used for natural gas and oxygen/or air, water vapour catalyzed conversion preparing synthetic gas.
The objective of the invention is to reach through following measure:
Catalyst provided by the invention, its carrier are integral foam carborundum, and active component is Ni and one of them kind of Rh; Its loading can add auxiliary agents such as Mg, La from 0.1-25wt%; This catalyst has three-dimensional connected pore channel structure, and its big I in through hole road is in 0.1mm-6mm range regulation.
Said integral foam silicon carbide is by Al
2O
3, SiO
2, CeO
2In a kind of or modify more than two kinds, form the integral foam carborundum of coating, the weight load amount 5-15 wt % of coating on integral foam carborundum.
Also be added with a kind of among Mg, the La or two kinds in the said integer catalyzer as auxiliary agent, the loading of auxiliary agent on integer catalyzer is 1-5 wt%.
Preparation of catalysts method provided by the present invention is: the integral foam Carboround is impregnated in the solution that contains active component and/or auxiliary agent to support reactive metal, 100
oAfter the C drying at 800-900
oThe C roasting, this dipping and roasting process can repetitive operations.
The present invention is used for the production of natural gas catalyzed conversion preparing synthetic gas, and its charge ratio is: steam/hydrocarbons ratio is 1.0-3.0, and carbon ratio is 0.4-0.65.Only ratio is that steam/hydrocarbons ratio is 2, and carbon ratio is 0.5.Oxygen feed can be a purity oxygen, also can be air.Reaction condition is a stove catalyst temperature 750
oC-1000
oC, pressure are 0.1-3Mpa, and natural gas volume air speed is 1000-10000h
-1
The present invention has following advantage:
This integer catalyzer can be a synthesis gas with natural gas and water vapour, oxygen conversion, and integral foam carborundum catalyst can be realized strengthening the heat transmission, improves reaction bed temperature and distributes; Make the Temperature Distribution of beds more even.
The specific embodiment
Coating is (by Al
2O
3, SiO
2, CeO
2In a kind of or modify more than two kinds, constitute coating, the weight load amount 5-15 wt % of coating) the preparation process of integral foam carborundum following:
Integral foam carborundum is immersed the Al of 20 wt%
2O
3In the colloidal sol, rotation is got rid of and is removed unnecessary colloidal sol, obtains uniform Al on the surface
2O
3Coating is behind the air drying, 500
oThe C roasting.
(SiO
2And/or CeO
2Modification the same)
Embodiment 1
Get 4 integral foam Carborounds (the weight load of coating is measured 8 wt %) that aluminum oxide coating layer is arranged, earlier with (weight concentration 500 g/L) magnesium nitrate solution dipping, 100
o800 degree roasting 4h after the C drying, the gained calcining matter is again with (weight concentration 250 g/L) nickel nitrate and (weight concentration 30 g/L) lanthanum nitrate hexahydrate dipping, 100
oC oven dry back is at 800 degree roasting 4h.Repeated impregnations nickel nitrate and lanthanum nitrate be roasting process 5 times then, obtains required catalyst, and wherein the percentage by weight of Ni is 8%.
Wherein the oxide weight percentage of magnesium is 1%, and wherein the oxide weight percentage of lanthanum is 2%.
Embodiment 2
Get 4 integral foam Carborounds (the weight load of coating is measured 12 wt %) that aluminum oxide coating layer is arranged, use (weight concentration 40 g/L) rhodium chloride solution dipping, 100
o800 degree roasting 4h after the C drying.Repeat this dipping and roasting process and obtain required catalyst 5 times, wherein the percentage by weight of Rh is 1%.
Application examples 1
Get 4 external diameters according to method preparation in embodiment 1 or 2 and be 24mm, highly pack in the stainless steel fixed bed reactors for the catalyst of 8mm constitutes integral body, the oxygen distribution device of diameter 12mm is placed on the oxygen distribution passage of catalyst centre.Be warmed up to 800 in nitrogen atmosphere
oC reductase 12 h cools to 700 then
oC, raw natural gas is earlier through 380
oThe C desulfurization is gone into reactor then and is reacted after vaporizer and water vapour mixing, oxygen is introduced in the whole beds through the oxygen distribution device.Steam/hydrocarbons ratio is 2 in the raw material, and carbon ratio is 0.5.Slowly increase the natural gas air speed to 3000h
-1, increase reaction pressure to 1Mpa, control outlet temperature 835
oC, and reaction result (methane conversion 95.2%, dry gas is formed: H2:68.8%; CO:16.8%; .CH4:1.4%; CO2:12.7%) show that methane can transform near thermodynamical equilibrium.
Application examples 2
Get 4 external diameters and be 24mm, highly pack in the stainless steel fixed bed reactors for the catalyst formation integral body of 8mm according to method preparation among the embodiment 1; The oxygen distribution device of diameter 6mm is placed on the oxygen distribution passage in the middle of the catalyst, and fill with common Ni base beaded catalyst in the space between oxygen distribution device and the integer catalyzer.Be warmed up to 800 in nitrogen atmosphere
oC reductase 12 h cools to 700 then
oC, raw natural gas is earlier through 380
oThe C desulfurization is gone into reactor then and is reacted after vaporizer and water vapour mixing, oxygen is introduced in the whole beds through the oxygen distribution device.Steam/hydrocarbons ratio is 2 in the raw material, and carbon ratio is 0.5.Slowly increase the natural gas air speed to 3000h
-1, increase reaction pressure to 1Mpa, control outlet temperature 835
oC, reaction result (methane conversion 95.4%, form: H by dry gas
2: 69.7%; CO:16.7%; .CH4:1.5%; CO2:12.1%) show that reaction transforms near thermodynamical equilibrium.
Application examples 3
The external diameter of getting according to method preparation among the embodiment 1 is that the 48mm integer catalyzer reacts according to the method in the application examples 1 for the 36mm total height, and measured beds highest measurement temperature is 954
oC, radially the maximum temperature gradient 88
oC.
Comparative example 1
Use magnesium aluminate spinel to prepare beaded catalyst according to the method among the embodiment 1, use the beds volume the same with application examples 3 as the conventional catalyst of carrier.Method according in the application examples 1 is reacted, measured beds maximum temperature 1075
oC, high radial thermograde 250
oC.Thus it is clear that, beds maximum temperature and the high radial thermograde temperature in the application examples 3.
Claims (7)
1. integer catalyzer is characterized in that: adopting integral foam carborundum is carrier, supports a kind of or two kinds of active components among Ni, the Rh, and the loading of active component is 0.1-25wt%.
2. according to the described integer catalyzer of claim 1, it is characterized in that:
Said integral foam silicon carbide is by Al
2O
3, SiO
2, CeO
2In a kind of or modify more than two kinds, form the integral foam carborundum of coating, the weight load amount 5-15 wt % of coating on integral foam carborundum.
3. according to claim 1 or 2 described integer catalyzers, it is characterized in that: also be added with a kind of among Mg, the La or two kinds in the said integer catalyzer as auxiliary agent, the loading of auxiliary agent on integer catalyzer is 1-5 wt%.
4. according to claim 1 or 2 described integer catalyzers, it is characterized in that: described integral foam Carboround has the pore passage structure of three-dimensional communication; Pore diameter range is 0.1mm-6mm.
5. according to claim 1,2 or 3 described integer catalyzers, it is characterized in that:
Said catalyst adopts immersion process for preparing to obtain: the integral foam Carboround is impregnated in the solution that contains active component or active component and auxiliary agent or auxiliary agent with carrying metal, dry back is at 800-900
oThe C roasting gets product.
6. according to the described integer catalyzer of claim 5, it is characterized in that: said dipping and roasting process can repetitive operations.
7. the application of the said integer catalyzer of claim 1 in the gas renormalizing preparing synthetic gas is characterized in that: being used for natural gas and water vapour, oxygen or air catalyzed conversion is synthesis gas, and the natural gas catalyzed conversion is that the temperature of synthesis gas is 600
oC ~ 1200
oC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100308697A CN102614903A (en) | 2011-01-28 | 2011-01-28 | Monolithic catalyst and use of the monolithic catalyst in natural gas reforming for synthesis gas preparation |
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|---|---|---|---|
| CN2011100308697A CN102614903A (en) | 2011-01-28 | 2011-01-28 | Monolithic catalyst and use of the monolithic catalyst in natural gas reforming for synthesis gas preparation |
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ID=46555317
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941109A (en) * | 2012-11-16 | 2013-02-27 | 浙江大学 | Silicon carbide foam-containing noble metal catalyst |
| CN105728007A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A foam silicon carbide structured catalyst material used for a process of preparing synthesis gas through methane and steam reforming and a preparing method thereof |
| CN110508303A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol Ni-CeO2/SiC-SiO2And the preparation method and application thereof |
| CN110508305A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol Ni-La2O3/SiC-SiO2And the preparation method and application thereof |
| CN110508306A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol LaNiO3/SiC-SiO2- Foam and preparation method thereof |
| CN110508302A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol LaNiO3/SiC-SiO2- Fiber and preparation method |
| CN112684832A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Method and equipment for overcoming temperature reaction lag of silicon carbide annular carrier |
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| CN101856621A (en) * | 2009-04-10 | 2010-10-13 | 中国科学院大连化学物理研究所 | Monolithic catalyst for removing CO from hydrogen by selective oxidation and preparation thereof |
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2011
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| NOBUYUKI GOKON ET AL.,: "Ni/MgO-Al2O3 and Ni-Mg-O catalyzed SiC foam absorbers for high temperature solar reforming of methane", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941109A (en) * | 2012-11-16 | 2013-02-27 | 浙江大学 | Silicon carbide foam-containing noble metal catalyst |
| CN105728007A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | A foam silicon carbide structured catalyst material used for a process of preparing synthesis gas through methane and steam reforming and a preparing method thereof |
| CN110508303A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol Ni-CeO2/SiC-SiO2And the preparation method and application thereof |
| CN110508305A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol Ni-La2O3/SiC-SiO2And the preparation method and application thereof |
| CN110508306A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol LaNiO3/SiC-SiO2- Foam and preparation method thereof |
| CN110508302A (en) * | 2019-08-29 | 2019-11-29 | 华南农业大学 | Biogas full constituent inverting biological catalyst for methanol LaNiO3/SiC-SiO2- Fiber and preparation method |
| CN112684832A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Method and equipment for overcoming temperature reaction lag of silicon carbide annular carrier |
| CN112684832B (en) * | 2019-10-17 | 2022-01-28 | 中国石油化工股份有限公司 | Method and equipment for overcoming temperature reaction lag of silicon carbide annular carrier |
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| CB03 | Change of inventor or designer information |
Inventor after: Li Chunlin Inventor after: Xu Hengyong Inventor after: Hou Shoufu Inventor after: Zhang Jinsong Inventor after: Yang Zhenming Inventor before: Li Chunlin Inventor before: Xu Hengyong Inventor before: Hou Shoufu |
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| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: LI CHUNLIN XU HENGYONG HOU SHOUFU TO: LI CHUNLIN XU HENGYONG HOU SHOUFU ZHANG JINSONG YANG ZHENMING |
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Application publication date: 20120801 |