CN1047103C - Catalyst for converting methane into synthetic gas and its process - Google Patents
Catalyst for converting methane into synthetic gas and its process Download PDFInfo
- Publication number
- CN1047103C CN1047103C CN94103728A CN94103728A CN1047103C CN 1047103 C CN1047103 C CN 1047103C CN 94103728 A CN94103728 A CN 94103728A CN 94103728 A CN94103728 A CN 94103728A CN 1047103 C CN1047103 C CN 1047103C
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- methane
- catalyst
- synthetic gas
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a catalyst of synthetic gas through methane conversion. The catalyst of the present invention comprises at least one metallic element in the VIII group, at least one metallic element which can convert methane into synthetic gas, at least one alkaline and alkali earth metal element, and aluminium oxide or aluminium globules with proper specific surface areas and pore diameters. In the process of converting the methane into the synthetic gas, the methane and gas containing molecular oxygen contact the catalyst of the present invention at a temperature of 300 to 800 DEG C.
Description
The present invention relates to catalyzer that methane oxidation is become synthetic gas and uses thereof.
At present, the vapour reforming of industrial employing methane is produced synthetic gas:
T(k) 800 1000
ΔH(kCal/mol)
[1] 53.21 6.33
Δ G (kCal/mol) 53.87-6.47 these processes have some more serious defectives; (1) owing to reaction (1) absorb heat in a large number consume energy serious; (2) reaction (1) is subjected to the equilibrated restriction and need carries out under high temperature condition with pressure; (3) the synthetic gas H of Sheng Chenging
2Content is higher, is not suitable for doing the raw material of reaction such as synthol.
And come preparing synthetic gas by methane portion oxidation:
T(k) 298 500 700 1000
ΔH(kCal/mol
-1) -8.53 -7.00 -5.7 -5.37
Δ G (kCal/mol
-1Existing problem in the above-mentioned steam reforming reaction may be avoided fully from reaction and thermodynamic data thereof in)-20.58-29.34-36.6-52.52.Therefore over the past two years, people began this reaction is studied.
English Patent (application number 9018781.6) has been introduced to use and has been supported d district metal or d district metal oxide catalyst under 650～900 ℃, the condition of 10～600KPa, and methane portion oxidation is become synthetic gas.
Recently, Patrick D.F.Vernon etc. has reported about what methane oxidation is become synthetic gas and has supported noble metal catalyst and rare earth and noble metal composite oxide Ln
2M
2O
7(Ln is a rare earth element, and M is a precious metal element) catalyzer at 650～1050K, under 1～20atm condition, becomes synthetic gas with methane portion oxidation.These catalyzer can be obtained good reaction result (methane conversion reaches 90～95%, and the selectivity of hydrogen and carbon monoxide is all greater than 95%) down at high temperature (1050K).
The object of the invention just provides a kind of catalyzer, can with selectivity methane conversion be become synthetic gas with very high transformation efficiency under relatively low temperature.
The objective of the invention is to be achieved through the following technical solutions.
Catalyzer provided by the present invention has following two kinds of experience expressions, a kind of is expression with the catalyzer of coprecipitation method preparation: AaBbCcDdOx, in this catalyzer, A is the element of a kind of Ni of being selected from, Pd, Pt, Ir, Rh, Ru, Co, B is the element of a kind of Cu of being selected from, Ag, Zn, Cd, V, Cr, Mo, W, Mn, C is the element of a kind of Li of being selected from, Na, K, Rb, Be, Mg, Ca, Sr, Ba, D is the element of a kind of Si of being selected from, Al, Ti, Zr, wherein: b/a is 0.04-0.4, c/a is 0.4-20, and d/a is 0.5-10.
Above-mentioned catalyst A element is Ni preferably, and the B element is Cu preferably, and the C element is Ca preferably, and the D element is Al preferably.
Another kind is the expression with the supported catalyst of immersion process for preparing: the AaBbCcOx/ carrier, in this catalyzer, A is a kind of Ni of being selected from, Pd, Pt, Ir, Rh, Ru, the element of Co, B is a kind of Cu of being selected from, Ag, Zn, Cd, V, Cr, Mo, W, the element of Mn, C is a kind of Li of being selected from, Na, K, Rb, Be, Mg, Ca, Sr, the element of Ba, D is a kind of Si of being selected from, Al, Ti, the element of Zr, wherein: b/a is 0.04-0.4, c/a is 0.4-20, d/a is 0.5-10, and the loading of active ingredient is 0.01-50% (weight) in the supported catalyst, and catalyst-supporting support can be the silicon-dioxide bead with suitable specific surface area and aperture, the aluminium sesquioxide bead, silicon-dioxide-aluminium sesquioxide bead.
Above-mentioned catalyst A element is Ni preferably, and the B element is Cu preferably, and the C element is Ca preferably, and the D element is Al preferably, and the loading of active ingredient is preferably 1-30% (weight) most in the supported catalyst, and carrier is the aluminium sesquioxide bead preferably.
Catalyzer among the present invention can adopt general co-precipitation, the methods such as slurry or pickling process of mixing prepare.With co-precipitation, mix the catalyst precursor that slurry or pickling process make, 80～150 ℃ dry down, then 400～1000 ℃ of following roastings, concrete maturing temperature is different because of the difference of the raw material forming and select for use.
Methane conversion is become the process of synthetic gas by above-mentioned catalyzer, be with methane with to mix with the gas of molecule-containing keto before catalyzer contacts, the scope of methane/oxygen (mol ratio) is 1.9-2.5, and the gas hourly space velocity of reactor feed gas is controlled at 500-5000,000hr
-1(under the standard state) contacts with catalyzer then, reacts, and the temperature during reaction is 100-1000 ℃, and pressure is the 0.01-10 MPa.
Above-mentioned reaction methane/oxygen optimum is 2.0.
Optimum temps during reaction is controlled at 300-800 ℃.
Optimum pressure during reaction is 0.1 MPa.
The gas hourly space velocity of reactor feed gas is suitably 10,000-500,000hr
-1
Raw material methane can be pure methane, also can be the methane that contains a small amount of gaseous paraffin hydrocarbons.
The gas of molecule-containing keto can be pure oxygen, also can be the gas mixture of air or air and oxygen.
Compare with present methane steam reforming preparing synthetic gas, the present invention has the following advantages: (1) reacts micro-heat release, consumed energy no longer, CO/H in the synthetic gas that (2) make
2Near 0.5, be more suitable for being synthesizing methanol and fischer-tropsch synthetic raw material, low 600-700 ℃ of (3) temperature of reaction, (4) reaction efficiency height, the selectivity of methane conversion and carbon monoxide and hydrogen all can be higher than 95%.
Following comparative examples is further illustrated catalyzer of the present invention.Embodiment 1:
Take by weighing Ni (NO
3)
26H
2O 0.998 gram, Cu (NO
3)
23H
2O 0.166 gram, Al (NO
3)
39H
2O 3.001 grams, Ca (NO
3)
24H
2O 0.041 restrains and they is dissolved in the 20ml water, under agitation slowly adds 10% (NH then
4)
2CO
3Solution is until being completed into gel; With the gel detergent that obtains, in 110 ℃ of following dry 16hr, 750 ℃ of roasting 4hr promptly make catalyzer in the air afterwards.
Get 0.2ml20～40 purpose catalyzer and put into the quartz tube reactor that internal diameter is 8mm, following at 500 ℃ with containing 10%H
2N
2-H
2Gas mixture (flow 40ml/min) is handled 1hr and is reacted then, and gained the results are shown in Table 1:
Table 1
T(℃) XCH
4(％) XO
2(％) SCO(％) SH
2(％)
500 84.3 100 86.1 90.2
550 89.1 100 90.5 95.4
600 94.2 100 94.2 98.1
650 96.0 100 95.4 99.0
700 98.1 100 97.1 100 reaction conditionss: GHSV=3 * 10
4Hr
-1, CH
4: O
2: N
2=2: embodiment 2 in 1: 0:
Employed catalyzer and pretreatment condition all are same as embodiment 1 in this example, change the intake velocity of reactor feed gas, and the reaction result of gained is as shown in table 2:
Table 2
GHSV(hr
-1) XCH
4(％) XO
2(％) SCO(％) SH
2(％)
5.000 98.5 100 98.0 100
10.000 98.1 100 97.2 100
20.000 99.0 100 97.2 100
30.000 98.1 100 97.1 100
40.000 97.1 100 96.5 99.0
60.000 90.2 100 92.1 96.5
300.000 83.4 100 87.2 84.7 reaction conditions: T=700 ℃, CH
4: O
2: N
2=2: embodiment 3 in 1: 0:
Employed catalyzer and pretreatment condition all are same as embodiment 1 in this example, change the composition of reactor feed gas, and the reaction result of gained is as shown in table 3:
Table 3
CH
4∶O
2∶N
2 CH
4 XO
2 SCO SH
2
2∶1∶0 98.2 100 97.0 100
2∶1∶2 98.2 100 97.1 100
2: 1: 4 99.0 100 97.0 100 reaction conditions: T=700 ℃, GHSV=3 * 104hr
-1Embodiment 4:
Take by weighing Ni (NO
3)
26H
2O 0.931 gram, Zn (NO
3)
26H
2O 0.076 gram, Ca (NO
3)
24H
20.283 gram, Al (NO
3)
39H
2O 3.001 gram is dissolved in them in the 20ml water, slowly adds 10% (NH when stirring this mixing solutions
4)
2CO
3Solution is completed into gel until mixed solution.With gel detergent, 110 ℃ of following dry 16hr, 750 ℃ of roasting 4hr in the air, 500 ℃ of following reduction 1hr (10%H
2-N
2, GHSV=10,000h
-1) catalyzer gets product.
Get in the reactor of 0.2ml catalyzer in example 1 and react, change the temperature of reaction gained and the results are shown in Table 4.
Table 4
T(℃) GHSV(hr
-1) XCH
4 XO
2 SCO SH
2
600 30,000 78.2 100 90.1 90.3
700 30,000 84.6 100 93.2 9.21
750 30,000 89.2 100 94.6 95.0
750 60,000 91.0 100 95.2 93.8 reaction conditions: CH
4: O
2: N
2=2: embodiment 5 in 1: 0:
Take by weighing Al (NO
3)
39H
2O 3.60 grams, and be dissolved in the 15ml water, adding 10% (NH down stirred
4)
2CO
3Be about 8 to pH, with the at room temperature aging 24hr of gel that obtains, washing.Take by weighing Ni (NO
3)
26H
2O 1.98 grams, La (NO
3)
36H
2O 0.356 restrains, and mixes with the gel that makes previously, after the grinding evenly, and 110 ℃ of following dry 16hr, 750 ℃ of roasting 4hr in the air.Get 20～40 purpose catalyzer 0.2ml, at the O of 40ml/min
2Air-flow and 500 ℃ of following 1hr that handle react resulting result in the reactor in embodiment 1, see Table 5
Table 5
T(℃) XCH
4 XO
2 SCO SH
2
750 96.0 100 97.0 99.0
700 90.4 100 91.2 94.8
550 78.2 100 82.4 89.5 reaction conditionss: CH
4: O
2: N
2=2: 1: 0, GHSV=3 * 104hr
-1Embodiment 6:
Take by weighing 20～40 purpose Al
2O
3(specific surface 168m
2/ g) 1.608 restrain, be dissolved with 1.222 gram Ni (NO with 1.6ml
3)
26H
2O, 0.201 gram Cu (NO
3)
23H
2O, 0.051 gram Ca (NO
3)
24H
2The aqueous solution of O floods it, in the drying of 110 ℃ of following 16hr and air 750 ℃, after the roasting of 4hr, makes catalyzer.
Get the reactor that the 0.2ml catalyzer places example 1, use the O of 40ml/min earlier
2Handle 1hr down at 500 ℃, carry out the methane oxidation reaction then, reaction result such as table 6 expression
Table 6
T(℃) XCH
4(％) XO
2(％) SCO(％) SH
2(％)
750 90.8 100 95.2 99.0
700 93.6 100 94.0 98.0
600 90.2 100 90.1 94.6
500 82.1 100 85.7 90.1 reaction conditionss: GHSV=3 * 104hr
-1, CH
4: O
2: N
2=2: embodiment 7 in 1: 0:
Take by weighing 1.397 gram Ni (NO
3)
26H
2O, 0.232 gram Cu (NO
3)
23H
2O, 4.20 gram Al (NO
3)
39H
2O is dissolved in the 30ml water and is made into mixing solutions, stirs this mixed solution and adds 10% (NH
4)
2CO
3Solution is until being completed into gel.Detergent gel and at 110 ℃ of following dry 16hr, 750 ℃ of following roasting 4hr.
Get the reactor that the above-mentioned catalyzer of 0.2ml places example 1, at first at 500 ℃ of O that use 40ml/min down
2Handle 1hr, react then, the results are shown in Table 7.
Table 7
T(℃) GHSV(hr
-1) XCH
4(％) XO
2(％) SCO(％) SH
2(％)
700 3×104 96.8 100 96.0 100
600 3×104 91.7 100 93.2 98.0
500 3×104 84.5 100 87.0 90.8
700 6×104 92.1 100 93.8 95.6
700 3 * 105 84.0 100 88.0 87.2 reaction conditions: CH
4: O
2: N
2=2: embodiment 8 in 1: 0:
Take by weighing 20～40 purpose silicon bead (specific surface 196m
2/ g) 1.582 restrain, contain 1.339 gram Ni (NO with 1.6ml
3)
26H
2O, 0.225 gram Cu (NO
3)
23H
2Behind the aqueous solution dipping of O, dry 16hr under 110 ℃, 750 ℃ of roasting 4hr promptly make catalyzer
Get the reactor that the 0.2ml catalyzer places embodiment 1, the methane oxidation reaction result of gained sees Table 8
Table 8
T(℃) XCH
4(％) XO
2(％) SCO(％) SH
2(％)
750 92.1 100 92.7 95.0
700 88.6 100 89.6 91.4
600 80.1 100 83.7 86.2
500 75.4 100 80.1 80.9 reaction conditionss: GHSV=3 * 10
4Hr
-1, CH
4: O
2: N
2=2: embodiment 9 in 1: 0:
Catalyzer (1) (2) adopts the method for preparing catalyst among the embodiment 1 to prepare, and catalyzer (3) (4) adopts the method for preparing catalyst among the embodiment 6 to prepare, and carries out the methane oxidation reaction according to the response procedures among the embodiment 1, resultingly the results are shown in Table 9
Table 9
Numbering catalyzer XCH
4(%) XO
2(%) SCO (%) SH
2(%)
1 CoYb
0.2Mg
0.05Al
4Ox 92.1 100 92.7 95.0
2 CoNd
0.33Al
3.33Ox 88.6 100 89.6 91.4
3 1％Pt-0.38％Dy
2O
3/Al
2O
3 80.1 100 83.7 86.2
4 1%Ru-0.70%Eu
2O
3/ Al
2O
375.4 100 80.1 80.9 reaction conditionss: catalyst levels 0.2ml, T=700 ℃, GHSV=3 * 104hr
-1,
CH
4∶O
2∶N
2=2∶1∶0
Claims (8)
1. a catalyzer that is used for the methane conversion preparing synthetic gas is characterized in that the catalyzer expression with the coprecipitation method preparation is AaBbCcDdOx,
(1) A is the element of a kind of Ni of being selected from, Pd, Pt, Ir, Rh, Ru, Co,
(2) B is the element of a kind of Cu of being selected from, Ag, Zn, Cd, V, Cr, Mo, W, Mn,
(3) C is the element of a kind of Li of being selected from, Na, K, Rb, Be, Mg, Ca, Sr, Ba,
(4) D is the element of a kind of Si of being selected from, Al, Ti, Zr, and wherein: b/a is 0.04-0.4, and c/a is 0.4-20, and d/a is 0.5-10.
2. catalyzer as claimed in claim 1 is characterized in that elements A wherein is Ni, and element B is Cu, and Elements C is Ca, and element D is Al.
3. a catalyzer that is used for the methane conversion preparing synthetic gas is characterized in that the supported catalyst expression with immersion process for preparing is the AaBbCdOx/ carrier,
(1) A is the element of a kind of Ni of being selected from, Pd, Pt, Ir, Rh, Ru, Co,
(2) B is the element of a kind of Cu of being selected from, Ag, Zn, Cd, V, Cr, Mo, W, Mn,
(3) C is the element of a kind of Li of being selected from, Na, K, Rb, Be, Mg, Ca, Sr, Ba,
(4) D is a kind of element that is selected from Si, Al, Ti, Zr,
(5) catalyst-supporting support be silicon-dioxide bead or aluminium sesquioxide bead or, silicon-dioxide-aluminium sesquioxide bead, wherein, b/a is 0.04-0.4, and c/a is 0.4-20, d/a is 0.5-10, and the loading of active ingredient is 0.01-50% (weight) in the supported catalyst.
4. catalyzer as claimed in claim 3 is characterized in that elements A wherein is Ni, and element B is Cu, and Elements C is Ca, and D is Al.
5. catalyzer as claimed in claim 3 is characterized in that catalyst-supporting support wherein is Al
2O
3Bead.
6. catalyzer as claimed in claim 3 is characterized in that supported catalyst active principle loading wherein is 1-30% (weight).
7. the purposes of the catalyzer of claim 1 is characterized in that under 300-800 ℃ temperature, and the gas mixture that the methane and the gas of molecule-containing keto are made into contacts with the catalyzer of claim 1-2.
8. the purposes of the catalyzer of claim 3 is characterized in that under 300-800 ℃ temperature, and the gas mixture that the methane and the gas of molecule-containing keto are made into contacts with the catalyzer of claim 3-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94103728A CN1047103C (en) | 1994-04-05 | 1994-04-05 | Catalyst for converting methane into synthetic gas and its process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94103728A CN1047103C (en) | 1994-04-05 | 1994-04-05 | Catalyst for converting methane into synthetic gas and its process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1110248A CN1110248A (en) | 1995-10-18 |
| CN1047103C true CN1047103C (en) | 1999-12-08 |
Family
ID=5031245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94103728A Expired - Fee Related CN1047103C (en) | 1994-04-05 | 1994-04-05 | Catalyst for converting methane into synthetic gas and its process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1047103C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110362C (en) * | 1996-11-17 | 2003-06-04 | 中国石化齐鲁石油化工公司 | Energy-saving hydrocarbon steam conversion catalyst and use thereof |
| CN1087657C (en) * | 1996-12-30 | 2002-07-17 | 中国科学院成都有机化学研究所 | Process for preparing catalyst for producing synthetic gas from hydrocarbons |
| US7438889B2 (en) * | 2005-06-24 | 2008-10-21 | University Of South Carolina | Use of complex metal oxides in the autothermal generation of hydrogen |
| KR101404770B1 (en) * | 2006-09-20 | 2014-06-12 | 상하이 리서치 인스티튜트 오브 페트로케미칼 테크놀로지 시노펙 | A nickel catalyst for selective hydrogenation |
| 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 |
| CN104549265B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Catalyst for synthesizing ethylidene diacetate and application of catalyst |
| CN109718781B (en) * | 2017-10-27 | 2021-12-31 | 中国石油化工股份有限公司 | Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof |
| JP7100843B2 (en) * | 2018-04-11 | 2022-07-14 | 国立大学法人北海道大学 | Partial oxidation catalyst for light hydrocarbons and method for producing carbon monoxide using it |
| CN109876852A (en) * | 2019-03-27 | 2019-06-14 | 太原理工大学 | A PtO@MFI encapsulated structure catalyst for partial oxidation of methane to syngas and its preparation method and application |
| CN113058613B (en) * | 2021-03-18 | 2022-08-26 | 浙江师范大学 | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof |
| CN116651460A (en) * | 2023-05-31 | 2023-08-29 | 中国矿业大学 | Preparation method and application of a low loading Ni-Mo based catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU483999A1 (en) * | 1972-06-27 | 1975-09-15 | Институт Химии Ан Уз Сср | Catalyst for natural gas conversion |
| SU1734820A1 (en) * | 1990-05-21 | 1992-05-23 | Институт катализа СО АН СССР | Method of obtaining catalyst for methane conversion by steam |
| SU1747144A1 (en) * | 1990-04-28 | 1992-07-15 | Государственный Научно-Исследовательский Энергетический Институт Им.Г.М.Кржижановского | Catalyst for carbon dioxide conversion of methane |
-
1994
- 1994-04-05 CN CN94103728A patent/CN1047103C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU483999A1 (en) * | 1972-06-27 | 1975-09-15 | Институт Химии Ан Уз Сср | Catalyst for natural gas conversion |
| SU1747144A1 (en) * | 1990-04-28 | 1992-07-15 | Государственный Научно-Исследовательский Энергетический Институт Им.Г.М.Кржижановского | Catalyst for carbon dioxide conversion of methane |
| SU1734820A1 (en) * | 1990-05-21 | 1992-05-23 | Институт катализа СО АН СССР | Method of obtaining catalyst for methane conversion by steam |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1110248A (en) | 1995-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1121346C (en) | Process for preparation of synthesis gas | |
| CN1035161C (en) | Ethylene oxide catalyst and process | |
| CN1113681C (en) | Autothermic reactor comprising oxygen ion conducting dense ceramic membrane and process using autothermic reactor for producing synthesis gas | |
| JP5279227B2 (en) | Catalyst for fuel reforming reaction and method for producing hydrogen using the same | |
| CN1208236C (en) | Hydrogen Refining Unit | |
| JP3345782B2 (en) | Catalyst for syngas production and method for producing carbon monoxide | |
| CN1047103C (en) | Catalyst for converting methane into synthetic gas and its process | |
| US8834835B2 (en) | Ultra high temperature shift catalyst with low methanation | |
| CN1541139A (en) | Method for activating catalysts containing cobalt compounds and supports | |
| CN1473074A (en) | Catalyst for reforming hydrocarbons and method for reforming hydrocarbons using the catalyst | |
| JP5778309B2 (en) | Hydrogen production catalyst and hydrogen production method using the same | |
| CN86104014A (en) | The method of methane conversion and catalyzer | |
| CN1921937A (en) | Reforming catalyst for hydrocarbon, method for producing hydrogen using the same, and fuel cell system | |
| CN1303320A (en) | Catalyst and process for oxidation of ethane and/or ethylene | |
| TW200836833A (en) | Catalyst for carbon monoxide conversion and method of carbon monoxide modification with the same | |
| CN1016776B (en) | Improved process for converting methane to higher hydrocarbon products | |
| CN1646220A (en) | Catalyst for partial oxidation of hydrocarbon, process for producing the same, process for producing hydrogen-containing gas with the use of the catalyst and method of using hydrogen-containing gas pr | |
| JP2000176287A (en) | Catalyst for methanol synthesis and synthetic method of methanol | |
| CN85103997A (en) | Produce the method for alcohol from carbon monoxide and hydrogen with alkali-molybdenum sulfide catalyst | |
| US20090118119A1 (en) | Water gas shift catalyst | |
| CN1045198C (en) | Low temp. catalyst for methane oxidative coupling | |
| CN1623893A (en) | Modifying catalyst for partial oxidation and method for modification | |
| JP2004344721A (en) | Oxygen-containing hydrocarbon reforming catalyst, method for producing hydrogen or synthesis gas using the same, and fuel cell system | |
| CN1819871A (en) | Carbon monoxide removing catalyst and production process for the same as well as carbon monoxide removing apparatus | |
| CN1059318A (en) | A kind of catalysis process by hydrocarbon conversion and combustion reactions production of synthetic gas in next life |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |