CN101049566A - Ni base catalyst in use for producing synthesis gas by oxidizing methane partially, and preparation method - Google Patents
Ni base catalyst in use for producing synthesis gas by oxidizing methane partially, and preparation method Download PDFInfo
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- CN101049566A CN101049566A CNA2007100574307A CN200710057430A CN101049566A CN 101049566 A CN101049566 A CN 101049566A CN A2007100574307 A CNA2007100574307 A CN A2007100574307A CN 200710057430 A CN200710057430 A CN 200710057430A CN 101049566 A CN101049566 A CN 101049566A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 230000001590 oxidative effect Effects 0.000 title 1
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 229910007746 Zr—O Inorganic materials 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910018516 Al—O Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 6
- 239000003426 co-catalyst Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 206010013786 Dry skin Diseases 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000003483 aging Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000004939 coking Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229910004625 Ce—Zr Inorganic materials 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
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- Catalysts (AREA)
Abstract
本发明公开了一种用于甲烷部分氧化制合成气的Ni基催化剂及其制备方法。催化剂的载体为复合载体Mg－Al－Ce－Zr－O，其中，CeO2，ZrO2为助催化剂，含量为原始载体Mg－Al－O质量的5％～20％，催化剂活性组分为NiO，含量为原始载体Mg－Al－O质量的10％～15％。其制备方法包括以下过程：将Al、Mg、Ce、Zr的硝酸盐混合溶液滴加至氨水中，搅拌至沉淀完全，经陈化、洗涤、干燥、煅烧后制得Mg－Al－Ce－Zr－O复合载体。将制得载体浸于Ni(NO3)2溶液中，经静置、干燥、煅烧后制得NiO/Mg－Al－Ce－Zr－O催化剂。本发明的优点在于，所制得的催化剂用于甲烷部分氧化制合成气，甲烷转化率达到84％以上，CO选择性达到99％以上，抗积炭性能好，稳定性强，制备成本低。The invention discloses a Ni-based catalyst for producing synthesis gas by partial oxidation of methane and a preparation method thereof. The carrier of the catalyst is a composite carrier Mg-Al-Ce-Zr-O, wherein CeO 2 and ZrO 2 are co-catalysts, the content of which is 5% to 20% of the mass of the original carrier Mg-Al-O, and the active component of the catalyst is NiO , the content is 10%-15% of the original carrier Mg-Al-O mass. Its preparation method includes the following process: drop the nitrate mixed solution of Al, Mg, Ce and Zr into ammonia water, stir until the precipitation is complete, and prepare Mg-Al-Ce-Zr after aging, washing, drying and calcination. -O composite carrier. Immersing the obtained carrier in Ni(NO 3 ) 2 solution, standing still, drying and calcining to obtain NiO/Mg-Al-Ce-Zr-O catalyst. The invention has the advantages that the prepared catalyst is used for the partial oxidation of methane to produce synthesis gas, the conversion rate of methane reaches over 84%, the selectivity of CO reaches over 99%, the anti-coking performance is good, the stability is strong, and the preparation cost is low.
Description
Technical field
The present invention is a kind of Catalysts and its preparation method that is used for methane portion oxidation synthesis gas, belongs to the catalyst technology for preparing synthesis gas.
Background technology
Methane portion oxidation (POM) preparing synthetic gas is the exothermic reaction of a gentleness:
CH
4+1/2O
2→CO+2H
2 ΔH
298k＝-35.8kJ/mol
With traditional methane steam reforming reacting phase ratio, the reactor volume of methyl hydride catalyzed portion oxidation synthesis gas is little, efficient is high, energy consumption is low, can significantly reduce equipment investment and production cost, therefore is subjected to domestic and international extensive concern in recent years.In China, in the national great industrial technology exploitation special project that National Development and Reform Committee announces, propose preparing synthetic gas by natural gas partial oxidation raw catelyst, new technology integrated technique are developed the exploitation content as gas chemical industry's key technology.The catalyst development work of methane portion oxidation synthesis gas in recent years is very active, and the activity of such catalysts component mainly concentrates on Pt, Ru, Rh, Co, Ni, Ir grade in an imperial examination VIII family metal in the methane portion oxidation synthesis gas method according to the literature.The Ni base supported catalyst has higher catalytic activity, and cost is low, and the intensity height is easy to preparation, thereby has using value.But under the pyroreaction condition, active component Ni runs off and sintering easily, the easy coking deactivation of catalyst, poor stability.Noble metal catalyst also is the partial oxidation reaction of methane custom catalysts, and it is active suitable with nickel-base catalyst, and has stronger anti-carbon deposit performance, but noble metal catalyst costs an arm and a leg, and is 100-150 times of nickel-base catalyst, therefore uses less at home.At present, the catalyst system therefor active component mainly concentrates on precious metal in the patent report in Europe.As European patent 6405559 usefulness Pt elements (content is 0.1～20%), European patent 640561 is mainly used the Rh element, promptly mainly is Pt, Rh class noble metal.At present, the unit price of Pt is 320RMB/g, and the unit price of Rh is 1200RMB/g, expensive price limit the industrial applications of noble metal catalyst.Therefore, the catalyst of developing a kind of high activity and having a better anti-carbon deposit performance is the key that the methane portion oxidation technology is applied.
Summary of the invention
The purpose of this invention is to provide a kind of nickel-base catalyst that is used for methane portion oxidation synthesis gas and preparation method thereof, this Preparation of Catalyst cost is low, and catalytic activity is good, and stable and anti-carbon deposit performance is strong.
For achieving the above object, the present invention is realized that by following technical proposals a kind of nickel-base catalyst that is used for methane portion oxidation synthesis gas is characterized in that: the carrier of this catalyst is modification complex carrier Mg-Al-Ce-Zr-O, wherein, and Al
2O
3, MgO, CeO
2, ZrO
2Mass ratio be 140: (40～80): (5～10): (1～5), CeO
2, ZrO
2Be co-catalyst, content is 5%～20% of initial carrier Mg-Al-O quality, and the catalyst activity component is NiO, and content is 10～15% of initial carrier Mg-Al-O quality.
In the above-mentioned catalyst, CeO
2, ZrO
2Content be 8% of initial carrier Mg-Al-O quality.
Above-mentioned Preparation of catalysts method is characterized in that comprising following process: press Al
2O
3, MgO, CeO
2, ZrO
2Mass ratio be 140: (40～80): (5～10): the ratio of (1～5), with Al (NO
3)
3, Mg (NO
3)
2, Ce (NO
3)
3, ZrO (NO
3)
2Mixed solution drip and be 15～28% ammoniacal liquor to mass concentration, under the rotating speed of 100～200rpm, stirred 0.5～2 hour, precipitation fully after, 70～80 ℃ of water-bath ageings 3～12 hours, deionized water washing, 80～120 ℃ of dryings 6～12 hours, grind, calcined 3～5 hours for 400～600 ℃, make the Mg-Al-Ce-Zr-O complex carrier of Ce, Zr modification.Get above-mentioned carrier 3～5g, be dipped in mass fraction and be 50～80% Ni (NO
3)
2In the solution, sample behind the dipping left standstill 12～24 hours under 20 ℃～30 ℃, 80～120 ℃ of dryings 6～12 hours, 800～900 ℃ of following roastings 2～8 hours, through grinding, making granularity is the NiO/Mg-Al-Ce-Zr-O catalyst of 100～160 purpose Ce, Zr modification.
The invention has the advantages that:
Catalyst preparation process is simple, and prepared catalyst activity component Ni is in the carrier surface high degree of dispersion.This catalyst is used for methane portion oxidation synthesis gas, and methane conversion reaches more than 84%, and the CO selectivity reaches more than 99%, and this catalyst in use, and anti-carbon deposit performance is good, and stability is strong, and preparation cost is low.
The specific embodiment
Embodiment 1
Take by weighing 2.078g Al (NO
3)
36H
2O, 0.894g Mg (NO
3)
26H
2O, 0.673g Ce (NO
3)
36H
2O, 0.328gZrO (NO
3)
25H
2O, being mixed with and dropping to the 39.6ml mass concentration behind the mixed solution is in 25% the ammoniacal liquor, under the rotating speed of 150rpm, stirred 1 hour, precipitation fully after, 80 ℃ of water-bath ageings 8 hours then spend deionised water with the gained sediment, 120 ℃ of dryings 10 hours, grind, calcined 5 hours, and made the Mg-Al-Ce-Zr-O complex carrier of Ce, Zr modification for 400 ℃.Get and make complex carrier 3g, be dipped in the 3ml mass fraction and be 60% Ni (NO
3)
2In the solution, the sample behind the dipping at room temperature left standstill 12 hours, 120 ℃ of dryings 12 hours, and 900 ℃ of roastings 3.5 hours in Muffle furnace at last make catalyst NiO/Mg-Al-Ce-Zr-O that granularity is 100～120 purpose Ce, Zr modification through grinding.
This catalyst is used for the test of partial oxidation reaction of methane catalytic performance: adopt fixed-bed reactor, get catalyst 0.5g and be loaded in the crystal reaction tube that diameter is 12mm, reactant is CH
4With Air mixing gas, CH
4: air=2: 5 (mol ratio), flow are 350ml/min.Adopt Siemens's exhaust analyzer to measure product, frequency is 1/6s
-1The catalyst activity evaluation result is listed in table 1.
Table 1 NiO/Mg-Al-Ce-Zr-O catalytic performance is investigated
| Reaction bed temperature/℃ | 600 | 650 | 700 | 750 | 800 |
| CH 4Conversion ratio/% CO selectivity/% | 11 O | 67 89 | 78 94 | 85 97 | 90 99 |
Embodiment 2
Take by weighing 2.078g Al (NO
3)
36H
2O, 0.894g Mg (NO
3)
26H
2O, 1.346g Ce (NO
3)
36H
2O, 0.656gZrO (NO
3)
25H
2O, being mixed with and dropping to the 39.6ml mass concentration behind the mixed solution is in 25% the ammoniacal liquor, under the rotating speed of 150rpm, stirred 1 hour, precipitation fully after, 80 ℃ of water-bath ageings 8 hours then spend deionised water with the gained sediment, 120 ℃ of dryings 10 hours, grind, calcined 5 hours, and made the Mg-Al-Ce-Zr-O complex carrier of Ce, Zr modification for 500 ℃.Get and make complex carrier 3g, be dipped in the 3ml mass fraction and be 60% Ni (NO
3)
2In the solution, the sample behind the dipping at room temperature left standstill 12 hours, 120 ℃ of dryings 12 hours, and 850 ℃ of roastings 3.5 hours in Muffle furnace at last make catalyst NiO/Mg-Al-Ce-Zr-O that granularity is 100～120 purpose Ce, Zr modification through grinding.
The catalyst activity evaluation result is listed in table 2.
Table 2 NiO/Mg-Al-Ce-Zr-O catalytic performance is investigated
| Reaction bed temperature/℃ | 600 | 650 | 700 | 750 | 800 |
| CH 4Conversion ratio/% CO selectivity/% | 16 1 | 68 89 | 80 95 | 88 97 | 94 100 |
After the successive reaction 24 hours, the catalytic activity of catalyst changes little, and wherein methane conversion reduces to 92% by 94%, and carbon monoxide selective reduces to 97% by 100%, and coke content accounts for 11.2% of catalyst total quality.
Embodiment 3
Take by weighing 2.078g Al (NO
3)
36H
2O, 0.894g Mg (NO
3)
26H
2O, 2.019g Ce (NO
3)
36H
2O, 0.984gZrO (NO
3)
25H
2O, being mixed with and dropping to the 39.6ml mass concentration behind the mixed solution is in 25% the ammoniacal liquor, under the rotating speed of 150rpm, stirred 1 hour, precipitation fully after, 80 ℃ of water-bath ageings 8 hours are then washed the gained precipitate with deionized water, 120 ℃ of dryings 10 hours, grind, calcined 5 hours, and made the Mg-Al-Ce-Zr-O complex carrier of Ce, Zr modification for 600 ℃.Get and make complex carrier 3g, be dipped in the 3ml mass fraction and be 60% Ni (NO
3)
2In the solution, the sample behind the dipping at room temperature left standstill 12 hours, 120 ℃ of dryings 12 hours, and 900 ℃ of roastings 3.5 hours in Muffle furnace at last make catalyst NiO/Mg-Al-Ce-Zr-O that granularity is 100～120 purpose Ce, Zr modification through grinding.
The catalyst activity evaluation result is listed in table 3.
Table 3 NiO/Mg-Al-Ce-Zr-O catalytic performance is investigated
| Reaction bed temperature/℃ | 600 | 650 | 700 | 750 | 800 |
| CH 4Conversion ratio/% CO selectivity/% | 0 0 | 53 80 | 66 90 | 75 96 | 84 99 |
Claims (3)
1. a Ni who is used for methane portion oxidation synthesis gas is catalyst based, it is characterized in that: the carrier of this catalyst is modification complex carrier Mg-Al-Ce-Zr-O, wherein, and Al
2O
3, MgO, CeO
2, ZrO
2Mass ratio be 140: (40～80): (5～10): (1～5), CeO
2, ZrO
2Be co-catalyst, content is 5%～20% of initial carrier Mg-Al-O quality, and the catalyst activity component is NiO, and content is 10～15% of initial carrier Mg-Al-O quality.
2. catalyst based by the described Ni that is used for methane portion oxidation synthesis gas of claim 1, it is characterized in that: CeO in the catalyst
2, ZrO
2Content be 8% of initial carrier Mg-Al-O quality.
3. one kind prepares the described catalyst based method of Ni that is used for methane portion oxidation synthesis gas of claim 1, it is characterized in that comprising following process: with Al (NO
3)
3, Mg (NO
3)
2, Ce (NO
3)
3, ZrO (NO
3)
2(Al
2O
3: MgO: CeO
2: ZrO
2=140: (40～80): (5～10): (1～5), mass ratio) during mixed solution drips and is 15～28% ammoniacal liquor to 30～45ml mass concentration, mixture stirred under the rotating speed of 100～200rpm 0.5～2 hour, after precipitation is complete, 70～80 ℃ of water-bath ageings 3～12 hours, the deionized water washing, 80～120 ℃ of dryings 6～12 hours, grind, calcined 3～5 hours for 400～600 ℃, make the Mg-Al-Ce-Zr-O complex carrier of Ce, Zr modification, get above-mentioned carrier 3～5g, be dipped in 2.5～3ml mass fraction and be 50～80% Ni (NO
3)
2In the solution, the sample behind the dipping at room temperature left standstill 12～24 hours, 80～120 ℃ of dryings 6～12 hours, and 800～900 ℃ of following roastings 2～8 hours make the NiO/Mg-Al-Ce-Zr-O catalyst of Ce, Zr modification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100574307A CN101049566A (en) | 2007-05-23 | 2007-05-23 | Ni base catalyst in use for producing synthesis gas by oxidizing methane partially, and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100574307A CN101049566A (en) | 2007-05-23 | 2007-05-23 | Ni base catalyst in use for producing synthesis gas by oxidizing methane partially, and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101049566A true CN101049566A (en) | 2007-10-10 |
Family
ID=38781287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100574307A Pending CN101049566A (en) | 2007-05-23 | 2007-05-23 | Ni base catalyst in use for producing synthesis gas by oxidizing methane partially, and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101049566A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837304A (en) * | 2010-04-29 | 2010-09-22 | 清华大学 | Carrier for preparing syngas Ni-based catalyst through methane partial oxidation |
| EP2308594A2 (en) * | 2008-08-01 | 2011-04-13 | Hyundai Heavy Industries Co., Ltd. | Catalyst for preparing synthesis gas from natural gas and carbon dioxide, and preparation method thereof |
| CN102133532A (en) * | 2010-12-20 | 2011-07-27 | 昆明理工大学 | Method for preparing honeycomb integrated catalyst for catalyzing partial oxidized methane to prepare synthesis gas |
| CN104994953A (en) * | 2013-11-19 | 2015-10-21 | 气体化学技术有限责任公司 | Method for preparing refractory alloy-based polymetallic oxide catalysts for the partial oxidation of hydrocarbons into synthesis gas |
| CN105562003A (en) * | 2016-01-29 | 2016-05-11 | 太原理工大学 | Synthesis gas methanation catalyst and preparation method and application |
| CN105642288A (en) * | 2014-12-06 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of catalyst for partial oxidation of methane to prepare syngas |
| CN105727976A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for partial oxidation of methane to synthetic gas |
| CN110267741A (en) * | 2016-12-29 | 2019-09-20 | 科学研究高等机关 | Process for the production of a catalyst of the formula My(Ce1-xLxO2-x/2)1-y for the reverse water gas shift reaction and partial oxidation of methane to synthesis gas by means of combustion in solution |
-
2007
- 2007-05-23 CN CNA2007100574307A patent/CN101049566A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8524119B2 (en) * | 2008-08-01 | 2013-09-03 | Hyundai Heavy Industries Co., Ltd. | Catalyst for preparing synthesis gas from natural gas and carbon dioxide, and preparation method thereof |
| EP2308594A2 (en) * | 2008-08-01 | 2011-04-13 | Hyundai Heavy Industries Co., Ltd. | Catalyst for preparing synthesis gas from natural gas and carbon dioxide, and preparation method thereof |
| US20110114892A1 (en) * | 2008-08-01 | 2011-05-19 | Ki Won Jun | Catalyst for preparing synthesis gas from natural gas and carbon dioxide, and preparation method thereof |
| CN102112227A (en) * | 2008-08-01 | 2011-06-29 | 现代重工业株式会社 | Catalyst for preparing synthesis gas from natural gas and carbon dioxide and preparation method thereof |
| EP2308594A4 (en) * | 2008-08-01 | 2012-11-21 | Hyun Dai Heavy Ind Co Ltd | CATALYST FOR THE MANUFACTURE OF SYNTHESIS GAS FROM NATURAL GAS AND CARBON DIOXIDE, AND PREPARATION METHOD THEREOF |
| CN102112227B (en) * | 2008-08-01 | 2015-05-20 | 现代重工业株式会社 | Catalyst for producing synthesis gas from natural gas and carbon dioxide and method for its production |
| CN101837304A (en) * | 2010-04-29 | 2010-09-22 | 清华大学 | Carrier for preparing syngas Ni-based catalyst through methane partial oxidation |
| CN101837304B (en) * | 2010-04-29 | 2011-12-28 | 清华大学 | Carrier for preparing syngas Ni-based catalyst through methane partial oxidation |
| CN102133532A (en) * | 2010-12-20 | 2011-07-27 | 昆明理工大学 | Method for preparing honeycomb integrated catalyst for catalyzing partial oxidized methane to prepare synthesis gas |
| CN102133532B (en) * | 2010-12-20 | 2013-04-10 | 昆明理工大学 | Method for preparing honeycomb integrated catalyst for catalyzing partial oxidized methane to prepare synthesis gas |
| CN104994953A (en) * | 2013-11-19 | 2015-10-21 | 气体化学技术有限责任公司 | Method for preparing refractory alloy-based polymetallic oxide catalysts for the partial oxidation of hydrocarbons into synthesis gas |
| CN105642288A (en) * | 2014-12-06 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of catalyst for partial oxidation of methane to prepare syngas |
| CN105727976A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for partial oxidation of methane to synthetic gas |
| CN105642288B (en) * | 2014-12-06 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of preparation method of methane portion oxidation synthesis gas catalyst |
| CN105727976B (en) * | 2014-12-06 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst for methane portion oxidation synthesis gas |
| CN105562003A (en) * | 2016-01-29 | 2016-05-11 | 太原理工大学 | Synthesis gas methanation catalyst and preparation method and application |
| CN110267741A (en) * | 2016-12-29 | 2019-09-20 | 科学研究高等机关 | Process for the production of a catalyst of the formula My(Ce1-xLxO2-x/2)1-y for the reverse water gas shift reaction and partial oxidation of methane to synthesis gas by means of combustion in solution |
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