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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- 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 Ni-based catalyst (NiO/Mg-Al-Ce-Zr-O) for preparing synthetic gas by partially oxidizing methane is composed of the carrier Mg-Al-Ce-Zr-O, where Mg-Al-O is primary carrier and CeO2 and ZrO2 are the co-catalyst, and the active component NiO. Its preparing process includes such steps as mixing the nitrate solutions of Al, Mg, Ce and Zr, dripping the mixture into ammonia water, stirring until full deposition, ageing, washing, drying, calcining to obtain said compound carrier, immersing it in the solution of Ni(NO3)2, laying aside, drying and calcining. It has high conversion rate, selectivity, resistance to carbon deposit, and stability.
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 |
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|---|---|---|---|
| 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 |
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|---|---|
| CN101049566A true CN101049566A (en) | 2007-10-10 |
Family
ID=38781287
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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 | Reverse water-gas-shift reaction is used for by the method production burnt in solution and methane portion oxidation is the formula M of synthesis gasy(Ce1-xLxO2-x/2)1-yCatalyst method |
-
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 preparing 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 preparing synthesis gas from natural gas and carbon dioxide, and preparation method thereof |
| 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 | Reverse water-gas-shift reaction is used for by the method production burnt in solution and methane portion oxidation is the formula M of synthesis gasy(Ce1-xLxO2-x/2)1-yCatalyst method |
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