CN1344671A - Catalyst for reforming mathand and carbon dioxide to synthesize gas - Google Patents

Catalyst for reforming mathand and carbon dioxide to synthesize gas Download PDF

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Publication number
CN1344671A
CN1344671A CN 01135912 CN01135912A CN1344671A CN 1344671 A CN1344671 A CN 1344671A CN 01135912 CN01135912 CN 01135912 CN 01135912 A CN01135912 A CN 01135912A CN 1344671 A CN1344671 A CN 1344671A
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China
Prior art keywords
catalyst
methane
carbon dioxide
reforming
carrier
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Pending
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CN 01135912
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Chinese (zh)
Inventor
王晓来
�田宏
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Priority to CN 01135912 priority Critical patent/CN1344671A/en
Publication of CN1344671A publication Critical patent/CN1344671A/en
Pending legal-status Critical Current

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Abstract

The catalyst for reforming methane and carbon dioxide to synthesize gas has SiO2 or gamma-Al2O3 carrier and contains Ni 6-13 wt% and MoO3 or WO3 1.5-3.5 wt%. The catalyst is prepared through soaking process and has the features of high activity, sintering resistance, high carbon deposit resisting capacity, etc. In the conditions of normal pressure, 780 deg.c temperature, space velocity 8400 ml/g.hr, and methane to carbon dioxide ratio of 1, the conversino rate of methane and carbon dioxide may be maintained over 90 % in the reaction process of 20 hr.

Description

Methane and CO 2 reformation catalyst for preparing synthetic gas
The present invention relates to a kind of methane and CO 2 reformation catalyst for preparing synthesized gas and preparation method thereof.
Methane and CO 2 reformation preparing synthetic gas; can not only catalytic activation enrich inexpensive methane and carbonic acid gas and produce the synthetic gas of rich carbon monoxide; also because the strong heat absorptivity of this reaction is having wide application prospect aspect the chemical energy storage, make this be reflected at and effectively utilize Sweet natural gas, alleviate Greenhouse effect, slow down aspect such as energy dilemma and all have important practical significance.
The catalyzer that is used for methane and CO 2 reformation preparing synthetic gas at present mainly contains Pt family noble metal catalyst and Fe is a transition-metal catalyst.The advantage of noble metal catalyst is the catalytic activity height, and anti-carbon deposit performance is strong, and weak point is that noble metal catalyst costs an arm and a leg.Loading type nickel-based catalyst has good catalytic activity, but because carbon deposit, sintering and and carrier between shortcomings such as solid state reaction, cause the very fast decline of catalyst activity.Therefore, changing the catalyst based existence of cheap transition metal Ni, improve its catalytic activity and stability, is one of present this field problem anxious to be solved.
The purpose of this invention is to provide the strong methane of a kind of active height and anti-carbon deposit, caking power and the Catalysts and its preparation method of CO 2 reformation preparing synthetic gas.
Support of the catalyst of the present invention is SiO 2Or γ-Al 2O 3, active ingredient is by 6%～13% weight Ni, 1.5%～3.5% weight MoO 3Or WO 3Form.
Catalyzer of the present invention adopts immersion process for preparing, it is characterized in that elder generation is made into its ammonia complex solution with the salt of Ni, adds with ammoniacal liquor to urge molten Mo or the salts solution of W again, and the mixture that is made into comes impregnated carrier as steeping fluid.After 100～120 ℃ of dryings, again through 500～800 ℃ of roasting 4-8 hours, use 600～800 ℃ of following reduction activations of hydrogen at last, make catalyzer.
The corresponding salt of the used nickel of catalyzer of the present invention is a nickelous nitrate.Used Mo or W salt are respectively ammonium molybdate and ammonium tungstate.This catalyzer used carrier is SiO 2Or γ-Al 2O 3The employing fixed bed is a reactor, and gas hourly space velocity is 8400mlg -1H -1, normal pressure is reaction down, and under 780 ℃, the transformation efficiency of methane and carbonic acid gas all remains on more than 90% in 20 hours reaction process.
Embodiment 1: adopt 2.0gSiO 2Carrier, its shape and size are 30～60 purpose particles.The 0.8919g nickelous nitrate is made into its ammonia complex solution, adds then with the short 0.0602 molten (NH of ammoniacal liquor 4) 6Mo 7O 244H 2O, the mixture that is made into is as the steeping fluid impregnated carrier.Stir, 100～120 ℃ were descended dry 2 hours, and again through 600 ℃ of roasting 4-8 hours, promptly obtained finished catalyst.
Get 0.3g30～this catalyzer of 60 orders and place the quartz tube reactor of φ 6mm.Feed 1: 1 CH 4And CO 2Reaction gas, its air speed are 8400mlg -1H -1, successive reaction 20h under 780 ℃ of normal pressures.Reaction result is listed in table 1.
The transformation efficiency of table 1. methane and carbonic acid gas and yield are with the variation in reaction times
Time (h) ??X CH4(％) ??X CO2(％) ??Y CO(％) ??Y H2(％)
????0 ????95.5 ????95.9 ????95.7 ????95.4
????2 ????96.0 ????97.0 ????96.5 ????95.5
????4 ????96.2 ????97.2 ????96.7 ????95.7
????6 ????96.1 ????96.9 ????96.5 ????95.7
????8 ????96.5 ????97.4 ????96.9 ????96.0
???10 ????96.2 ????96.6 ????96.3 ????95.9
???12 ????95.5 ????96.4 ????95.9 ????95.0
???14 ????95.5 ????96.3 ????95.9 ????95.1
???16 ????95.7 ????96.3 ????96.0 ????95.4
???18 ????96.5 ????96.5 ????96.5 ????96.5
???20 ????96.2 ????96.6 ????96.4 ????96.0
X CH4: CH 4Transformation efficiency X CO2: CO 2Transformation efficiency Y CO: CO yield Y H2: H 2Yield
Embodiment 2: adopt 2.0gSiO 2Carrier, its shape and size are 30～60 purpose particles.The 0.8919g nickelous nitrate is made into its ammonia complex solution, adds then with the short molten 0.0910g (NH of ammoniacal liquor 4) 5H 5[H 2(WO 4) 6] 4H 2O, following step is with embodiment 1.Get 0.3g30～this catalyzer of 60 orders, adopt reaction unit and the reaction conditions of embodiment 1.Reaction result is listed in table 2.
The transformation efficiency of table 2. methane and carbonic acid gas and yield are with the variation in reaction times
Time (h) ??X CH4(％) ??X CO2(％) ??Y CO(％) ??Y H2(％)
?????0 ????89.7 ????91.6 ????90.6 ????88.7
?????2 ????89.4 ????92.0 ????90.7 ????88.0
?????4 ????92.1 ????93.8 ????92.9 ????91.3
?????6 ????92.3 ????94.5 ????93.4 ????91.2
?????8 ????92.1 ????94.2 ????93.2 ????91.0
????10 ????92.4 ????94.5 ????93.4 ????91.4
????12 ????92.5 ????94.5 ????93.5 ????91.5
????14 ????92.5 ????94.0 ????93.2 ????91.7
????16 ????92.9 ????94.3 ????93.6 ????92.2
????18 ????93.2 ????93.6 ????93.4 ????92.9
????20 ????92.8 ????94.4 ????93.6 ????92.6
X CH4: CH 4Transformation efficiency X CO2: CO 2Transformation efficiency Y CO: CO yield Y H2: H 2Yield
Embodiment 3: adopt 2.0g γ-Al 2O 3Carrier, its shape and size are 30～60 purpose particles.Following step is with embodiment 1.
Get 0.3g30～this catalyzer of 60 orders, adopt reaction unit and the reaction conditions of embodiment 1.Reaction result is listed in table 3.
The transformation efficiency of table 3 methane and carbonic acid gas and yield are with the variation in reaction times
Time (h) ??X CH4(％) ??X CO2(％) ??Y CO(％) ??Y H2(％)
?????0 ????95.5 ????96.3 ????96.0 ????95.4
?????2 ????95.6 ????96.5 ????96.2 ????95.5
?????4 ????95.1 ????95.9 ????95.5 ????95.0
?????6 ????95.0 ????95.9 ????95.5 ????95.0
?????8 ????94.7 ????96.2 ????95.5 ????94.6
????10 ????94.5 ????95.7 ????95.1 ????94.4
????12 ????93.5 ????94.8 ????94.1 ????93.5
Time (h) ??X CH4(％) ??X CO2(％) ??Y CO(％) ??Y H2(％)
????14 ????93.9 ????95.2 ????94.6 ????93.9
????16 ????93.9 ????95.3 ????94.6 ????93.9
????18 ????93.9 ????95.2 ????94.5 ????93.8
????20 ????92.6 ????94.4 ????93.5 ????92.4
X CH4: CH 4Transformation efficiency X CO2: CO 2Transformation efficiency Y CO: CO yield Y H2: H 2Yield
Embodiment 4: adopt 2.0g γ-Al 2O 3Carrier, its shape and size are 30～60 purpose particles.Following step is with embodiment 2.
Get 0.3g30～this catalyzer of 60 orders, adopt reaction unit and the reaction conditions of embodiment 1.Reaction result is listed in table 4.
The transformation efficiency of table 4. methane and carbonic acid gas and yield are with the variation in reaction times
Time (h) ??X CH4(％) ??X CO2(％) ??Y CO(％) ??Y H2(％)
?????0 ????91.6 ????92.0 ????90.5 ????90.0
?????2 ????91.6 ????92.1 ????91.5 ????90.2
?????4 ????91.7 ????92.3 ????91.6 ????90.0
?????6 ????91.5 ????92.0 ????91.4 ????90.6
?????8 ????91.7 ????92.4 ????91.5 ????90.3
????10 ????91.7 ????92.3 ????91.2 ????90.1
????12 ????91.7 ????92.3 ????91.5 ????90.5
????14 ????90.4 ????90.9 ????90.3 ????90.1
????16 ????90.4 ????91.0 ????90.4 ????90.2
????18 ????90.3 ????91.2 ????90.5 ????90.3
????20 ????90.1 ????90.9 ????90.7 ????90.0
X CH4: CH 4Transformation efficiency X CO2: CO 2Transformation efficiency Y CO: CO yield Y H2: H 2Yield

Claims (2)

1. methane and CO 2 reformation catalyst for preparing synthetic gas is characterized in that carrier is SiO 2Or γ-Al 2O 3, active ingredient is by 6%～13% weight Ni, 1.5%～3.5% weight MoO 3Or WO 3Form.
2. Preparation of catalysts method as claimed in claim 1, adopt immersion process for preparing, it is characterized in that earlier nickelous nitrate being made into its ammonia complex solution, add with ammoniacal liquor again and urge the molten ammonium molybdate or the salts solution of ammonium tungstate, the mixture that is made into comes impregnated carrier as steeping fluid; After 100～120 ℃ of dryings, again through 500～800 ℃ of roasting 4-8 hours, use 600～800 ℃ of following reduction activations of hydrogen at last, make catalyzer.
CN 01135912 2001-10-17 2001-10-17 Catalyst for reforming mathand and carbon dioxide to synthesize gas Pending CN1344671A (en)

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Application Number Priority Date Filing Date Title
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102745648A (en) * 2011-04-22 2012-10-24 太原理工大学 Preparation method of catalyst for producing synthetic gas by methane and carbon dioxide reformation
CN101347735B (en) * 2007-07-19 2013-02-06 中国石油化工股份有限公司 Methanation catalyst for removing trace amounts of oxycarbide
CN103055868A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Nickel-based catalyst and preparation method thereof
CN103058138A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Preparation method of synthesis gas
CN104971784A (en) * 2015-07-07 2015-10-14 厦门大学 Preparation method of supported metal catalysts
WO2016011970A1 (en) * 2014-07-25 2016-01-28 苏州汉瀚储能科技有限公司 Use of tungsten-containing material
CN106944071A (en) * 2016-01-07 2017-07-14 中国石油化工股份有限公司 The preparation method of methane portion oxidation synthesis gas catalyst
CN109718799A (en) * 2017-10-31 2019-05-07 中国石油化工股份有限公司 The method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas
CN110980639A (en) * 2019-12-31 2020-04-10 湘潭大学 Method for directly producing hydrogen by methane conversion under microwave catalysis
CN112275293A (en) * 2020-09-07 2021-01-29 昆明理工大学 Preparation and reforming method of catalyst for low-carbon alkane reforming hydrogen production and application thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101347735B (en) * 2007-07-19 2013-02-06 中国石油化工股份有限公司 Methanation catalyst for removing trace amounts of oxycarbide
CN102745648A (en) * 2011-04-22 2012-10-24 太原理工大学 Preparation method of catalyst for producing synthetic gas by methane and carbon dioxide reformation
CN103055868A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Nickel-based catalyst and preparation method thereof
CN103058138A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Preparation method of synthesis gas
CN103058138B (en) * 2011-10-24 2014-12-10 中国石油化工股份有限公司 Preparation method of synthesis gas
WO2016011970A1 (en) * 2014-07-25 2016-01-28 苏州汉瀚储能科技有限公司 Use of tungsten-containing material
CN104971784A (en) * 2015-07-07 2015-10-14 厦门大学 Preparation method of supported metal catalysts
CN106944071A (en) * 2016-01-07 2017-07-14 中国石油化工股份有限公司 The preparation method of methane portion oxidation synthesis gas catalyst
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
CN109718799A (en) * 2017-10-31 2019-05-07 中国石油化工股份有限公司 The method of loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas
CN110980639A (en) * 2019-12-31 2020-04-10 湘潭大学 Method for directly producing hydrogen by methane conversion under microwave catalysis
CN110980639B (en) * 2019-12-31 2021-10-26 湘潭大学 Method for directly producing hydrogen by methane conversion under microwave catalysis
CN112275293A (en) * 2020-09-07 2021-01-29 昆明理工大学 Preparation and reforming method of catalyst for low-carbon alkane reforming hydrogen production and application thereof
CN112275293B (en) * 2020-09-07 2024-03-15 昆明理工大学 Preparation method and reforming method of catalyst for low-carbon alkane reforming hydrogen production and application of catalyst

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