CN1309079A - Catalyst for preparing synthetic gas by reforming methane and CO2 - Google Patents
Catalyst for preparing synthetic gas by reforming methane and CO2 Download PDFInfo
- Publication number
- CN1309079A CN1309079A CN00135648A CN00135648A CN1309079A CN 1309079 A CN1309079 A CN 1309079A CN 00135648 A CN00135648 A CN 00135648A CN 00135648 A CN00135648 A CN 00135648A CN 1309079 A CN1309079 A CN 1309079A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reforming methane
- molecular sieve
- methane
- yield
- 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.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 238000002407 reforming Methods 0.000 title claims abstract 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract 3
- 239000001569 carbon dioxide Substances 0.000 claims abstract 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000011068 loading method Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 235000011089 carbon dioxide Nutrition 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种甲烷和二氧化碳重整制合成气催化剂及其制备方法。甲烷和二氧化碳重整制合成气催化剂以中孔分子筛MCM－41为载体,活性组分为3%－13%(重量)Ni,采用浸渍法制备。催化剂的特点是金属担载量较低,在较低的温度下可以达到较高的转化率和收率。The invention discloses a catalyst for producing synthesis gas by reforming methane and carbon dioxide and a preparation method thereof. The catalyst for reforming methane and carbon dioxide to produce synthesis gas uses mesoporous molecular sieve MCM-41 as a carrier, the active component is 3%-13% (weight) Ni, and is prepared by impregnation. The catalyst is characterized by low metal loading, and can achieve high conversion and yield at low temperature.
Description
The present invention relates to a kind of methane and CO 2 reformation catalyst for preparing synthetic gas and preparation method thereof.
Sweet natural gas (main component methane) transforms preparing synthetic gas and provides cheap raw material for C-1 chemistry industry, for solving energy shortage, shortage of resources and environment protection important meaning is arranged.Many important technological processs,, synthol synthetic as F-T, synthetic ammonia all need to have the synthetic gas of different ratios.Now existing nearly 10% Sweet natural gas is used to make Chemicals in the world, and wherein the throughput of methyl alcohol has surpassed annual 2200 ten thousand tons, and the Ammonia Production ability also surpasses annual 100000000 tons, wherein accounts for 80% and 76% of ultimate production respectively by gas production.
Make inertia micro-molecular gas CH
4And CO
2Activation is also carried out the orientation conversion, and its key is to select suitable catalyzer.Being used for this catalyst for reaction at present mainly is loading type Rh, Ru, Pt, Ir, Ni, Co grade in an imperial examination VIII family metal catalyst.Noble metal catalyst has the catalytic activity height, carbon distribution is few or the advantage of carbon distribution not, and regrettably noble metal catalyst costs an arm and a leg, and high temperature easily runs off and sintering.Therefore, develop that non-precious metal catalyst is used for methane and CO 2 reforming reaction is a valuable job.
The purpose of this invention is to provide a kind of have the at a lower temperature methane of higher catalytic activity and the Catalysts and its preparation method of CO 2 reformation preparing synthetic gas.
Support of the catalyst of the present invention is mesoporous molecular sieve MCM-41, its specific surface area 1000 ± 200m
2/ g, active ingredient is made up of 3%～13% (weight) Ni.
Catalyzer of the present invention adopts immersion process for preparing, it is characterized in that elder generation is immersed in the saline solution of nickel on the mesoporous molecular sieve MCM-41, 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, and the employing fixed bed is a reactor, and gas hourly space velocity is 8400mlg
-1h
-1, normal pressure is reaction down, under 700 ℃, and CH
4And CO
2Transformation efficiency all can reach more than 90%.
Embodiment 1: adopting mesoporous molecular sieve MCM-41 is carrier, take by weighing 2.0g mesoporous molecular sieve MCM-41, be dissolved in 10 ml distilled waters with the 0.2973g nickelous nitrate, this nitrate solution is immersed among the mesoporous molecular sieve MCM-41, stir, drying is 2 hours under 100～120 ℃, again through 500～800 ℃ of roasting 4-8 hours, promptly obtains finished catalyst.
Get 0.3g30～this catalyzer of 50 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, temperature programming successive reaction under normal pressure.Reaction result is listed in table 1.
The transformation efficiency of methane and carbonic acid gas and yield under table 1. differing temps
| Temperature (℃) | X CH4(％) | X CO2(％) | Y CO(％) | Y H2(％) |
| ????500 | ????24.2 | ????34.5 | ????29.4 | ????32.0 |
| ????550 | ????44.2 | ????54.1 | ????49.2 | ????51.6 |
| ????600 | ????65.5 | ????73.6 | ????69.6 | ????71.6 |
| ????650 | ????83.2 | ????87.7 | ????85.5 | ????86.7 |
| ????700 | ????92.3 | ????94.2 | ????93.3 | ????93.9 |
| ????750 | ????97.0 | ????97.8 | ????97.4 | ????97.6 |
| ????800 | ????98.5 | ????98.8 | ????98.6 | ????98.7 |
X
CH4: CH
4Transformation efficiency X
CO2: CO
2Transformation efficiency Y
CO: CO yield Y
H2: H
2Yield
Embodiment 2: adopting mesoporous molecular sieve MCM-41 is carrier, takes by weighing 2.0g mesoporous molecular sieve MCM-41, is dissolved in 10 ml distilled waters with the 0.6936g nickelous nitrate, and following step is with embodiment 1.
Get 0.3g30～this catalyzer of 50 orders, adopt reaction unit and the reaction conditions of embodiment 1.Reaction result is listed in table 2.
The transformation efficiency of methane and carbonic acid gas and yield under table 2. differing temps
X
CH4: CH
4Transformation efficiency X
CO2: CO
2Transformation efficiency Y
CO: CO yield Y
H2: H
2Yield embodiment 3: adopting mesoporous molecular sieve MCM-41 is carrier, takes by weighing 2.0g mesoporous molecular sieve MCM-41, is dissolved in 10 ml distilled waters with the 1.0904g nickelous nitrate, and following step is with embodiment 1.
| Temperature (℃) | X CH4(％) | X CO2(％) | Y CO(％) | Y H2(％) |
| ????500 | ????30.5 | ????22.8 | ????26.6 | ????34.4 |
| ????550 | ????51.2 | ????45.7 | ????48.4 | ????53.9 |
| ????600 | ????69.3 | ????67.9 | ????68.6 | ????70.0 |
| ????650 | ????83.5 | ????83.6 | ????83.6 | ????83.4 |
| ????700 | ????92.1 | ????94.4 | ????93.3 | ????90.9 |
| ????750 | ????97.2 | ????98.1 | ????97.7 | ????96.8 |
| ????800 | ????98.7 | ????99.3 | ????99.0 | ????98.5 |
Get 0.3g30～this catalyzer of 50 orders, adopt reaction unit and the reaction conditions of embodiment 1.Reaction result is listed in table 3.
The transformation efficiency of methane and carbonic acid gas and yield under table 3. differing temps
| Temperature (℃) | X CH4(％) | X CO2(％) | Y CO(％) | Y H2(％) |
| ????500 | ????31.4 | ????24.6 | ????28.0 | ????34.9 |
| ????550 | ????53.0 | ????47.5 | ????50.3 | ????55.8 |
| ????600 | ????70.9 | ????71.9 | ????71.4 | ????70.5 |
| ????650 | ????83.9 | ????87.8 | ????85.9 | ????82.1 |
| ????700 | ????92.6 | ????94.2 | ????93.4 | ????91.8 |
| ????750 | ????98.2 | ????98.8 | ????98.5 | ????98.0 |
| ????800 | ????99.0 | ????99.4 | ????99.2 | ????98.8 |
X
CH4: CH
4Transformation efficiency X
CO2: CO
2Transformation efficiency Y
CO: CO yield Y
H2: H
2Yield
Embodiment 4: adopting mesoporous molecular sieve MCM-41 is carrier, takes by weighing 2.0g mesoporous molecular sieve MCM-41, is dissolved in 10 ml distilled waters with the 1.2880g nickelous nitrate, and following step is with embodiment 1.
Get 0.3g30～this catalyzer of 50 orders, adopt reaction unit and the reaction conditions of embodiment 1.Reaction result is listed in table 4.
The transformation efficiency of methane and carbonic acid gas and yield under table 4. differing temps
| Temperature (℃) | X CH4(％) | X CO2(％) | Y CO(％) | Y H2(％) |
| ????500 | ????30.5 | ????22.8 | ????26.6 | ????34.4 |
| ????550 | ????51.2 | ????45.7 | ????48.4 | ????53.9 |
| ????600 | ????69.3 | ????67.9 | ????68.6 | ????70.0 |
| ????650 | ????83.5 | ????83.6 | ????83.6 | ????83.4 |
| ????700 | ????93.3 | ????93.5 | ????93.4 | ????93.1 |
| ????750 | ????97.2 | ????96.9 | ????97.1 | ????97.4 |
| ????800 | ????98.3 | ????97.9 | ????98.1 | ????98.5 |
X
CH4: CH
4Transformation efficiency X
CO2: CO
2Transformation efficiency Y
CO: CO yield Y
H2: H
2Yield
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00135648A CN1309079A (en) | 2000-12-14 | 2000-12-14 | Catalyst for preparing synthetic gas by reforming methane and CO2 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00135648A CN1309079A (en) | 2000-12-14 | 2000-12-14 | Catalyst for preparing synthetic gas by reforming methane and CO2 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1309079A true CN1309079A (en) | 2001-08-22 |
Family
ID=4596794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00135648A Pending CN1309079A (en) | 2000-12-14 | 2000-12-14 | Catalyst for preparing synthetic gas by reforming methane and CO2 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1309079A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6680006B2 (en) * | 2001-12-17 | 2004-01-20 | Natural Resources Canada | Conversion of natural gas to synthesis gas using nickel catalyst |
| CN1297345C (en) * | 2004-01-13 | 2007-01-31 | 厦门大学 | Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method |
| CN100388975C (en) * | 2005-09-29 | 2008-05-21 | 北京化工大学 | Metal carrier catalyst for producing synthetic gas by methane carbon dioxide reformation and its production |
| 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 |
| CN102886272A (en) * | 2012-04-26 | 2013-01-23 | 华东理工大学 | Supported catalyst, preparation method and application thereof |
| CN103191744A (en) * | 2013-04-17 | 2013-07-10 | 中国科学院新疆理化技术研究所 | Modified vermiculite supported nickel catalyst and preparation method thereof |
| CN115854725A (en) * | 2022-11-16 | 2023-03-28 | 中国建材国际工程集团有限公司 | System and method for recycling waste heat of high-temperature flue gas of glass kiln |
-
2000
- 2000-12-14 CN CN00135648A patent/CN1309079A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6680006B2 (en) * | 2001-12-17 | 2004-01-20 | Natural Resources Canada | Conversion of natural gas to synthesis gas using nickel catalyst |
| CN1297345C (en) * | 2004-01-13 | 2007-01-31 | 厦门大学 | Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method |
| CN100388975C (en) * | 2005-09-29 | 2008-05-21 | 北京化工大学 | Metal carrier catalyst for producing synthetic gas by methane carbon dioxide reformation and its production |
| 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 |
| CN102886272A (en) * | 2012-04-26 | 2013-01-23 | 华东理工大学 | Supported catalyst, preparation method and application thereof |
| CN102886272B (en) * | 2012-04-26 | 2014-12-24 | 华东理工大学 | Supported catalyst, preparation method and application thereof |
| CN103191744A (en) * | 2013-04-17 | 2013-07-10 | 中国科学院新疆理化技术研究所 | Modified vermiculite supported nickel catalyst and preparation method thereof |
| CN103191744B (en) * | 2013-04-17 | 2015-07-08 | 中国科学院新疆理化技术研究所 | Modified vermiculite supported nickel catalyst and preparation method thereof |
| CN115854725A (en) * | 2022-11-16 | 2023-03-28 | 中国建材国际工程集团有限公司 | System and method for recycling waste heat of high-temperature flue gas of glass kiln |
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