CN104857965A - Preparation method and application process of catalyst for producing hydrogen by methanol steam reformation - Google Patents
Preparation method and application process of catalyst for producing hydrogen by methanol steam reformation Download PDFInfo
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- CN104857965A CN104857965A CN201510281810.3A CN201510281810A CN104857965A CN 104857965 A CN104857965 A CN 104857965A CN 201510281810 A CN201510281810 A CN 201510281810A CN 104857965 A CN104857965 A CN 104857965A
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- catalyst
- hydrogen
- methanol
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Abstract
The invention relates to a catalyst for producing hydrogen by methanol steam reformation. The catalyst consists of the following components in percentage by weight: 10% to 20% of Cu, 5% to 10% of ZrO2, 2% to 10% of CeO2 and 68% to 80% of carrier gamma-Al2O3. The catalyst is prepared according to an immersion method, and the technological conditions for preparing hydrogen by methanol steam reformation are as follows: the reaction temperature is 220 to 300 DEG C; the reaction pressure is ordinary pressure; the feed is mixed liquor of methanol and water (at a molar ratio of 1: 1.2); the mass space velocity of the feed is 1.8-7.2h<-1>. Under an optimal reaction condition, the conversion rate of methanol can reach 99.5%, and the selectivity of hydrogen reaches 99%.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of Catalysts and its preparation method by preparing hydrogen by reforming methanol-water steam and reaction process.
Background technology
Hydrogen Energy more and more comes into one's own as a kind of efficient, clean alternative energy source.Mid-term 21 century progressively will enter hydrogen energy era.Chemistry hydrogen manufacturing is the hydrogen manufacturing mode be most widely used at present, and wherein water-gas shift and catalytic reforming remain the main flow of hydrogen manufacturing.And hydrogen production from methanol-steam reforming technology enjoys the concern of vast scientific research scholar, main cause is that the output of methyl alcohol is very high, for being only second to the third-largest commodity chemical of ethene, ammonia, particularly in China, the U.S., coal poly-generation system can the methyl alcohol of a large amount of replacement liquid fluid fuel of output; The temperature of methanol catalytically reforming hydrogen producing is 150 ~ 300 DEG C, pressure be normal pressure to middle pressure, lower than hydrocarbon compound, its conversion process is simple efficient, economically feasible, can produce the hydrogen of high volume ratio, storage, convenient transportation, and subsequent purification program is simple.
Although hydrogen production from methanol-steam reforming reaction have studied a lot of year, the catalyst that can be applied to suitability for industrialized production is still few, therefore works out activity higher, and the major issue that will solve studied from now on by the selective and better catalyst of stability.In recent years, there is some catalyst about hydrogen production from methanol-steam reforming report, as selected the metal oxide of active component Cu and Zn; Carrier is the catalyst of the metal oxide composition of Ce, Zr or Ce and Zr, adopts coprecipitation method preparation (Chinese patent CN103566941A), has a kind of catalyst with ZnO for main active component, comprise Cr
2o
3, ZrO
2, CeO
2deng composite oxides as catalysis and thermally-stabilised auxiliary agent and carrier, this catalyst is suitable for carrying out methanol steam reforming reaction higher reaction temperatures 430 ~ 480 DEG C, in reformed gas, hydrogen content is greater than 74% (mol), methanol conversion, more than 93%, is applicable to the process (Chinese patent CN101612563) of carrying out methanol steam reforming original position making pure hydrogen in palladium film reactor.Have using one or more metal oxide containing precious metals as active component, rare earth oxide and compound transition metal oxide are as the noble metal catalyst (Chinese patent CN101053833) of carrier and auxiliary agent, catalyst is also had to be the two co-precipitation type palladium zinc based catalyst (Chinese patent CN102872867A) etc. promoted of CNT and scandium, but these catalyst have respective shortcoming: preparation process is complicated, cost is higher, or limits the application of these preparation methods to problems such as environment pollute to some extent.
For above problem, the present invention for goal in research with hydrogen production from methanol-steam reforming reaction system, is intended to exploitation and has high H
2selective, low CO is selective, the copper-based catalysts of high stability.In the catalyst studied, copper is proved to be a kind of most active ingredient to catalyst for preparing hydrogen by reforming methanol and water vapour, and adopts merely copper, poor catalyst stability, easy-sintering, causes catalysqt deactivation.The present invention take copper as main active component, add cerium oxide and zirconia is co-catalyst, the catalyst obtained makes the reaction temperature of hydrogen production from methanol-steam reforming be reduced to 220 DEG C ~ 280 DEG C, and the conversion ratio of methyl alcohol and hydrogen is selective higher, and the content of CO reduces greatly simultaneously.
Summary of the invention
The present invention aims to provide one with copper for main active constituent, and cerium oxide and zirconia are co-catalyst, γ-Al
2o
3for the preparation method of the hydrogen production from methanol-steam reforming new catalyst of carrier, prepared catalyst activity is high, good stability, long service life, effectively can improve the conversion ratio of methyl alcohol and the selective of hydrogen.
Catalyst for preparing hydrogen by reforming methanol and water vapour of the present invention comprises catalyst activity component, co-catalyst, catalyst carrier; Wherein, catalyst activity component is Cu, and co-catalyst is the metal oxide of Zr, Ce; Catalyst carrier is γ-Al
2o
3.When described catalyst is the combination of copper zirconium cerium catalyst, the mass fraction of copper is 10% ~ 20%, and zirconic mass fraction is 5% ~ 10%, and the mass fraction of cerium oxide is 2% ~ 10%, and all the other are carrier γ-Al
2o
3, mass fraction is 68% ~ 80%.
In described catalyst, Cu derives from its slaine Cu (NO
3)
23H
2o, ZrO
2derive from its slaine Zr (NO
3)
45H
2o, CeO
2derive from its slaine Ce (NO
3)
26H
2o.
The preparation method of the described catalyst for hydrogen production from methanol-steam reforming is as follows:
(1) Cu (NO will measured
3)
23H
2o, Zr (NO
3)
45H
2o, Ce (NO
3)
26H
2o is dissolved in the deionized water of certain volume, adds a certain amount of γ-Al until completely dissolved
2o
3, stir, flood 12 hours under normal temperature;
(2) by the catalyst precarsor that flooded at 110 DEG C dry 12 hours, roasting 3 hours at 500 DEG C.
(3) catalyst of oxidation state is led to hydrogen and nitrogen mixed gas reduction, then carry out compressing tablet, sieve out 40 ~ 80 object particles and namely obtain catalyst.
Catalyst for hydrogen production from methanol-steam reforming carries out on the atmospheric fixed bed reactor of continuous flowing type the catalytically active assessment of the steam reforming reaction of methyl alcohol.Before reaction, a certain amount of catalyst is placed in the constant temperature zone of reactor, add quartz sand up and down, catalyst is first led at 300 DEG C Hydrogen activation and be cooled to the temperature needing reaction after 1 hour, after temperature stabilization, start charging, range of reaction temperature is at 220 DEG C ~ 300 DEG C; The mol ratio of charging methyl alcohol and water is 1:1.2; The mass space velocity of charging is 1.8 ~ 7.2h
-1.Reacted product is by six-way valve hand sampling, carry out on-line analysis with gas chromatograph, the conversion ratio of methyl alcohol is 36% ~ 99.5%, and the selective of hydrogen is 90% ~ 99%, the selective of carbon monoxide is 0.1% ~ 9%, and the selective of carbon dioxide is 90% ~ 99.5%.
Detailed description of the invention
Embodiment 1
The preparation of 1# catalyst (consists of Cu:10%, ZrO
2: 5%, CeO
2: 5%, γ-Al
2o
3: 80%).
Take 1.4156gCu (NO
3)
23H
2o, 0.6533g Zr (NO
3)
45H
2o and 0.473gCe (NO
3)
26H
2o adds deionized water dissolving, mixes, then by 3g γ-Al
2o
3join in nitrate solution, flood 12 hours under room temperature, put it into baking oven at 110 DEG C dry 12 hours, subsequently in tube furnace in 500 DEG C of roastings 3 hours, with hydrogen nitrogen mixed gas (hydrogen 15%) at 300 DEG C of reductase 12s hour, after being cooled to room temperature, compression molding sieves out 40 ~ 80 object particles again, namely obtains 1# catalyst.
Embodiment 2
The preparation of 2# catalyst (consists of Cu:15%, ZrO
2: 5%, CeO
2: 10%, γ-Al
2o
3: 70%).
Take 2.4459gCu (NO
3)
23H
2o, 0.7466g Zr (NO
3)
45H
2o and 1.0812gCe (NO
3)
26H
2o adds deionized water dissolving, mixes, then by 3g γ-Al
2o
3join in nitrate solution, flood 12 hours under room temperature; Put it into baking oven at 110 DEG C dry 12 hours, subsequently in tube furnace in 500 DEG C of roastings 3 hours, with hydrogen nitrogen mixed gas (hydrogen 15%) at 300 DEG C of reductase 12s hour, after being cooled to room temperature, compression molding sieves out 40 ~ 80 object particles again, namely obtains 2# catalyst.
Embodiment 3
The preparation of 3# catalyst (consists of Cu:15%, ZrO
2: 7%, CeO
2: 2%, γ-Al
2o
3: 76%).
Take 2.2352gCu (NO
3)
23H
2o, 0.9627g Zr (NO
3)
45H
2o and 0.1992gCe (NO
3)
26H
2o adds deionized water dissolving, mixes, then by 3g γ-Al
2o
3join in nitrate solution, flood 12 hours under room temperature; Put it into baking oven at 110 DEG C dry 12 hours, subsequently in tube furnace in 500 DEG C of roastings 3 hours, with hydrogen nitrogen mixed gas (hydrogen 15%) at 300 DEG C of reductase 12s hour, after being cooled to room temperature, compression molding sieves out 40 ~ 80 object particles again, namely obtains 3# catalyst.
Embodiment 4
The preparation of 4# catalyst (consists of Cu:15%, ZrO
2: 10%, CeO
2: 5%, γ-Al
2o
3: 70%).
Take 2.4268gCu (NO
3)
23H
2o, 1.4932g Zr (NO
3)
45H
2o and 0.5406gCe (NO
3)
26H
2o adds deionized water dissolving, mixes, then by 3g γ-Al
2o
3join in nitrate solution, flood 12 hours under room temperature, put it into baking oven at 110 DEG C dry 12 hours, subsequently in tube furnace in 500 DEG C of roastings 3 hours, with hydrogen nitrogen mixed gas (hydrogen 15%) at 300 DEG C of reductase 12s hour, after being cooled to room temperature, compression molding sieves out 40 ~ 80 object particles again, namely obtains 4# catalyst.
Embodiment 5
The preparation of 5# catalyst (consists of Cu:20%, ZrO
2: 5%, CeO
2: 7%, γ-Al
2o
3: 68%).
Take 3.3571gCu (NO
3)
23H
2o, 0.7686g Zr (NO
3)
45H
2o and 0.7791gCe (NO
3)
26H
2o adds deionized water dissolving, mixes, then by 3g γ-Al
2o
3join in nitrate solution, flood 12 hours under room temperature, put it into baking oven at 110 DEG C dry 12 hours, subsequently in tube furnace in 500 DEG C of roastings 3 hours, with hydrogen nitrogen mixed gas (hydrogen 15%) at 300 DEG C of reductase 12s hour, after being cooled to room temperature, compression molding sieves out 40 ~ 80 object particles again, namely obtains 5# catalyst.
Embodiment 6
The atmospheric fixed bed reactor of continuous-flow is adopted to investigate catalyst activity.Take a certain amount of 1# (or 2# ~ 5#) catalyst and be placed in reaction tube constant temperature zone, logical hydrogen (30mLmin
-1) at 300 DEG C, activate 1h; Temperature control to 260 DEG C, pass into the raw material (first alcohol and water) after gasification, water alcohol mol ratio is 1.2:1, and the mass space velocity of charging is 3.6h
-1, product carries out on-line analysis by gas-chromatography.The evaluation result of 1# ~ 5# catalyst is in table 1.
Table 11 ~ 5# catalyst at 260 DEG C to hydrogen production from methanol-steam reforming reaction catalytic activity
Embodiment 7
Take a certain amount of 3# catalyst and be placed in reaction tube constant temperature zone, logical hydrogen (30mLmin
-1) at 300 DEG C, activate 1h; Investigating temperature range is 220 DEG C ~ 300 DEG C, and pass into the raw material (first alcohol and water) after gasification, water alcohol mol ratio is 1.2:1, and the mass space velocity of charging is 3.6h
-1, product carries out on-line analysis by gas-chromatography, and evaluation result is in table 2.
Table 2 3# catalyst is at different temperatures to the catalytic activity of hydrogen production from methanol-steam reforming reaction
Embodiment 8
Take a certain amount of 4# catalyst and be placed in reaction tube constant temperature zone, logical hydrogen (30mLmin
-1) at 300 DEG C, activate 1h; Investigating temperature range is 220 DEG C ~ 300 DEG C, and pass into the raw material (first alcohol and water) after gasification, water alcohol mol ratio is 1.2:1, and the mass space velocity of charging is 3.6h
-1, product carries out on-line analysis by gas-chromatography, and evaluation result is in table 3.
Table 3 4# catalyst is at different temperatures to the catalytic activity of hydrogen production from methanol-steam reforming reaction
Embodiment 9
The atmospheric fixed bed reactor of continuous-flow is adopted to investigate catalyst activity.Take a certain amount of 3# catalyst and be placed in reaction tube constant temperature zone, logical hydrogen (30mLmin
-1) at 300 DEG C, activate 1h; Temperature control to 260 DEG C, pass into the raw material (first alcohol and water) after gasification after stable, water alcohol mol ratio is 1.2:1, and the mass space velocity of charging is 1.8 ~ 7.2h
-1, product carries out on-line analysis by gas-chromatography, and evaluation result is in table 4.
Table 4 3# catalyst under different quality air speed to hydrogen production from methanol-steam reforming reaction catalytic activity
Claims (4)
1. a catalyst for preparing hydrogen by reforming methanol-water steam, is characterized in that the active component of catalyst selects Cu, and co-catalyst is ZrO
2and CeO
2, carrier is γ-Al
2o
3.
2. according to the catalyst of preparing hydrogen by reforming methanol-water steam described in claim 1, it is characterized in that: the mass fraction of copper is 10% ~ 20%, and zirconic mass fraction is 5% ~ 10%, the mass fraction of ceria is 2% ~ 10%, carrier γ-Al
2o
3mass fraction be 68% ~ 80%.
3. the preparation method of the catalyst of preparing hydrogen by reforming methanol-water steam according to claim 1, is characterized in that: adopt customary commercial γ-Al
2o
3(specific area is 345.97m
2/ g) for carrier is by preparation catalyst, its concrete preparation process is as follows: (1) is by a certain amount of Cu (NO
3)
23H
2o, Zr (NO
3)
45H
2o, Ce (NO
3)
26H
2o is dissolved in the deionized water of certain volume, adds a certain amount of γ-Al until completely dissolved
2o
3, stir, flood 12 hours under normal temperature.(2) by the catalyst precarsor that flooded at 110 DEG C dry 12 hours, roasting 3 hours at 500 DEG C, use hydrogen nitrogen mixed gas (hydrogen 15%) at 300 DEG C of reductase 12s hour after being down to room temperature, carry out compressing tablet again after being down to room temperature, grinding screen separates 40-60 order catalyst.
4. the technique for applying of preparing hydrogen by reforming methanol-water steam catalyst described in claim 1: adopt the atmospheric fixed bed reactor of continuous flowing type, before reaction, a certain amount of catalyst is placed in constant temperature zone, add quartz sand up and down, first at 300 DEG C, logical Hydrogen activation is cooled to the temperature needing reaction after 1 hour, and reaction temperature is 220 DEG C ~ 300 DEG C; The methyl alcohol of reactor feed and the mol ratio of water are 1:1.2; The mass space velocity of raw material is 1.8 ~ 7.2h
-1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669819A (en) * | 2016-12-23 | 2017-05-17 | 常州大学 | Method and process for preparing Cu, Fe and MgO loaded AlPO<4>-5 molecular sieve for catalysis of hydrogen production from steam reforming of methanol |
| CN106905112A (en) * | 2017-03-07 | 2017-06-30 | 王亚壮 | A kind of method and system of new synthesizing methanol |
| CN109569628A (en) * | 2018-12-20 | 2019-04-05 | 常州大学 | For efficiently producing the preparation method of the catalyst of neopentyl glycol and the preparation method of neopentyl glycol |
| CN109718777A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of alcohol reforming catalyst for preparing hydrogen and its preparation method and application and alcohol reforming hydrogen production process |
| CN110329992A (en) * | 2019-07-25 | 2019-10-15 | 常州北化澳联环保科技有限公司 | Low-temperature methanol steam reforming catalyst for preparing hydrogen and preparation method thereof |
| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
| CN116037132A (en) * | 2022-12-28 | 2023-05-02 | 鄂尔多斯市瀚博科技有限公司 | For CO 2 Catalyst for preparing methanol by hydrogenation, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280953A (en) * | 2000-08-14 | 2001-01-24 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing hydrogen by reforming methanol and water vapour and its application |
| CN1772378A (en) * | 2005-11-03 | 2006-05-17 | 复旦大学 | Cu-Zr catalyst for steam reforming of methanol to prepare hydrogen and its prepn |
| CN101474563A (en) * | 2009-01-13 | 2009-07-08 | 上海应用技术学院 | Preparation method of catalyst for hydrogen production from methanol-steam reforming |
| CN102198935A (en) * | 2010-03-23 | 2011-09-28 | 张家港惠尔化学科技有限公司 | Method for preparing hydrogen by reforming methanol and water |
-
2015
- 2015-05-28 CN CN201510281810.3A patent/CN104857965A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280953A (en) * | 2000-08-14 | 2001-01-24 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing hydrogen by reforming methanol and water vapour and its application |
| CN1772378A (en) * | 2005-11-03 | 2006-05-17 | 复旦大学 | Cu-Zr catalyst for steam reforming of methanol to prepare hydrogen and its prepn |
| CN101474563A (en) * | 2009-01-13 | 2009-07-08 | 上海应用技术学院 | Preparation method of catalyst for hydrogen production from methanol-steam reforming |
| CN102198935A (en) * | 2010-03-23 | 2011-09-28 | 张家港惠尔化学科技有限公司 | Method for preparing hydrogen by reforming methanol and water |
Non-Patent Citations (1)
| Title |
|---|
| SAN PATEL ETC.: ""Influence of preparation method on performance of Cu(Zn)(Zr)-alumina catalysts for the hydrogen production via steam reforming of methanol"", 《JOURNAL OF POROUS MATERIALS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669819A (en) * | 2016-12-23 | 2017-05-17 | 常州大学 | Method and process for preparing Cu, Fe and MgO loaded AlPO<4>-5 molecular sieve for catalysis of hydrogen production from steam reforming of methanol |
| CN106905112A (en) * | 2017-03-07 | 2017-06-30 | 王亚壮 | A kind of method and system of new synthesizing methanol |
| CN109718777A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of alcohol reforming catalyst for preparing hydrogen and its preparation method and application and alcohol reforming hydrogen production process |
| CN109718777B (en) * | 2017-10-27 | 2022-02-08 | 中国石油化工股份有限公司 | Catalyst for hydrogen production by alcohol reforming, preparation method and application thereof, and hydrogen production method by alcohol reforming |
| CN109569628A (en) * | 2018-12-20 | 2019-04-05 | 常州大学 | For efficiently producing the preparation method of the catalyst of neopentyl glycol and the preparation method of neopentyl glycol |
| CN110329992A (en) * | 2019-07-25 | 2019-10-15 | 常州北化澳联环保科技有限公司 | Low-temperature methanol steam reforming catalyst for preparing hydrogen and preparation method thereof |
| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
| CN116037132A (en) * | 2022-12-28 | 2023-05-02 | 鄂尔多斯市瀚博科技有限公司 | For CO 2 Catalyst for preparing methanol by hydrogenation, preparation method and application thereof |
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