CN108686661A - A kind of preparation method of the methanation of carbon monoxide catalyst - Google Patents
A kind of preparation method of the methanation of carbon monoxide catalyst Download PDFInfo
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- CN108686661A CN108686661A CN201710219070.XA CN201710219070A CN108686661A CN 108686661 A CN108686661 A CN 108686661A CN 201710219070 A CN201710219070 A CN 201710219070A CN 108686661 A CN108686661 A CN 108686661A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
Abstract
A kind of preparation method of the methanation of carbon monoxide catalyst, will contain Al3+, Ni2+Mixed nitrate solution be added to the water with alkaline precipitating agent cocurrent, be put into micro-wave oven, aging, supernatant liquor is outwelled, and volatile organic solvent and reducing agent are added into remaining wet feed, mixture is placed into dry in micro-wave oven, heat treatment, sheetmolding is finally beaten by remaining solid.The method of the present invention can methanation catalyst obtained there is good catalytic activity and coking resistivity.
Description
Technical field
The invention belongs to catalysis technical fields, and in particular to a kind of preparation method of the methanation of carbon monoxide catalyst.
Background technology
Methanation catalyst is usually with Al2O3For carrier, methanation catalyst is with high-purity as disclosed in patent US 3933833
γ-Al2O3For carrier, load active component nickel oxide and cobalt oxide.Methanation catalyst disclosed in patent CN 1043639A with
Al2O3For carrier, nickel is active component, using rare earth metal or alkaline-earth metal or alkaline-earth metal as co-catalyst.Complex catalyst precursor
Body preparation is usually subjected to the processes such as aging, washing, drying, roasting, and these processes are all very time-consuming, are typically at least needed
3 ~ 4 days even for more time.
Methanation catalyst disclosed in patent CN 1043449A, nickel are active component, and rare earth metal and magnesium are co-catalysis
Agent, remaining is aluminium oxide.For these methanation catalysts using aluminium oxide as carrier, active component is nickel.General type existing for nickel
For Ni2+, and the nickel with methanation performance is metal simple-substance nickel.Therefore, before methanation reaction starts, catalyst is carried out
Reduction treatment.
Chinese patent CN 1054269 discloses a kind of methanation catalyst preparation method of producing synthesis gas from coal, catalyst
Active component is nickel, Al2O3For carrier, catalyst is using preceding needing with 10% H2/N2Program is warming up to 250 DEG C ~ 350 DEG C reduction
2h~6h。
Reduction activation process before nickel-base catalyst use needs to consume H2, and usually need to take a long time, it gives
Catalyst brings additional energy and inconvenience using process.The above process all causes the decline of catalyst production efficiency.
Traditional heating mode is so that heat is reached material heat, heat from outside according to heat transfer, convection current and radiation theory
It always from outward appearance to inner essence transmits and carries out heated material, temperature gradient is inevitably present in material, therefore the material heated is uneven,
Material is caused hot-spot occur, microwave heating technique is different from traditional heating mode, it is by heated object internal dipole
Molecule high-frequency reciprocating moves, and generates " interior frictional heat " and heating object material temperature degree is made to increase, be not necessary to any heat transfer process, energy
Make material inside and outside portion while heating while heating up, heating speed is fast and uniformly, it is only necessary to several points of the energy consumption of traditional heating mode it
Once or 1/tens can reach heating purpose.
Invention content
The present invention provides a kind of preparation methods of the methanation of carbon monoxide catalyst.The aging of catalyst, drying, at heat
Reason process all carries out under microwave environment, substantially reduces the manufacturing cycle of catalyst, and introduce and restore in heat treatment process
Agent eliminates catalyst using preceding needing to restore this time-consuming step, shortens manufacturing cycle 2 days or more, is urged to greatly improve
The production efficiency of agent.Using this method can methanation catalyst obtained there is good catalytic activity and stability.
The present invention's is mainly characterized by, and microwave heating is introduced in the aging, drying and heat treatment process of catalyst preparation,
Reducing agent is introduced in hot place's process, greatly reduces the manufacturing cycle of catalyst, improves the production efficiency of catalyst.
The technical scheme is that:Al will be contained3+, Ni2+Mixed nitrate solution and alkaline precipitating agent cocurrent be added
Into water, and maintain pH value of solution=7 ~ 8;Said mixture is put into micro-wave oven, and regulation power makes in-furnace temperature reach 60 ~ 90
DEG C, aging 15 ~ 30 minutes;Mixture is taken out from micro-wave oven after aging, supernatant liquor is outwelled, and to remaining wet feed
Volatile organic solvent and reducing agent is added;Mixture is placed into micro-wave oven, regulation power make in-furnace temperature reach 50 ~
It is 100 DEG C, 30 ~ 60 minutes dry;Regulation power makes in-furnace temperature reach 120 ~ 300 DEG C, is heat-treated 60 ~ 120 minutes;It will be remaining
Solid finally beat sheetmolding.
Usually, in nitrate solution of the present invention the ratio between amount of substance of Ni elements and Al elements for 0.2 ~
1.0:1。
Also contain Mg in mixed nitrate solution of the present invention2+,La3+,Zr4+,Ce3+And Ga3+In one kind or more
Kind, the ratio between the amount of total substance and the amount of Al elemental substances are 0.01 ~ 0.2:1.
Alkaline precipitating agent used in the present invention is Na2CO3,NaHCO3,K2CO3Or KHCO3At least one of aqueous solution.
Volatile organic solvent of the present invention is at least one of ethyl alcohol, acetone, ether.
The ratio between volatile organic solvent usage amount of the present invention and the amount of Al elemental substances in filter cake are 0.01 ~ 0.2:
1。
Reducing agent of the present invention is H2C2O4。
The ratio between reducing agent usage amount of the present invention and the amount of Al elemental substances in wet feed are 0.01 ~ 0.2:1.
Using the aging, drying, heat treatment process of the methanation catalyst prepared by the present invention all under microwave environment into
Row, substantially reduces the manufacturing cycle of catalyst, and introduces reducing agent in heat treatment process, eliminates catalyst using preceding needing
It restores this time-consuming step, shortens manufacturing cycle 2 days or more, to greatly improve the production efficiency of catalyst.Utilize the party
Method can methanation catalyst obtained there is good catalytic activity and coking resistivity.
Specific implementation mode
The following describes the present invention in detail with reference to examples.
Comparative example
Weigh 302.0g Al (NO3)3·9H2O,87.8g Ni(NO3)2·3H2O,2.06g Ga(NO3)3It is dissolved in aqueous solution and matching
At solution, by the Na of mixed nitrate solution and 1mol/L2CO3Solution cocurrent mixes, and maintains pH=7 ~ 8;It is put into bath temperature
After reaching 60 DEG C of aging 15min;Mixture is washed 3 times after aging, oven temperature is put into after washing and reaches 100
DEG C, it is 24 hours dry;It is put into muffle furnace after drying, temperature reaches 550 DEG C, is heat-treated 120 minutes;It will after heat treatment
Remaining solid finally beats sheetmolding, obtains catalyst.Catalyst is using preceding needing with 10% H2/N2Program is warming up to 350 DEG C also
Former 6h.
Embodiment 1
Weigh 302.0g Al (NO3)3·9H2O,87.8g Ni(NO3)2·3H2O,2.06g Ga(NO3)3It is dissolved in aqueous solution and matching
At solution, by the Na of mixed nitrate solution and 1mol/L2CO3Solution cocurrent mixes, and maintains pH=7 ~ 8;It is put into micro-wave oven,
After regulation power makes in-furnace temperature reach 60 DEG C of aging 15min;Mixture is taken out from micro-wave oven after aging, upper layer
Clear liquid is outwelled and adds 3L ethyl alcohol and 4.0g H2C2O4;Mixture is placed into micro-wave oven, regulation power makes in-furnace temperature reach
It is 30 minutes dry to 50 DEG C;Regulation power makes in-furnace temperature reach 120 DEG C, is heat-treated 60 minutes;Remaining solid is last
Sheetmolding is beaten, catalyst I is obtained.
Embodiment 2
Weigh 150.0g Al (NO3)3·9H2O,43.9g Ni(NO3)2·3H2O,5.0g Mg(NO3)2·6H2O is dissolved in aqueous solution
In be made into total salt concentration be 1mol/L solution, by the NaHCO of mixed nitrate solution and 1mol/L3Solution cocurrent mixes, and ties up
Hold pH=7 ~ 8;It is put into micro-wave oven, after regulation power makes in-furnace temperature reach 90 DEG C of aging 30min;It will be mixed after aging
It closes object to take out from micro-wave oven, supernatant liquor is outwelled and adds 3L acetone and 80.0g H2C2O4;Mixture is placed into micro-wave oven
In, regulation power makes in-furnace temperature reach 100 DEG C, drying 60 minutes;Regulation power makes in-furnace temperature reach 300 DEG C, heat
Processing 120 minutes;Remaining solid is finally beaten into sheetmolding, obtains catalyst II.
Embodiment 3
Weigh 302.0g Al (NO3)3·9H2O,87.8g Ni(NO3)2·3H2O,5.0g Ce(NO3)3·6H2O is dissolved in aqueous solution
In be made into total salt concentration be 1mol/L solution, by the K of mixed nitrate solution and 1mol/L2CO3Solution cocurrent mixes, and maintains
pH=7~8;It is put into micro-wave oven, after regulation power makes in-furnace temperature reach 75 DEG C of aging 20min;It will mixing after aging
Object takes out from micro-wave oven, and supernatant liquor is outwelled and adds 3L ether and 42.0g H2C2O4;Mixture is placed into micro-wave oven,
Regulation power makes in-furnace temperature reach 75 DEG C, drying 45 minutes;Regulation power makes in-furnace temperature reach 200 DEG C, heat treatment
90 minutes;Remaining solid is finally beaten into sheetmolding, obtains catalyst III.
Embodiment 4
Weigh 302.0g Al (NO3)3·9H2O,87.8g Ni(NO3)2·3H2O,5.0g La(NO3)3·6H2O is dissolved in aqueous solution
In be made into total salt concentration be 1mol/L solution, by the KHCO of mixed nitrate solution and 1mol/L3Solution cocurrent mixes, and maintains
pH=7~8;It is put into micro-wave oven, after regulation power makes in-furnace temperature reach 90 DEG C of aging 30min;It will mixing after aging
Object takes out from micro-wave oven, and supernatant liquor is outwelled and adds 3L ethyl alcohol and 80.0g H2C2O4;Mixture is placed into micro-wave oven,
Regulation power makes in-furnace temperature reach 100 DEG C, drying 60 minutes;Regulation power makes in-furnace temperature reach 300 DEG C, heat treatment
120 minutes;Remaining solid is finally beaten into sheetmolding, obtains catalyst IV.
Embodiment 5
Weigh 302.0g Al (NO3)3·9H2O,87.8g Ni(NO3)2·3H2O,5.0g Zr(NO3)3·5H2O is dissolved in aqueous solution
In be made into total salt concentration be 1mol/L solution, by the Na of mixed nitrate solution and 1mol/L2CO3Solution cocurrent mixes, and maintains
pH=7~8;It is put into micro-wave oven, after regulation power makes in-furnace temperature reach 90 DEG C of aging 30min;It will mixing after aging
Object takes out from micro-wave oven, and supernatant liquor is outwelled and adds 3L ethyl alcohol and 42.0g H2C2O4;Mixture is placed into micro-wave oven,
Regulation power makes in-furnace temperature reach 75 DEG C, drying 45 minutes;Regulation power makes in-furnace temperature reach 200 DEG C, heat treatment
90 minutes;Remaining solid is finally beaten into sheetmolding, obtains catalyst V.
Methanation catalyst I, II, III, IV, V is seated in fixed-bed tube reactor respectively, and reaction condition is:Pressure
3.0MPa, gas form H249.12 CH433.08, CO 6.30, N211.50, gas space velocity is 5000 ~ 30000h-1, 600
After DEG C reaction 500h, the activity of catalyst keeps good, and wherein CO conversion ratios close to 100%, close to 100% tear open by methane selectively
The catalytic mechanical intensity drawn off is still very high, and the surface area carbon amounts of catalyst is less.
| Catalyst | Gas space velocity(h-1) | CO total conversions(%) | Methane selectively (%) | Carbon deposition quantity (%) |
| Comparative example | 30000 | 99.0 | 99.0 | 9.7 |
| Ⅰ | 30000 | 99.1 | 99.5 | 3.2 |
| Ⅱ | 20000 | 99.3 | 99.0 | 2.9 |
| Ⅲ | 10000 | 99.4 | 98.9 | 2.7 |
| Ⅳ | 8000 | 99.6 | 99.1 | 3.1 |
| Ⅴ | 5000 | 99.2 | 99.3 | 2.8 |
Claims (8)
1. a kind of preparation method of the methanation of carbon monoxide catalyst, it is characterised in that Al will be contained3+, Ni2+Mixed nitrate
Solution is added to the water with alkaline precipitating agent cocurrent, and maintains pH value of solution=7 ~ 8;Said mixture is put into micro-wave oven, adjusts temperature
Degree reaches 60 ~ 90 DEG C, aging 15 ~ 30 minutes;The supernatant liquor of mixture is outwelled after aging, and into remaining wet feed
Volatile organic solvent and reducing agent is added;Mixture is placed into micro-wave oven, temperature is adjusted and reaches 50 ~ 100 DEG C, drying 30
~ 60 minutes;It adjusts temperature and reaches 120 ~ 300 DEG C, be heat-treated 60 ~ 120 minutes;Remaining solid is finally beaten into sheetmolding.
2. the preparation method of catalyst according to claim 1, it is characterised in that in the nitrate solution Ni elements with
The ratio between amount of Al elemental substances is 0.2 ~ 1.0:1.
3. the preparation method of catalyst according to claim 1, it is characterised in that also contain in the mixed nitrate solution
There is Mg2+,La3+,Zr4+,Ce3+And Ga3+At least one of, the ratio between the amount of total substance and the amount of Al elemental substances are 0.01
~0.2:1。
4. the preparation method of catalyst according to claim 1, it is characterised in that alkaline precipitating agent used is Na2CO3,
NaHCO3,K2CO3And KHCO3At least one of aqueous solution.
5. the preparation method of catalyst according to claim 1, it is characterised in that volatile organic solvent be ethyl alcohol, acetone,
At least one of ether.
6. according to the preparation method of the catalyst of claim 1 or 5, it is characterised in that the volatile organic solvent uses
The ratio between amount and the amount of Al elemental substances in wet feed are 0.01 ~ 0.2:1.
7. the preparation method of catalyst according to claim 1, it is characterised in that the reducing agent is H2C2O4。
8. the preparation method of catalyst according to claim 1, it is characterised in that in the reducing agent usage amount and wet feed
The ratio between amount of Al elemental substances is 0.01 ~ 0.2:1.
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| CN201710219070.XA CN108686661A (en) | 2017-04-06 | 2017-04-06 | A kind of preparation method of the methanation of carbon monoxide catalyst |
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| CN201710219070.XA CN108686661A (en) | 2017-04-06 | 2017-04-06 | A kind of preparation method of the methanation of carbon monoxide catalyst |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480375A (en) * | 2013-09-29 | 2014-01-01 | 福州大学 | Carbon monoxide methanating catalyst and preparation method thereof |
| KR20140087264A (en) * | 2012-12-28 | 2014-07-09 | 재단법인 포항산업과학연구원 | Mesoporous Ni-X-Al2O3 xerogel catalyst, preparation method thereof, and method for preparing methane using said catalyst |
| CN104275185A (en) * | 2013-07-12 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of copper-based hydrogenation catalyst without reduction activation |
| CN104907075A (en) * | 2015-05-19 | 2015-09-16 | 中国华能集团清洁能源技术研究院有限公司 | High-temperature-resistant methanation catalyst and preparation method thereof |
-
2017
- 2017-04-06 CN CN201710219070.XA patent/CN108686661A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140087264A (en) * | 2012-12-28 | 2014-07-09 | 재단법인 포항산업과학연구원 | Mesoporous Ni-X-Al2O3 xerogel catalyst, preparation method thereof, and method for preparing methane using said catalyst |
| CN104275185A (en) * | 2013-07-12 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of copper-based hydrogenation catalyst without reduction activation |
| CN103480375A (en) * | 2013-09-29 | 2014-01-01 | 福州大学 | Carbon monoxide methanating catalyst and preparation method thereof |
| CN104907075A (en) * | 2015-05-19 | 2015-09-16 | 中国华能集团清洁能源技术研究院有限公司 | High-temperature-resistant methanation catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 工业和信息化部节能与综合利用司: "《工业清洁生产关键共性技术案例 2015年版》", 30 June 2015, 北京：冶金工业出版社 * |
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Application publication date: 20181023 |