CN103611541B - A kind of low temperature methane steam reformation Catalysts and its preparation method - Google Patents
A kind of low temperature methane steam reformation Catalysts and its preparation method Download PDFInfo
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Abstract
The invention provides a kind of preparation method of low temperature methane steam reformation catalyst, comprise the following steps: carrier, activating agent are pulverized together with auxiliary agent and obtain mixture, wherein, activating agent is nickel compound containing, auxiliary agent is nitrate; Mixture is carried out ball-milling treatment, obtains nano-powder; Nano-powder is calcined, obtains fine-particle powder; And fine-particle powder is carried out compressing tablet, fragmentation, process of sieving.Method of the present invention decreases processing step, therefore reduces the time of explained hereafter significantly, improves production efficiency.The methane reforming catalyst prepared by the inventive method has more excellent changing effect than other catalyst of the prior art in methane steam reformation reaction.
Description
Technical field
The present invention relates to catalyst field, in particular to a kind of low temperature methane steam reformation Catalysts and its preparation method.
Background technology
Along with the continuous minimizing of fossil resources, environmental pollution is day by day serious, and the demand of human society to the energy continues to increase, and the utilization ratio improving fossil resources becomes the extremely urgent task of the mankind.
Along with the increase of natural gas proved reserves, and the technology of producing synthesis gas from natural gas is constantly ripe, and the efficiency utilization of natural gas is brought into schedule gradually.The main component of natural gas is methane, and methane vapor reforming preparing synthetic gas is one of effective way of reasonable efficiency utilization methane resource.
In the field of existing manufacture catalyst, disclose a kind of CH
4reformation CO
2the preparation method of the carbon base catalyst of preparing synthetic gas reaction, it is characterized in that forming steps is as follows: a. adopts ball mill raw coal to be crushed to less than 80 μm particles, then raw coal particle is mixed with alkaline earth metal compound, the part by weight that raw coal particle mixes with alkaline earth metal compound is: 1.5:1-19:1, alkaline earth metal compound is added in the mode of mechanical mixture, the mixture of obtained raw coal particle and alkaline earth metal compound, b. mixture obtained for a step is stirred, then pyrolysis under 900--1250 DEG C of condition, separate out to there is no fugitive constituent, obtained block carbon base catalyst, c. carbon base catalyst obtained for b step is crushed to required granular size.But the serviceability temperature of the carbon base catalyst prepared by this method is higher, usually reach about 1000 DEG C; And the carbon base catalyst catalytic efficiency manufactured by this method is also not fully up to expectations, is not therefore suitable for large-scale industrial production.
In addition, in prior art use the additive method of such as infusion process and the precipitation method low for equipment requirements because of it, can produce in a large number and be widely used.But there are liquid and solid waste to produce in these methods, have certain pollution to environment.Meanwhile, higher for the preparation of the preparation cost of the method for methane vapor reforming nickel-base catalyst in prior art, the production cycle is longer and catalytic effect not exclusively fully up to expectations.Therefore a kind of catalyst that can overcome above-mentioned shortcoming of exploitation is expected.
Summary of the invention
For in prior art in prior art, preparation cost is high, and the production cycle is grown and the problem of catalytic effect difference, and one aspect of the present invention proposes a kind of preparation method of low temperature methane steam reformation catalyst, comprises the following steps:
Carrier, activating agent are pulverized together with auxiliary agent and obtain mixture, wherein, activating agent is nickel compound containing, auxiliary agent is nitrate;
Mixture is carried out ball-milling treatment, obtains nano-powder;
Nano-powder is calcined, obtains fine-particle powder; And
Fine-particle powder is carried out compressing tablet, fragmentation, process of sieving.
According to the present invention, carrier is nanometer Al
2o
3, cordierite nano-powder, Nano-meter SiO_2
2in a kind of or their any combination;
Nickel compound containing comprises a kind of in nickel hydroxide, nickel nitrate, nickelous carbonate, nickel chloride and nickel acetate or their any combination; And
Auxiliary agent comprises zirconium nitrate, potassium nitrate, a kind of in magnesium nitrate, calcium nitrate, cerous nitrate, lanthanum nitrate, manganese nitrate or their any combination,
Wherein the mass ratio of carrier, activating agent and auxiliary agent is 10:(0.5-2.5): (0.05-1).
According to the present invention, the step that carrier, activating agent are pulverized together with auxiliary agent is comprised further:
Use pulverizer to implement pulverising step under the condition of rotating speed in 10000r/m to 25000r/m scope, the amount of filler of pulverizer is in the scope of 30% to 70%, and the grinding time of pulverizer is in the scope of 10 minutes to 20 minutes.
According to the present invention, the step that mixture carries out ball-milling treatment is comprised further:
Use high energy ball mill to implement the step of ball-milling treatment, rotating speed is in the scope of 300r/m to about 700r/m, and the time is in the scope of 10 minutes to 30 minutes.
According to the present invention, the diameter of nano-powder is in the scope of 60nm to 100nm.
According to the present invention, nano-powder is carried out the temperature of the step of calcining between 300 DEG C to 500 DEG C, and the time of enforcement is little in the scope of 4 hours between 2.
According to the present invention, by fine-particle powder being carried out the step of compressing tablet process, being pulverized by fine-particle powder is 60 order to 100 object particles.
According to the present invention, carrier is nanometer Al
2o
3, activating agent is nickel nitrate, and auxiliary agent comprises cerous nitrate and the zirconium nitrate of mass ratio 3:2, and wherein, the mass ratio of carrier, activating agent and auxiliary agent is 10:2:0.5.
According to the present invention, carrier is nanometer Al
2o
3, activating agent is nickel nitrate, and auxiliary agent comprises the cerous nitrate of mass ratio 2:1:1, zirconium nitrate and manganese nitrate, and wherein, the mass ratio of carrier, activating agent and auxiliary agent is 10:1.5:0.2.
Another aspect of the present invention provides a kind of low temperature methane steam reformation catalyst prepared according to said method.
The low temperature methane steam reformation catalyst prepared by preparation method of the present invention can effectively avoid preparation cost in prior art high, and the production cycle is grown and the problem of catalytic effect difference.Method of the present invention decreases processing step, therefore shortens the time of explained hereafter significantly, improves production efficiency.Under identical experiment condition, the low temperature methane steam reformation catalyst prepared by the inventive method has more excellent changing effect than other catalyst of the prior art in methane steam reformation reaction.
Accompanying drawing explanation
Fig. 1 is the flow chart for the preparation of catalyst.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain, all belongs to the scope of protection of the invention.
the preparation method of catalyst
As shown in the step S101 of Fig. 1, carrier, activating agent are put into pulverizer together with auxiliary agent and pulverizes.The pulverizer used is small-size laboratory frequency control pulverizer (model be RT ?08SC).In certain embodiments, the amount of filler of pulverizer is 30% to 70%, and controller rotating speed is in the scope of about 10000r/m to about 25000r/m.In certain embodiments, by the time controling pulverized 10 point in the scope of 20 minutes.In a preferred embodiment, carrier comprises nanometer Al
2o
3, cordierite nano-powder and Nano-meter SiO_2
2deng; Activating agent is the nickel compound containing comprising a kind of in nickel hydroxide, nickel nitrate, nickelous carbonate, nickel chloride and nickel acetate or their any combination, and auxiliary agent comprises zirconium nitrate, potassium nitrate, the nitrate of a kind of in magnesium nitrate, calcium nitrate, cerous nitrate, lanthanum nitrate, manganese nitrate or their any combination.Should be appreciated that; although only use above-mentioned nickel compound containing as an example in an embodiment of the present invention; but those of ordinary skill in the art should be clear; all nickel all can be reached the technique effect identical with nickel compound containing as the material of active component; that is, all the compound of nickel as active component to be included within protection scope of the present invention.Similarly, auxiliary agent all with involved in the present invention has the zirconates, sylvite, magnesium salts, calcium salt etc. of same effect all within protection scope of the present invention.In certain embodiments, the mass ratio joining the carrier in pulverizer, activating agent and auxiliary agent be 10:(0.5 ?2.5): (0.05 ?1).
As shown in the step S103 of Fig. 1, the mixture obtained after pulverizing in step S101 is carried out secondary pulverizing.In certain embodiments, in high energy ball mill, implement the step pulverized by mixture secondary.In secondary pulverising step, the rotating speed of high energy ball mill is in the scope of about 300r/m to about 700r/m, and Ball-milling Time is in the scope of about 10 minutes to about 30 minutes.The nano-powder that particle diameter is 60nm-100nm is obtained after ball-milling technology completes.After secondary is pulverized, obtain complex catalyst precursor powder.In secondary pulverising step of the present invention, because high-energy ball milling brings out Low Temperature Thermal chemical reaction, therefore part nitrate is divided into corresponding metal oxide.Such as, in secondary crushing process, active component nickel nitrate can be decomposed into nickel oxide, and auxiliary agent cerous nitrate can be decomposed into cerium oxide.Meanwhile, in high energy ball mill, carrier, contact mixing fully between active component with auxiliary agent, the interface enhancing active component and formed between auxiliary agent and carrier.Facilitate the diffusion of solid ionic, thus the ion of amount of activated component and auxiliary agent can be aligned in the lattice of carrier.Therefore, the catalyst using method of the present invention to prepare can effectively prevent due to the catalysqt deactivation phenomenon of reuniting between particulate and lattice growth causes, thus the further stability strengthened catalysis and add.In addition, in separating twice process, carrier, between active component and auxiliary agent, there is fierce collision, make the crystalline surface of active component can produce more lattice defect, this lattice defect as the avtive spot of catalyst, can improve the catalytic performance of catalyst further.
As shown in the step S105 of Fig. 1, the particle mixture obtained after being pulverized by secondary in step S103 is calcined.In an embodiment of the present invention, the time of calcining is little in the scope of 4 hours between about 2, and calcining temperature between about 300 DEG C in the scope of 500 DEG C.
As shown in the step S107 of Fig. 1, the fine-particle powder that obtains after calcining in step S105 is carried out compressing tablet, fragmentation, process of sieving.In certain embodiments, use desk type powder tablet press machine by the fine-particle powder compressing tablet, the fragmentation that obtain after calcining, sieve, and finally obtain 60 order to 100 order catalyst granules.
Compared with the method preparing methane vapor reforming nickel-base catalyst of the prior art, method of the present invention has multiple advantageous feature.In the method for the invention, do not use infusion process or the precipitation method, but be only applicable to the mode with ball milling of grinding, therefore, while Kaolinite Preparation of Catalyst, do not produce any type of liquid and solid waste.Meanwhile, first grinding that method of the present invention adopts makes the particle diameter of catalyst fines mixture reach the less level of expectation in the process of ball milling, and then can effectively reduce calcining heat and shorten calcination time in calcine technology subsequently.In addition, due to compared with prior art, method of the present invention decreases processing step, therefore shortens the time of explained hereafter significantly, improves production efficiency.
embodiment 1
By nanometer Al
2o
3, nickel nitrate and auxiliary agent in mass ratio 10:2:0.5 put into pulverizer, wherein, auxiliary agent comprises cerous nitrate and zirconium nitrate, and its mass ratio 3:2.The amount of filler of pulverizer is 40%, and the rotating speed controlling pulverizer is 10000r/m, and grinding time is 10 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 400r/m, and it is 25 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 3 hours at 400 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 60-80 order particle, finally obtains catalyst granules.
embodiment 2
By nanometer Al
2o
3, nickel nitrate and auxiliary agent in mass ratio 10:1.5:0.2 put into pulverizer, wherein, auxiliary agent comprises cerous nitrate, zirconium nitrate and manganese nitrate, and its mass ratio 2:1:1.The amount of filler of pulverizer is 45%, and the rotating speed controlling pulverizer is 15000r/m, and grinding time is 12 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 500r/m, and it is 20 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 3 hours at 500 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 60-80 order particle, finally obtains catalyst granules.
embodiment 3
By nanometer Al
2o
3, nickel nitrate and auxiliary agent in mass ratio 10:1.5:0.2 put into pulverizer, wherein, auxiliary agent comprises cerous nitrate and lanthanum nitrate, and its mass ratio 1:1.The amount of filler of pulverizer is 60%, and the rotating speed controlling pulverizer is 20000r/m, and grinding time is 15 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 600r/m, and it is 25 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 4 hours at 350 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 80-100 order particle, finally obtains catalyst granules.
embodiment 4
By nanometer Al
2o
3, nickel nitrate and auxiliary agent in mass ratio 10:1.5:0.5 put into pulverizer, wherein, auxiliary agent comprises cerous nitrate and manganese nitrate, and its mass ratio 4:1.The amount of filler of pulverizer is 70%, and the rotating speed controlling pulverizer is 25000r/m, and grinding time is 20 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 700r/m, and it is 30 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 4 hours at 450 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 80-100 order particle, finally obtains catalyst granules.
embodiment 5
By nanometer Al
2o
3, nickel nitrate and auxiliary agent in mass ratio 10:2.5:1 put into pulverizer, wherein, auxiliary agent comprises cerous nitrate and zirconium nitrate, and its mass ratio 3:2.The amount of filler of pulverizer is 30%, and the rotating speed controlling pulverizer is 10000r/m, and grinding time is 10 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 400r/m, and it is 25 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 3 hours at 300 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 80-100 order particle, finally obtains catalyst granules.
embodiment 6
By nanometer Al
2o
3, nickel nitrate and auxiliary agent in mass ratio 10:0.5:0.05 put into pulverizer, wherein, auxiliary agent comprises cerous nitrate and zirconium nitrate, and its mass ratio 3:2.The amount of filler of pulverizer is 30%, and the rotating speed controlling pulverizer is 10000r/m, and grinding time is 10 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 300r/m, and it is 10 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 2 hours at 350 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 60-80 order particle, finally obtains catalyst granules.
embodiment 7
By cordierite nano-powder, nickel hydroxide and auxiliary agent in mass ratio 10:2:0.5 put into pulverizer, wherein, auxiliary agent comprises potassium nitrate and zirconium nitrate, and its mass ratio 3:2.The amount of filler of pulverizer is 30%, and the rotating speed controlling pulverizer is 10000r/m, and grinding time is 10 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 400r/m, and it is 25 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 3 hours at 400 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 60-80 order particle, finally obtains catalyst granules.
embodiment 8
By cordierite nano-powder, nickelous carbonate and auxiliary agent in mass ratio 10:1.5:0.2 put into pulverizer, wherein, auxiliary agent comprises magnesium nitrate and zirconium nitrate, and its mass ratio 3:2.The amount of filler of pulverizer is 40%, and the rotating speed controlling pulverizer is 15000r/m, and grinding time is 12 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 500r/m, and it is 20 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 2 hours at 500 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 60-80 order particle, finally obtains catalyst granules.
embodiment 9
By Nano-meter SiO_2
2, nickel chloride and auxiliary agent in mass ratio 10:1.5:0.2 put into pulverizer, wherein, auxiliary agent comprises calcium nitrate and zirconium nitrate, and its mass ratio 3:2.The amount of filler of pulverizer is 50%, and the rotating speed controlling pulverizer is 20000r/m, and grinding time is 15 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 600r/m, and it is 25 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 3 hours at 400 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 80-100 order particle, finally obtains catalyst granules.
embodiment 10
By Nano-meter SiO_2
2, nickel acetate and auxiliary agent in mass ratio 10:1.2:0.5 put into pulverizer, wherein, auxiliary agent comprises potassium nitrate and calcium nitrate, and its mass ratio 3:2.The amount of filler of pulverizer is 30%, and the rotating speed controlling pulverizer is 25000r/m, and grinding time is 20 minutes.Then the mixture obtained after pulverizing is put into high energy ball mill, control drum's speed of rotation is 300r/m, and it is 10 minutes that Ball-milling Time controls, and the particle mixture obtained is complex catalyst precursor powder.By the precursor powder that obtains in the ball-milling technology temperature lower calcination 4 hours at 300 DEG C, obtain fine-particle powder.The catalyst fines compressing tablet obtained is crushed to 80-100 order particle, finally obtains catalyst granules.
test 1 catalyst activity test
Active testing is carried out to the catalyst granules finally obtained in embodiment 1 to embodiment 6.Get 5g testing sample and be filled in methane steam reformation reactor.In reactor, pass into hydrogen and under the condition of 500 DEG C, make catalyst granules carry out reduction 1 hour.After reduction reaction completes, passed in reactor by the mixture of methane and steam and carry out active testing, wherein the mol ratio of methane and steam is 1:2.Experimental result is as shown in table 1.
table 1 catalyst activity test result
| Reaction time (h) | 1 | 2 | 3 | 4 | 5 |
| Embodiment 1 | 24.2 | 25.0 | 24.7 | 24.4 | 24.8 |
| Embodiment 2 | 22.7 | 22.5 | 23.2 | 23.6 | 22.9 |
| Embodiment 3 | 21.8 | 22.9 | 21.5 | 22.4 | 22.5 |
| Embodiment 4 | 21.2 | 21.0 | 22.4 | 22.1 | 22.3 |
| Embodiment 5 | 23.2 | 23.5 | 23.0 | 22.8 | 22.6 |
| Embodiment 6 | 21.3 | 21.5 | 21.2 | 21.4 | 21.6 |
| Embodiment 7 | 22.1 | 22.3 | 22.2 | 22.4 | 22.2 |
| Embodiment 8 | 22.3 | 22.2 | 22.5 | 22.4 | 22.5 |
| Embodiment 9 | 21.5 | 21.8 | 21.6 | 21.5 | 21.7 |
| Embodiment 10 | 21.7 | 21.4 | 21.8 | 21.7 | 21.6 |
In table 1, data all represent CH after the corresponding reaction time
4conversion ratio (%).
Can be learnt by the data in table 1, under same test condition, the catalyst prepared by the inventive method has good performance.The catalyst prepared by method provided by the invention can effectively be reacted by catalysis low temperature methane steam reformation, and CH
4conversion ratio the highlyest can reach 25%.Further, what adopt due to method of the present invention is the mode of first grinding again high-energy ball milling, therefore, in the present invention obviously reduced produce the load capacity of catalyst.
These are only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for low temperature methane steam reformation catalyst, is characterized in that, comprises the following steps:
Carrier, activating agent are pulverized together with auxiliary agent and obtains mixture, wherein, described activating agent is nickel compound containing, described auxiliary agent is nitrate, and the mass ratio of wherein said carrier, activating agent and auxiliary agent is 10:(0.5-2.5): (0.05-1);
Described mixture is carried out ball-milling treatment, obtains nano-powder, wherein, the rotating speed of described ball-milling treatment is in the scope of 300r/m to 700r/m, and the time is in the scope of 10 minutes to 30 minutes, and described ball-milling treatment brings out Low Temperature Thermal chemical reaction;
Described nano-powder is calcined, obtains fine-particle powder; And
Described fine-particle powder is carried out compressing tablet, fragmentation, process of sieving.
2. method according to claim 1, is characterized in that:
Described carrier is nanometer Al
2o
3, cordierite nano-powder, Nano-meter SiO_2
2in a kind of or their any combination;
Described nickel compound containing comprises a kind of in nickel hydroxide, nickel nitrate, nickelous carbonate, nickel chloride and nickel acetate or their any combination; And
Described auxiliary agent comprises zirconium nitrate, potassium nitrate, a kind of in magnesium nitrate, calcium nitrate, cerous nitrate, lanthanum nitrate, manganese nitrate or their any combination.
3. method according to claim 1, is characterized in that, the step that carrier, activating agent are pulverized together with auxiliary agent is comprised further:
Use pulverizer to implement described pulverising step under the condition of rotating speed in 10000r/m to 25000r/m scope, the amount of filler of described pulverizer is in the scope of 30% to 70%, and the grinding time of pulverizer is in the scope of 10 minutes to 20 minutes.
4. method according to claim 1, is characterized in that, the step that described mixture carries out ball-milling treatment is comprised further:
High energy ball mill is used to implement the step of described ball-milling treatment.
5. the method according to claim 1 or 4, is characterized in that, the diameter of described nano-powder is in the scope of 60nm to 100nm.
6. method according to claim 1, is characterized in that, described nano-powder is carried out the temperature of the step of calcining between 300 DEG C to 500 DEG C, and the time of enforcement is little in the scope of 4 hours between 2.
7. method according to claim 1, is characterized in that, by described fine-particle powder being carried out the step of compressing tablet process, being pulverized by described fine-particle powder is 60 order to 100 object particles.
8. method according to claim 1, is characterized in that, described carrier is nanometer Al
2o
3, described activating agent is nickel nitrate, and described auxiliary agent comprises cerous nitrate and the zirconium nitrate of mass ratio 3:2, and wherein, the mass ratio of described carrier, activating agent and auxiliary agent is 10:2:0.5.
9. method according to claim 1, is characterized in that, described carrier is nanometer Al
2o
3, described activating agent is nickel nitrate, and described auxiliary agent comprises the cerous nitrate of mass ratio 2:1:1, zirconium nitrate and manganese nitrate, and wherein, the mass ratio of described carrier, activating agent and auxiliary agent is 10:1.5:0.2.
10. the low temperature methane steam reformation catalyst prepared of the method according to any one of claim 1-9.
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| CN104258867B (en) * | 2014-08-22 | 2016-06-29 | 江西庞泰环保股份有限公司 | Natural gas steam reforming catalyst and preparation method thereof |
| CN104258864A (en) * | 2014-09-03 | 2015-01-07 | 中国科学院上海高等研究院 | Nanocomposite catalyst and preparation method and application thereof |
| CN105688916B (en) * | 2016-02-23 | 2018-10-26 | 中国科学院上海高等研究院 | A kind of high dispersive high load high activity low temperature methane reforming nickel-base catalyst and its application |
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| CN1939587A (en) * | 2005-09-29 | 2007-04-04 | 北京化工大学 | Metal carrier catalyst for producing synthetic gas by methane carbon dioxide reformation and its production |
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| CN1939587A (en) * | 2005-09-29 | 2007-04-04 | 北京化工大学 | Metal carrier catalyst for producing synthetic gas by methane carbon dioxide reformation and its production |
| CN101224427A (en) * | 2008-02-01 | 2008-07-23 | 汉能科技有限公司 | Catalyst for hydrogen production from methane vapor reforming and preparing method thereof |
| CN101406843A (en) * | 2008-11-27 | 2009-04-15 | 浙江大学 | Nano-catalyst of sodium aluminum hydride complex hydride as well as preparation method and application thereof |
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