CN106423172B - The inlaid hollow structure nickel-base catalyst and preparation method of carbon dioxide thermal reforming - Google Patents
The inlaid hollow structure nickel-base catalyst and preparation method of carbon dioxide thermal reforming Download PDFInfo
- Publication number
- CN106423172B CN106423172B CN201610725877.6A CN201610725877A CN106423172B CN 106423172 B CN106423172 B CN 106423172B CN 201610725877 A CN201610725877 A CN 201610725877A CN 106423172 B CN106423172 B CN 106423172B
- Authority
- CN
- China
- Prior art keywords
- nickeliferous
- carbon ball
- catalyst
- hollow structure
- processing
- 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.)
- Expired - Fee Related
Links
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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses inlaid hollow structure nickel-base catalysts of a kind of carbon dioxide thermal reforming and its preparation method and application.The present invention prepares nickeliferous carbon ball first with the absorption property of oxygen-containing functional group, after using nickeliferous carbon ball as the Ni-based CO 2 reformation catalyst of template two-step method hydrothermal synthesis inlaid hollow structure, i.e., metallic Ni particles be embedded in spinel structure MgAl2O4Shell has many advantages, such as that simple process, at low cost, operation are easy, without precipitating reagent, and gained active component nickel size is small, good dispersion, and high-temperature stability is good.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of inlaid hollow structure nickel of carbon dioxide thermal reforming
Base catalyst and preparation method and application.
Background technique
The key of Reforming methane with carbon dioxide preparing synthetic gas technology is the exploitation of catalyst, and noble metal catalyst usually has
There are higher reactivity and coking resistivity, but noble metal is expensive rare, therefore to CH4-CO2Reforming reaction catalyst is ground
Study carefully and concentrates on in transition-metal catalyst, the especially improvement of Ni base catalyst.
In general, the prior art is concentrated mainly on support type for the research of methane and carbon dioxide catalytic reforming catalyst
Catalyst, generally selection Al2O3、SiO2、MgO、CaO、TiO、ZrO2, silica, foamed ceramics, rare earth oxide and some
Metal composite oxide and molecular sieve are as catalyst carrier.
《The research of methane and carbon dioxide catalytic reforming preparing synthetic gas Ni base catalyst》,《Methane and carbon dioxide is in catalyst
The experimental study of upper preparing synthetic gas by reforming》With《The research of methane reforming with carbon dioxide catalyst》Equal researchs are investigated respectively
The influence of different carriers and carried metal for gained catalyst.However, these research institutes obtain catalyst for activated centre
Protectiveness is not strong, and catalyst is easily inactivated because reuniting with sintering.
Although some study obtains the catalyst of core-shell structure, there are still raw materials more expensive, gained core-shell structure pattern
The disadvantages of being difficult to control.
Summary of the invention
In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a kind of Ni-based dioxies of inlaid hollow structure
Change the preparation method of carbon reforming catalyst, this approach includes the following steps：
(1) by weight, by 3.75~18.75 parts of glucose and 0.01~0.1 part of Nickel dichloride hexahydrate be dissolved in from
In sub- water；Be then transferred in water heating kettle, in 140~180 DEG C react 6~for 24 hours, obtain suspension；Suspension is washed supreme
Clear liquid is colourless, takes precipitating, precipitating is dried, and obtains nickeliferous carbon ball；
(2) nickeliferous carbon ball obtained by step (1) is placed in sodium hydroxide solution, is activated in oil bath；Processing
It mixes, is substantially soluble in ethylene glycol solution with metal salt again afterwards；The metal salt is made of magnesium nitrate and aluminum nitrate；The metal
The mass ratio of nickeliferous carbon ball is 3 after salt and activation:0.3~0.7；
(3) step (2) gains are transferred in water heating kettle, react 12-24h at 140-180 DEG C, obtains suspension；
Suspension is centrifuged, washed, is dried；
(4) step (3) gains are carried out to calcination processing at 700-800 DEG C to get the catalyst precursor；
(5) H is utilized2High temperature reduction processing is carried out to get the catalyst to step (4) catalyst precursor.
The present invention is to polymerize nucleation at high temperature under high pressure with glucose, and adsorbing metal nickel ion, syntrophism forms nickeliferous
Carbon ball presoma.Using the more oxygen-content active functional group in nickeliferous carbon ball surface, magnesium-aluminum metal ion is adsorbed under high-temperature solvent,
Under prolonged high temperature and pressure, strong interaction occurs for nickel particles and magnalium particle, forms magnalium shell and coats nickeliferous carbon ball
Presoma goes template agent removing carbon ball at high temperature, and nickel particles are embedded in magnalium shell, and it is small to form nickel oxide particle, and disperses equal
Even NiO@MgAl2O4Catalyst precursor, through H2NiO@MgAl is obtained after reduction2O4Catalyst.This method is environmentally protective, and can be with
Partial size by controlling nickeliferous carbon ball controls the size of catalyst granules.
Preferably, in step (1), the suspension is cleaned using deionized water and dehydrated alcohol.
Preferably, in step (1), dry temperature is 60 DEG C.
Preferably, in step (2), the molar ratio of magnesium nitrate and aluminum nitrate is 1 in the metal salt:2.
Preferably, in step (2), when carrying out the activation processing, oil bath temperature is 150 DEG C, and the processing time is 3h.
Preferably, 5, in step (2), nickeliferous carbon ball and metal salt are placed in ethylene glycol solution, in power 90W, frequency
20-30min is handled under the conditions of the ultrasonic treatment of 40KHz sufficiently to be dissolved.
Preferably, in step (4), the time of calcination processing is 4-6h.
Preferably, in step (5), the condition of the high temperature reduction processing is：It is 500 DEG C in temperature, H2Flow is 30mL/
Reduction treatment 1h under conditions of min.
It is a further object to provide the Ni-based titanium dioxides of inlaid hollow structure prepared by the above method
Carbon reforming catalyst.
It is a further object to provide the Ni-based CO 2 reformation catalyst of above-mentioned inlaid hollow structure in first
Application in terms of alkane carbon dioxide conversion preparing synthetic gas.
Beneficial effects of the present invention：
1, the present invention have simple process and low cost, morphology controllable, be not necessarily to precipitating reagent the advantages of；
2, the present invention gained active component particles of catalyst are small, the good advantage of good dispersion, high temperature sintering resistant ability.
Detailed description of the invention
Fig. 1 is the SEM spectrogram that nickeliferous carbon ball is prepared under different Ni contents；
Fig. 2 is the SEM spectrogram that nickeliferous carbon ball is prepared under the different hydro-thermal times；
Fig. 3 is the SEM spectrogram of preparation gained catalyst under different solvents；
Fig. 4 is that the Mapping of nickeliferous carbon ball schemes；
Fig. 5 is SEM the and TEM spectrogram tested in preparation process；
Fig. 6 is the XRD spectra of gained catalyst；
In Fig. 1：A, b, c are respectively the nickeliferous carbon ball that Ni content is 0.01g, 0.02 and 0.1g preparation；
In Fig. 2：A, b is respectively the nickeliferous carbon ball prepared for 6h, 12h the hydro-thermal time；
In Fig. 3：A, b is respectively water, the sample that ethylene glycol is solvent preparation；
In Fig. 5：A indicates the nickeliferous carbon ball SEM spectrogram that 0.1gNi content hydro-thermal time 12h is obtained；B indicates magnesium-aluminum metal salt
Nickeliferous carbon ball SEM spectrogram after package；The TEM spectrogram of c expression catalyst with core-casing structure.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
It is further detailed in the present invention, should not be understood as limiting the scope of the invention, which is skilled in technique
Some nonessential modifications and adaptations that personnel are made according to foregoing invention content, still fall within protection scope of the present invention.
Embodiment 1：
1) nickeliferous carbon ball is prepared
1.1) using glucose and nickel chloride as raw material, 0.01g, 0.2g and 0.1g Nickel dichloride hexahydrate and three parts are weighed
Three parts of glucose are dissolved in deionized water with nickel chloride respectively, form clear solution A, B and C by 3.75g glucose；
1.2) solution A obtained in step 1.1), B and C are transferred in water heating kettle, respectively in 160 DEG C of reaction 12h；It will
Water heating kettle naturally cools to room temperature, obtains dark brown suspension；
1.3) deionized water and dehydrated alcohol is used successively to wash, be centrifuged respectively suspension obtained in step 1.2), until
Supernatant obtains two parts of dark browns precipitatings in colourless；
1.4) it will be deposited in 60 DEG C obtained in step 1.3) to be dried overnight, obtains nickeliferous carbon ball particle；
2) the resulting nickeliferous carbon ball of 0.4g step 1) is taken to be added separately in the 1mol/L NaOH solution of 40mL, 150 DEG C of oil
Bathe 3h.It uses deionized water and dehydrated alcohol successively to wash respectively obtained suspension again, be centrifuged, is dry, it is heavy to obtain black
It forms sediment；
3) metal salt 2g is weighed, the metal salt is made of magnesium nitrate and aluminum nitrate, the molar ratio of magnesium nitrate and aluminum nitrate
It is 1:2, it is added in 50mL ethylene glycol solution together with the black precipitate 0.2g in step 2), ultrasonic 20-30min (power
90W, frequency 40KHz)；
4) mixed solution obtained in step 3) is transferred to 180 DEG C of solvent heats of water heating kettle for 24 hours；By water heating kettle natural cooling
To room temperature, black suspension D, E and F are obtained；
5) black suspension D obtained in step 4), E and F are centrifuged, are washed, 60 DEG C are dried overnight, and respectively obtain
Dark brown powder；
6) dark brown powder obtained in step 5) is calcined to 4h at 700 DEG C and removes carbon ball to get under different Ni contents
Ni-based core-shell structure copolymer methane carbon dioxide reformation catalyst.
The micro-structure of the catalyst sample of different Ni content preparations is as shown in Figure 1：
A in Fig. 1, b and c are the sample prepared with different Ni contents respectively.
Scheme a：When Ni content is 0.01g, it is preferably spherical to form pattern, diameter about 200nm or so；
Scheme b：When Ni content is 0.02g, it is preferably spherical to form pattern, diameter about 600nm or so；
Scheme c：When Ni content is 0.1g, it is preferably spherical to form pattern, diameter about 700nm or so；
Embodiment 2：
1) nickeliferous carbon ball is prepared
1.1) using glucose and nickel chloride as raw material, 3.75g glucose is weighed, 0.1g Nickel dichloride hexahydrate is molten by the two
In deionized water, clear solution A is formed；Above-mentioned weighing step is repeated, identical clear solution B is obtained；
1.2) solution A obtained in step 1.1) and B are transferred in water heating kettle, respectively in 160 DEG C of reaction 6h and 12h；
Water heating kettle is naturally cooled into room temperature, obtains dark brown suspension；
1.3) suspension obtained in step 1.2) washed with deionized water and dehydrated alcohol respectively, be centrifuged, obtain three
Part dark brown precipitating；
1.4) it will be deposited in 60 DEG C of dryings obtained in step 1.3) for 24 hours, obtain nickeliferous carbon ball particle；
2) the resulting nickeliferous carbon ball of 0.4g step 1) is taken to be added separately in the 1mol/LNaOH solution of 40mL, 150 DEG C of oil
Bathe 3h.Obtained suspension is successively washed with deionized water and dehydrated alcohol respectively again, be centrifuged, is dried overnight, is obtained black
Color precipitating；
3) metal salt 3g is weighed, the metal salt is made of magnesium nitrate and aluminum nitrate, the molar ratio of magnesium nitrate and aluminum nitrate
It is 1:2, it is added in 50mL ethylene glycol solution together with the black precipitate 0.7g in step 2), ultrasonic 20-30min (power
90W, frequency 40KHz)；
4) mixed solution obtained in step 3) is transferred to 180 DEG C of solvent heats of water heating kettle for 24 hours；By water heating kettle natural cooling
To room temperature, black suspension C and D are respectively obtained；
5) three parts of black suspensions obtained in step 4) are successively centrifuged to, washing colourless to supernatant, 60 DEG C dry
It is dry overnight, respectively obtain dark brown powder；
6) the dark brown powder respectively obtained in step 5) is calcined to 4h at 700 DEG C and removes carbon ball to get different hydro-thermals
Ni-based core-shell structure copolymer methane carbon dioxide reformation catalyst under time.
The micro-structure of the catalyst sample of different hydro-thermal time preparations is as shown in Figure 2：
A, b and c are hydro-thermal time 6h, the sample of 12h preparation respectively in Fig. 2
Scheme a：It is not scatter also between nickeliferous carbon ball as shown in figure a using the nickeliferous carbon ball that 6h is formed as the hydro-thermal time；
Scheme b：Using the nickeliferous carbon ball that 12h is formed as the hydro-thermal time, as shown in figure b, as the reaction time extends, nickeliferous carbon
Ball dispersion is more uniform；
Embodiment 3：
1) nickeliferous carbon ball is prepared
1.1) using glucose and nickel chloride as raw material, 3.75g glucose is weighed, 0.1g Nickel dichloride hexahydrate is molten by the two
In deionized water, clear solution A is formed；Above-mentioned weighing step is repeated, identical clear solution B is obtained；
1.2) solution A obtained in step 1.1) and B are transferred in water heating kettle, respectively in 160 DEG C of reaction 12h；By water
Hot kettle naturally cools to room temperature, obtains dark brown suspension；
1.3) suspension obtained in step 1.2) washed with deionized water and dehydrated alcohol respectively, be centrifuged, obtain two
Part dark brown precipitating；
1.4) it will be deposited in 60 DEG C of dryings obtained in step 1.3) for 24 hours, obtain nickeliferous carbon ball particle C and D；
2) the resulting nickeliferous carbon ball C and D of 0.4g step 1) is taken to be added in the 1mol/L NaOH solution of 40mL, 150 DEG C of oil
Bathe 3h.Obtained suspension is washed with deionized water and dehydrated alcohol respectively again, is centrifuged, is dry, obtains black precipitate；
3) metal salt 1g is weighed, the metal salt is made of magnesium nitrate and aluminum nitrate, the molar ratio of magnesium nitrate and aluminum nitrate
It is 1:2, it is separately added into 50mL ethylene glycol and the aqueous solution of 50mL with the black precipitate 0.2g in step 2), ultrasonic 20-
30min (power 90W, frequency 40KHz)；
4) mixed solution obtained in step 3) is transferred to 180 DEG C of solvent heats of water heating kettle and hydro-thermal for 24 hours respectively；By hydro-thermal
Kettle naturally cools to room temperature, obtains black suspension E and F；
5) black suspension E and F obtained in step 4) are centrifuged, are washed, 60 DEG C of dry 12-24h are respectively obtained
Dark brown powder；
6) dark brown powder obtained in step 5) is calcined to 4h at 700 DEG C and removes carbon ball to get under different solvents
Ni-based core-shell structure copolymer methane carbon dioxide reformation catalyst.
The micro-structure of the catalyst sample of different solvents preparation is as shown in Figure 3：
A and b is the sample prepared with different solvents respectively in Fig. 3.
Scheme a：When solvent is water, fail to form pattern preferably spherical；
Scheme b：When solvent is ethylene glycol, it is preferably spherical pattern to be formed.
Claims (10)
1. a kind of preparation method of the inlaid hollow structure nickel-base catalyst of carbon dioxide thermal reforming, which is characterized in that described
Method includes the following steps：
(1) by weight, 3.75~18.75 parts of glucose and 0.01~0.1 part of Nickel dichloride hexahydrate are dissolved in deionized water
In；Be then transferred in water heating kettle, in 140~180 DEG C react 6~for 24 hours, obtain suspension；Suspension is washed to supernatant
It is colourless, precipitating is taken, precipitating is dried, obtains nickeliferous carbon ball；
(2) nickeliferous carbon ball obtained by step (1) is placed in sodium hydroxide solution, is activated in oil bath；After processing again
It mixes, is substantially soluble in ethylene glycol solution with metal salt；The metal salt is made of magnesium nitrate and aluminum nitrate；The metal salt with
The mass ratio of nickeliferous carbon ball is 3 after activation:0.3~0.7；
(3) step (2) gains are transferred in water heating kettle, react 12-24h at 140-180 DEG C, obtains suspension；It will hang
Supernatant liquid is centrifuged, is washed, is dried；
(4) step (3) gains are carried out to calcination processing at 700-800 DEG C to get the catalyst precursor；
(5) H is utilized2High temperature reduction processing is carried out to get the catalyst to step (4) catalyst precursor.
2. the method according to claim 1, wherein in step (1), using deionized water and dehydrated alcohol to institute
Suspension is stated to be cleaned.
3. the method according to claim 1, wherein dry temperature is 60 DEG C in step (1).
4. the method according to claim 1, wherein in step (2), magnesium nitrate and aluminum nitrate in the metal salt
Molar ratio be 1:2.
5. the method according to claim 1, wherein in step (2), when carrying out the activation processing, oil bath temperature
Degree is 150 DEG C, and the processing time is 3h.
6. the method according to claim 1, wherein nickeliferous carbon ball and metal salt are placed in second two in step (2)
In alcoholic solution, power 90W, frequency 40KHz ultrasonic treatment under the conditions of processing 20-30min sufficiently dissolved.
7. the method according to claim 1, wherein the time of calcination processing is 4-6h in step (4).
8. the method according to claim 1, wherein in step (5), the condition of the high temperature reduction processing is：
It is 500 DEG C in temperature, H2Flow is reduction treatment 1h under conditions of 30mL/min.
9. being catalyzed by the Ni-based CO 2 reformation of inlaid hollow structure that any one of claim 1-8 the method is prepared
Agent.
10. the Ni-based CO 2 reformation catalysis of the inlaid hollow structure that any one of claim 1-8 the method is prepared
Application of the agent in terms of Reforming methane with carbon dioxide preparing synthetic gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610725877.6A CN106423172B (en) | 2016-08-26 | 2016-08-26 | The inlaid hollow structure nickel-base catalyst and preparation method of carbon dioxide thermal reforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610725877.6A CN106423172B (en) | 2016-08-26 | 2016-08-26 | The inlaid hollow structure nickel-base catalyst and preparation method of carbon dioxide thermal reforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106423172A CN106423172A (en) | 2017-02-22 |
| CN106423172B true CN106423172B (en) | 2018-11-20 |
Family
ID=58182170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610725877.6A Expired - Fee Related CN106423172B (en) | 2016-08-26 | 2016-08-26 | The inlaid hollow structure nickel-base catalyst and preparation method of carbon dioxide thermal reforming |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423172B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586026A (en) * | 2019-10-09 | 2019-12-20 | 东南大学 | Adsorbent for removing heavy metal arsenic and preparation method and application thereof |
| CN112206789A (en) * | 2020-09-03 | 2021-01-12 | 天津大学 | Catalyst for preparing synthesis gas by reforming methane and carbon dioxide and preparation method and application thereof |
| CN113813942B (en) * | 2021-08-20 | 2022-12-09 | 西安交通大学 | Carbon sphere ZrO 2 Ni-based catalyst with shell-layer coating structure and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389801A (en) * | 2011-09-28 | 2012-03-28 | 新疆大学 | Nickel-based catalyst for obtaining synthetic gas through carbon dioxide reforming of methane and preparation method for nickel-based catalyst |
| CN102416328A (en) * | 2011-08-29 | 2012-04-18 | 重庆大学 | Catalyst for preparing synthesis gases through dry methane reforming (DMR) and preparation method thereof |
| CN102744072A (en) * | 2012-08-03 | 2012-10-24 | 太原理工大学 | Catalyst used for reforming synthesis gas of methane carbon dioxide and preparation method and application thereof |
| CN105366700A (en) * | 2015-04-29 | 2016-03-02 | 重庆大学 | Method for synthesizing petal-shaped magnesium-aluminum spinel nano empty sphere with high specific surface |
| CN105771995A (en) * | 2016-03-31 | 2016-07-20 | 山西大学 | Encapsulating nanometer material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101405517B1 (en) * | 2013-05-22 | 2014-06-11 | 한국과학기술연구원 | Process for preparing nickel based catalysts for SCR of natural gas |
-
2016
- 2016-08-26 CN CN201610725877.6A patent/CN106423172B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416328A (en) * | 2011-08-29 | 2012-04-18 | 重庆大学 | Catalyst for preparing synthesis gases through dry methane reforming (DMR) and preparation method thereof |
| CN102389801A (en) * | 2011-09-28 | 2012-03-28 | 新疆大学 | Nickel-based catalyst for obtaining synthetic gas through carbon dioxide reforming of methane and preparation method for nickel-based catalyst |
| CN102744072A (en) * | 2012-08-03 | 2012-10-24 | 太原理工大学 | Catalyst used for reforming synthesis gas of methane carbon dioxide and preparation method and application thereof |
| CN105366700A (en) * | 2015-04-29 | 2016-03-02 | 重庆大学 | Method for synthesizing petal-shaped magnesium-aluminum spinel nano empty sphere with high specific surface |
| CN105771995A (en) * | 2016-03-31 | 2016-07-20 | 山西大学 | Encapsulating nanometer material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106423172A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105050714B (en) | For the catalyst containing six nickel aluminates of reforming hydrocarbon in the presence of carbon dioxide | |
| Banerjee et al. | A comprehensive study on Pt/Al2O3 granular catalyst used for sulfuric acid decomposition step in sulfur–iodine thermochemical cycle: Changes in catalyst structure, morphology and metal-support interaction | |
| CN106391028B (en) | A kind of methanation catalyst and preparation method thereof for fluidized bed | |
| CN106423172B (en) | The inlaid hollow structure nickel-base catalyst and preparation method of carbon dioxide thermal reforming | |
| CN105562113B (en) | The method of catalyst carrier and loaded catalyst and its preparation method and application and methane dry reforming preparing synthetic gas | |
| CN108855197B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN106622331B (en) | A kind of preparation method of high-specific surface area graphite phase carbon nitride photochemical catalyst | |
| CN106518045A (en) | Magnesia alumina spinel and high temperature methanation catalyst and preparation methods thereof | |
| CN104549411A (en) | Preparation method of nickel-based catalyst based on SBA-15 and application of nickel-based catalyst in SNG preparation | |
| CN103347605A (en) | Catalysts | |
| Herwig et al. | Hierarchically Structured porous spinels via an epoxide-mediated sol–gel process accompanied by polymerization-induced phase separation | |
| CN109718787B (en) | Cerium/yttrium stabilized zirconia support and catalyst | |
| CN101723333A (en) | Method for preparing mesoporous metallic oxides with different appearances | |
| CN108855201B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN108855198B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN105498852A (en) | Nickel-based catalyst carrier and preparation method and application thereof, and nickel-based catalyst and preparation method and application thereof | |
| CN108479761B (en) | Method for preparing spherical perovskite catalyst by taking casein as biological template | |
| CN107746074B (en) | A kind of titanium dioxide of core-shell structure mesoporous material and preparation method thereof with cavity | |
| CN107638883B (en) | Catalyst for directly synthesizing low-carbon olefin by Fischer-Tropsch synthesis, preparation and application | |
| CN108525668B (en) | Preparation method of sepiolite nanofiber loaded cobalt-aluminum composite oxide | |
| CN107983385B (en) | Nickel-based magnetic composite material and synthesis method and application thereof | |
| CN109382131B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN105772108B (en) | A kind of methane synthesizing catalyst layered vector and preparation method thereof | |
| CN105709741B (en) | A kind of preparation method of the non-uniformly distributed Catalyst for Low-Temperature Methanation of active component | |
| CN109012716A (en) | A kind of sulphur carbon ball supported precious metal catalyst and its preparation and the application in synthesis N, N '-dibenzyl-ethylenediamin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Min Inventor after: Fu Xiaojin Inventor after: Liu Yong Inventor after: Zheng Xiaogang Inventor after: Dong Lichun Inventor before: Fu Xiaojin Inventor before: Liu Yong Inventor before: Zheng Xiaogang Inventor before: Dong Lichun |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181120 Termination date: 20190826 |