CN106607065B - A kind of propane dehydrogenation catalyst and preparation method - Google Patents
A kind of propane dehydrogenation catalyst and preparation method Download PDFInfo
- Publication number
- CN106607065B CN106607065B CN201510696918.9A CN201510696918A CN106607065B CN 106607065 B CN106607065 B CN 106607065B CN 201510696918 A CN201510696918 A CN 201510696918A CN 106607065 B CN106607065 B CN 106607065B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- accordance
- dense
- platinum
- carbon nanotube
- 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.)
- Active
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
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of propane dehydrogenation catalyst, the multi-walled carbon nanotube of the P and 92~99.7 mass % of Pt, 0.2~5.0 mass % including 0.1~3.0 mass %.The present invention is carrier using multi-walled carbon nanotube, after it is carried out oxidation processes with high concentration mixed acid, then Supported Pt Nanoparticles and phosphorus, obtain the multi-walled carbon nanotube catalyst for carrying platinum and phosphorus.The catalyst preparation is simply used for dehydrogenating propane reaction, reaction stability and Propylene Selectivity with higher.
Description
Technical field
The present invention relates to a kind of propane dehydrogenation catalyst and preparation methods, specifically, being one kind with carbon nano-tube material
For the propane dehydrogenation catalyst and preparation method of carrier.
Background technique
Pt series catalysts are that dehydrogenating propane reacts one of common catalyst.Dehydrogenating propane is highly endothermic, molecular number increase
Reversible reaction, high temperature and low pressure is conducive to the progress of dehydrogenation reaction, and common reaction temperature is 600 DEG C or so, higher anti-
It answers temperature that Deposition During Propane Pyrolysis and propane deep dehydrogenation degree is caused to aggravate, reduces Propylene Selectivity, while can also aggravate catalyst
Surface carbon deposit leads to catalyst inactivation in turn.By Al2O3The catalyst of carrier loaded Pt is bifunctional catalyst, and there are Pt on surface
Center and acid centre, the center Pt therein can be divided into single center Pt and more centers Pt again, and more centers Pt are suitable for hydrogenolysis, carbon deposit etc.
The generation of structure sensitive reaction, single center Pt is suitable for the generation of the structure insensitive reactions such as dehydrogenation and isomerization, and catalyst carries
The acid centre of body then easily causes the reactions such as skeletal isomerization, cracking and olefinic polymerization and then coking is caused to be reacted, and alkene
Interaction between Pt is stronger, and alkene will be faster than alkane in the reaction that the surface Pt occurs.Therefore, it is advantageous to increase the list center Pt
It is reacted in dehydrogenating propane, the dispersion degree for increasing Pt can get more list centers Pt.It generally uses and the auxiliary agents such as Sn is added to improve
The introducing of the dispersion degree of Pt metal, alkali or alkaline-earth metal etc. can neutralize the acidity of single Pt catalyst carrier, so as to improve catalysis
The activity and stability of agent, alkene and the interaction of Pt can also be weakened by introducing auxiliary agent, to improve, catalyst is whole to be taken off
Hydrogen performance.
Conventional dehydrogenation catalyst carrier, such as Al2O3Equal high temperature opportunity tool performance and hot property are unstable, the surface Yi Yuqi gold
Symbolic animal of the birth year interaction causes metallic particles to be sintered.In recent years, studying hotter nano-carbon material has good pore structure, less
Defect and impurity content, good antioxygenic property and preferable electronics and heat transfer function.As carrier, nano-carbon material
There is characteristic not available for conventional catalyst support simultaneously, such as acidproof alkaline media, surface chemical property is adjustable, can basis
It is specific to react the pore size distribution needed and promote metal precursor in the distribution etc. of carbon material surface by surface functional group.
As the carbon nanomaterial-carbon nanotube (CNTs) being widely studied, before as catalyst carrier, lead to
Often need use the method for oxidation processes to remove the impurity such as the required metallic catalyst of its synthesis and amorphous carbon, while into
Row oxidation processes can also create more defective bits on the surface of CNTs, truncated, be open to CNTs, and increase its surface
Oxygen content and oxygenated species to preferably be anchored metal etc..However, dehydrogenating propane reaction is (600 DEG C) progress at high temperature
Reaction, high temperature will cause oxygenated species fall off be unfavorable for anchoring to metal, and easily cause catalyst performance not
Stablize.(Y WANG, N SHAH, the GP HUFFMAN.Pure hydrogen production by partial such as Wang
dehydrogenation of cyclohexane and methylcyclohexane over nanotube-supported
Pt and Pd catalysts [J] .Energy and Fuels, 2004,18 (5): 1429-1433.) it is prepared using infusion process
It is de- for hexamethylene and methyl ring methane to accumulate the Pt-SC-CNT catalyst that taper carbon nanotube (SC-CNT) is carrier
Hydrogen reaction, it is found that the product of cyclohexane dehydrogenation only includes H2And benzene, and the product of hexahydrotoluene dehydrogenation only includes for H2And first
Benzene, and Pt content is the conversion ratio of 0.25wt.%Pt-SC-CNT catalyst and platinum content is 1wt.%Pt/Al2O3Commercialization urge
Agent is suitable.
(Y WANG, N SHAH, FE HUGGINS, the et al.Hydrogen production by such as Wang
catalytic dehydrogenation of tetralin and decalin over stacked cone carbon
Nanotube-supported Pt catalysts [J] .Energy and Fuels, 2006,20 (6): 2612-2615.) it adopts
The dehydrogenation reaction evaluation that tetrahydronaphthalene and decahydronaphthalenes have also been carried out with Pt-SC-CNT catalyst, finds the activity of the catalyst
Better than using carbon black and aluminium oxide as the Pt catalyst of carrier, and tetrahydronaphthalene can be fully converted to naphthalene and H by the catalyst2,
Decahydronaphthalenes can be nearly fully converted to naphthalene and H2。
(R WANG, X SUN, B ZHANG, the et al.Hybrid Nanocarbon as a Catalyst for such as Wang
Direct Dehydrogenation of Propane:Formation of an Active and Selective Core-
Shell sp2/sp3Nanocomposite Structure [J] .Chemistry-A European Journal, 2014,20
(21): 6324-6331. the diamond kernel (sp with different proportion) is had studied2)/graphite shells (sp3) composite Nano carbon
The dehydrogenating propane performance of material finds the performance of the material better than single Nano diamond and graphite.
Summary of the invention
The object of the present invention is to provide a kind of propane dehydrogenation catalyst and preparation method, which reacts in dehydrogenating propane
In show it is good activity and stability.
Propane dehydrogenation catalyst provided by the invention, the P of Pt, 0.2~7.0 mass % including 0.1~5.0 mass % and
The multi-walled carbon nanotube of 88~99.7 mass %.
The present invention is carrier using multi-walled carbon nanotube, and catalyst is made in supporting Pt and P component, and catalyst obtained is used for
Propane hydrocarbon dehydrogenation reaction, activity and stability with higher.
Specific embodiment
The present invention is carrier using multi-walled carbon nanotube, after it is carried out oxidation processes with high concentration mixed acid, then is loaded
Platinum and phosphorus obtain the multi-walled carbon nanotube catalyst of Supported Pt Nanoparticles and phosphorus.The catalyst preparation is simple, reacts for dehydrogenating propane,
Reaction stability and Propylene Selectivity with higher.
Catalyst of the present invention includes multi-walled carbon nanotube, platinum and phosphorus, preferably include 0.2~3.0 mass % Pt,
The multi-walled carbon nanotube of the P of 0.5~5.0 mass % and 92~99.3 mass %.
The aperture of catalyst of the present invention preferably 30.0~40.0nm, specific surface area preferably 200~250m2/ g, total hole
Volume preferably 0.1~2.0cm3/g。
The multi-walled carbon nanotube for being used to prepare carrier is prepared using chemical vapour deposition technique (CVD), catalysis used
Agent is supported cobalt catalysts, and raw material is hydrocarbon, and preparation temperature is 600~800 DEG C.
The preparation method of catalyst provided by the invention, includes the following steps:
(1) with dense H2SO4With dense HNO3Impregnation mixture multi-walled carbon nanotube carry out oxidation processes,
(2) by the multi-walled carbon nanotube after (1) step oxidation processes, impregnated with phosphorus-containing compound solution, it is dry after again with containing
Platinum compounds solution dipping is roasted in 400~800 DEG C in inert gas after dry, is then restored.
The method of the present invention (1) step is to carry out oxidation processes, the dense H to multi-walled carbon nanotube2SO4Concentration is 95~98
Quality %, dense HNO3Concentration is 65~68 mass %, the dense H2SO4With dense HNO3Volume be 1~5:1, preferably 2~4:1,
The liquid/solid ratio of mixed acid used and multi-wall carbon nano-tube tube material is 40~60mL/g, and the time of oxidation processes preferably 2~12 is small
When, it is 2~10 hours more preferable.
With dense H2SO4With dense HNO3Impregnation mixture multi-wall carbon nano-tube tube material carry out oxidation processes temperature be 20~
70 DEG C, preferably 20~50 DEG C.
The method of the present invention (2) step is Supported Pt Nanoparticles and phosphorus prepares catalyst, and dipping draws compound containing platinum described in platinum and is selected from nitre
Sour platinum, chloroplatinic acid, potassium chloroplatinate, tetraammineplatinum chloride or acetylacetone,2,4-pentanedione platinum.The phosphorus-containing compound be selected from diammonium hydrogen phosphate,
Ammonium dihydrogen phosphate or phosphoric acid.When dipping the liquid/solid ratio of maceration extract and multi-walled carbon nanotube used be 1~20mL/g, preferably 1~
15mL/g, preferably 20~50 DEG C of dipping temperature.Phosphorus content preferably 0.5~7mg/mL in the phosphorus-containing compound solution is impregnated, is contained
Platinum content preferably 0.3~8mg/mL in platinum compounds solution.
(2) dipping described in step introduces phosphorus and standing infusion process can be used in platinum, and preferred method is will be more after oxidation processes
Wall carbon nano tube is put into maceration extract, first uses ultrasonication, then stand dipping.With time preferably 0.3 of ultrasonication~
3.0h stands dip time preferably 4~36h, more preferable 10~30h.
(2) after step dipping introduces phosphorus and introduces platinum, obtained solid needs drying, and preferably 60~150 DEG C of drying temperature, when dry
Between preferably 8~15h.
It is above-mentioned draw platinum it is dry after solid roasted in inert gas, the preferred nitrogen of the inert gas.The roasting
Preferably 500~700 DEG C of temperature are burnt, calcining time preferably 2~6h.Hydrogen reducing, the temperature of reduction preferably 500 are preferably used after roasting
~800 DEG C, recovery time preferably 0.5~4h.
Catalyst provided by the invention be suitable for preparing propylene by dehydrogenating propane, applicable dehydrogenating propane reaction temperature be 500~
650 DEG C, pressure be 0.1~0.5MPa, propane is passed through catalyst bed after being diluted with nitrogen, the propane content in nitrogen can be
3~10 volume %, propane feed mass space velocity preferably 0.5~10h-1。
Below by example, present invention be described in more detail, but the present invention is not limited thereto.
Example 1
It prepares catalyst of the present invention and carries out dehydrogenating propane evaluation
(1) multi-walled carbon nanotube carrier is prepared
Taking 10g multi-walled carbon nanotube, (purity > 95wt.%, ash content < 1.5wt.%, Metal Inst., Chinese Academy of Sciences mention
For number GT-300 is prepared using chemical vapour deposition technique (CVD), and used catalyst is supported cobalt catalysts, preparation temperature
600~800 DEG C of degree) the dense H that is 3:1 with 500mL volume ratio2SO4/ dense HNO3Mixed acid carry out oxidation processes 7 in 25 DEG C of dippings
Hour, the dense H2SO4Concentration be 98 mass %, dense HNO3Concentration be 66 mass %, solid is washed with deionized water after dipping
Wash, 120 DEG C air drying 12 hours, obtain multi-walled carbon nanotube support C NTs.
(2) catalyst is prepared
The ammonium dihydrogen phosphate that multi-walled carbon nanotube support C NTs, P content after taking 1.0g oxidation processes are 5mg/mL
1mL and deionized water 6mL are placed in crucible, in 25 DEG C with ultrasonication 0.5h, then are stood dipping 23.5h, are taken solid in 120
DEG C dry 12h, the Pt content for placing into 5.2mL is to use ultrasonic wave in the platinum acid chloride solution and 1.8mL deionized water of 5.8mg/mL
0.5h is handled, then stands dipping 23.5h, solid is in 120 DEG C of dry 12h after dipping, and 600 DEG C in N2Middle roasting 4h, 580 DEG C in H2
Middle reduction 1h obtains catalyst A, aperture 35.6nm, specific surface area 206m2/ g, total pore volume 1.304cm3/ g (root
According to nitrogen suction-desorption curve, specific surface area is obtained using BET equation, aperture and total pore volume are obtained using BJH equation), catalysis
Platinum content and phosphorus content in agent A are shown in Table 1, and wherein Pt content, phosphorus content are measured by elemental microanalysis method.
Example 2
Catalyst is prepared by the method for example 1, the difference is that the ammonium dihydrogen phosphate that (2) step is added is 2mL, it is obtained
Platinum content and phosphorus content in catalyst B are shown in Table 1.
Example 3
Catalyst is prepared by the method for example 1, the difference is that the ammonium dihydrogen phosphate that (2) step is added is 4mL, it is obtained
Platinum content and phosphorus content in catalyst C are shown in Table 1.
Example 4
Catalyst is prepared by the method for example 1, the difference is that the ammonium dihydrogen phosphate that (2) step is added is 10mL, is made
Catalyst D in platinum content and phosphorus content be shown in Table 1.
Example 5
Catalyst is prepared by the method for example 1, the difference is that the ammonium dihydrogen phosphate that (2) step is added is 2mL, addition
Platinum acid chloride solution is 0.52mL, and the platinum content and phosphorus content in catalyst E obtained are shown in Table 1.
Example 6
Catalyst is prepared by the method for example 1, the difference is that the ammonium dihydrogen phosphate that (2) step is added is 2mL, addition
Platinum acid chloride solution is 1.7mL, and the platinum content and phosphorus content in catalyst F obtained are shown in Table 1.
Example 7
Catalyst is prepared by the method for example 1, the difference is that the ammonium dihydrogen phosphate that (2) step is added is 2mL, addition
Platinum acid chloride solution is 3.4mL, and the platinum content and phosphorus content in catalyst G obtained are shown in Table 1.
Example 8
Catalyst is prepared by the method for example 1, the difference is that the ammonium dihydrogen phosphate that (2) step is added is 2mL, addition
Platinum acid chloride solution is 8.6mL, and the platinum content and phosphorus content in catalyst H obtained are shown in Table 1.
Example 9
Catalyst is prepared by the method for example 1, the difference is that with dense H in (1) step2SO4/ dense HNO3Mixed acid in 50 DEG C
Multi-walled carbon nanotube is impregnated, the platinum content and phosphorus content in catalyst I obtained are shown in Table 1.
Comparative example 1
The multi-walled carbon nanotube support C NTs for taking 1.0g example 1 (1) step to prepare, the Pt content for being put into 5.2mL is 5.8mg/
In the platinum acid chloride solution and 1.8mL deionized water of mL, with ultrasonication 0.5h, then dipping 23.5h is stood, solid exists after dipping
120 DEG C of dry 12h, 600 DEG C in N2Middle roasting 4h, 580 DEG C in H2Middle reduction 1h, the obtained platinum content in catalyst M are shown in Table 1.
Comparative example 2
The multi-walled carbon nanotube support C NTs for taking 1.0g example 1 (1) step to prepare, the P content for being put into 2mL is the phosphorus of 5mg/mL
In acid dihydride ammonium salt solution and 5mL deionized water, with ultrasonication 0.5h, then dipping 23.5h is stood, solid is 120 after dipping
DEG C dry 12h, 600 DEG C in N2Middle roasting 4h, the obtained phosphorus content in catalyst n are shown in Table 1.
Example 10
The dehydrogenating propane performance of this example evaluation catalyst
Take 0.2g Catalyst packing in micro-reactor, the propane and N for being 5% with propane volume fraction2Mixture be
Reaction raw materials are 1.8h in 600 DEG C, 0.11MPa, propane feed mass space velocity-1Under conditions of react 5h, during calculating reaction
The average value of conversion of propane and Propylene Selectivity, each catalyst reaction the results are shown in Table 2.
Example 11
Take 0.2g example 2 prepare catalyst B, be loaded in micro-reactor, with propane volume fraction be 5% propane and
N2Mixture be reaction raw materials, 600 DEG C, 0.11MPa, propane feed mass space velocity be 1.8h-1Under conditions of carry out dehydrogenation
Reaction, reaction 9.5 hours the results are shown in Table 3.Table 3 shows that catalyst of the present invention has preferable dehydrogenating propane stability.
Comparative example 3
The catalyst M for taking 0.2g comparative example 1 to prepare, is loaded in micro-reactor, the propane for being 5% with propane volume fraction
And N2Mixture be reaction raw materials, 600 DEG C, 0.11MPa, propane feed mass space velocity be 1.8h-1Under conditions of taken off
Hydrogen reaction, reaction 9.5 hours the results are shown in Table 4.
By table 3,4 data of table it is found that catalyst of the present invention has preferable dehydrogenating propane stability.
Table 1
Table 2
| Catalyst number | Conversion of propane, quality % | Propylene Selectivity, quality % |
| A | 7.52 | 84.08 |
| B | 12.74 | 89.08 |
| C | 5.74 | 77.30 |
| D | 4.76 | 72.60 |
| E | 4.95 | 72.34 |
| F | 5.68 | 78.13 |
| G | 7.87 | 85.33 |
| H | 7.08 | 83.52 |
| I | 7.96 | 82.89 |
| M | 4.55 | 72.02 |
| N | 4.25 | 62.90 |
Table 3
Table 4
Claims (11)
1. a kind of propane dehydrogenation catalyst, the Pt of 0.2~5.0 mass % including load, 0.5~3.0 mass % P and 92~
The multi-walled carbon nanotube carrier of 99.3 mass %, the preparation method of the catalyst include the following steps:
(1) with dense H2SO4With dense HNO3Impregnation mixture multi-walled carbon nanotube carry out oxidation processes,
(2) it by the multi-walled carbon nanotube after (1) step oxidation processes, is impregnated with phosphorus-containing compound solution, again with platiniferous after drying
Polymer solution dipping roasts in 400~800 DEG C in inert gas after dry, then uses hydrogen reducing.
2. catalyst described in accordance with the claim 1, it is characterised in that the aperture of the catalyst is 30.0~40.0nm, compares table
Area is 200~250m2/ g, total pore volume are 0.1~2.0cm3/g。
3. catalyst described in accordance with the claim 1, it is characterised in that (1) dense H described in step2SO4Concentration is 95~98 matter
Measure %, dense HNO3Concentration is 65~68 mass %, the dense H2SO4With dense HNO3Volume be 1~5:1.
4. catalyst described in accordance with the claim 1, it is characterised in that (1) dense H described in step2SO4With dense HNO3Mixture and more
The liquid/solid ratio of wall carbon nano tube is 40~60mL/g, and the time for carrying out oxidation processes is 2~12 hours.
5. catalyst described in accordance with the claim 1, it is characterised in that (1) Bu Yongnong H2SO4With dense HNO3Impregnation mixture it is more
The temperature that wall carbon nano tube carries out oxidation processes is 20~70 DEG C.
6. catalyst described in accordance with the claim 1, it is characterised in that (2) inert gas described in step is nitrogen.
7. catalyst described in accordance with the claim 1, it is characterised in that (2) maturing temperature described in step is 500~700 DEG C.
8. catalyst described in accordance with the claim 1, it is characterised in that (2) compound containing platinum described in step is platinum nitrate, chlorine platinum
Acid, potassium chloroplatinate, tetraammineplatinum chloride or acetylacetone,2,4-pentanedione platinum.
9. catalyst described in accordance with the claim 1, it is characterised in that (2) phosphorus-containing compound described in step be diammonium hydrogen phosphate,
Ammonium dihydrogen phosphate or phosphoric acid.
10. catalyst described in accordance with the claim 1, it is characterised in that (2) it is to incite somebody to action that dipping described in step, which introduces phosphorus and the method for platinum,
Multi-walled carbon nanotube after oxidation processes is put into maceration extract, first uses ultrasonication, then stand dipping.
11. catalyst described in accordance with the claim 1, it is characterised in that (2) temperature of step reduction is 500~800 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510696918.9A CN106607065B (en) | 2015-10-23 | 2015-10-23 | A kind of propane dehydrogenation catalyst and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510696918.9A CN106607065B (en) | 2015-10-23 | 2015-10-23 | A kind of propane dehydrogenation catalyst and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106607065A CN106607065A (en) | 2017-05-03 |
| CN106607065B true CN106607065B (en) | 2019-11-15 |
Family
ID=58613813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510696918.9A Active CN106607065B (en) | 2015-10-23 | 2015-10-23 | A kind of propane dehydrogenation catalyst and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106607065B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109304189B (en) * | 2017-07-28 | 2022-01-04 | 中国石油化工股份有限公司 | Heteroatom-containing nano carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation reaction method |
| CN114436999B (en) * | 2020-10-30 | 2023-10-13 | 中国石油化工股份有限公司 | Method for preparing epoxypropane |
| CN112871189B (en) * | 2021-03-11 | 2022-06-28 | 福州大学 | Preparation method of non-metal modified platinum catalyst with nano diamond as carrier |
-
2015
- 2015-10-23 CN CN201510696918.9A patent/CN106607065B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Effect of surface oxygen containing groups on the catalytic activity of multi-walled carbon nanotube supported Pt catalyst;Xiaoming Wang et.al.;《Applied catalysis B: Environmental》;20101231;第101卷;第22页第2.1节、第23页第2.3节、摘要、第28页左栏第2段，表1 * |
| Pt supported on phosphorus-doped carbon nanotube as an anode catalyst for direct methanol fuel cells;Ziwu Liu,et.al.;《Electrochemistry Communications》;20111208;第16卷;摘要，第75页第3节，第76页第2段 * |
| 碳纳米管催化丙烷氧化脱氢反应活性中心的研究;黄瑞 等;《第十四届全国青年催化学术会议会议论文集》;20140930;正文第1-4段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106607065A (en) | 2017-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106607019B (en) | Propane dehydrogenation catalyst and preparation method | |
| EP3247494B1 (en) | Method for preparing highly nitrogen-doped mesoporous carbon composites | |
| Shah et al. | Smart designing of metal-support interface for imperishable dry reforming catalyst | |
| CN104870363B (en) | There is CNT and the manufacture method thereof of high-specific surface area | |
| Zhang et al. | Palladium cluster filled in inner of carbon nanotubes and their catalytic properties in liquid phase benzene hydrogenation | |
| CN105817247B (en) | Heteroatom-containing nano carbon material, preparation method and application thereof, and hydrocarbon dehydrogenation reaction method | |
| Pan et al. | The effects of confinement inside carbon nanotubes on catalysis | |
| Choi et al. | Highly active N-doped-CNTs grafted on Fe/C prepared by pyrolysis of dicyandiamide on Fe2O3/C for electrochemical oxygen reduction reaction | |
| CN106607018B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method and application | |
| Nieto-Márquez et al. | Carbon nanospheres: synthesis, physicochemical properties and applications | |
| CN101351404B (en) | Process for producing carbon nanotube and catalyst for carbon nanotube production | |
| JP6449251B2 (en) | Catalytic degradation of lower hydrocarbons to produce carbon oxide free hydrogen and bamboo structure carbon nanotubes | |
| US9379389B2 (en) | Method for producing porous carbon materials having mesopores and catalyst support for a fuel cell produced using same | |
| EP3047905A1 (en) | Method for preparing highly nitrogen-doped mesoporous carbon composites | |
| CN106607065B (en) | A kind of propane dehydrogenation catalyst and preparation method | |
| Khavarian et al. | The effects of process parameters on carbon dioxide reforming of methane over Co–Mo–MgO/MWCNTs nanocomposite catalysts | |
| CN101371988A (en) | Method for preparing transitional metal carbides catalytic material and use | |
| Wang et al. | Synthesis of three-dimensional nitrogen doped meso/macroporous carbon beads for heterogeneous catalytic solvent-free oxidation of ethylbenzene | |
| CN107159287B (en) | Pt/α-MoC1-xApplication of supported catalyst in catalytic hydrogenation reaction | |
| Wang et al. | Single-step pyrolytic preparation of Mo 2 C/graphitic carbon nanocomposite as catalyst carrier for the direct liquid-feed fuel cells | |
| CN104797338A (en) | Catalyst comprising iron and carbon nanotubes | |
| CN110624582A (en) | Catalyst for depositing metal particles in carbon nano tube and preparation and application thereof | |
| Huang et al. | Supported Ni2P catalysts derived from nickel phyllosilicate with enhanced hydrodesulfurization performance | |
| CN106607017B (en) | Catalyst for dehydrogenation of low-carbon paraffin and preparation and application | |
| CN1326613C (en) | Compound metal oxide catalyst for preparing carbon nanometer tube with high production rate and its preparing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |