CN110302770A - A kind of method of modifying of carbon nano-tube catalyst and its application - Google Patents
A kind of method of modifying of carbon nano-tube catalyst and its application Download PDFInfo
- Publication number
- CN110302770A CN110302770A CN201910449094.3A CN201910449094A CN110302770A CN 110302770 A CN110302770 A CN 110302770A CN 201910449094 A CN201910449094 A CN 201910449094A CN 110302770 A CN110302770 A CN 110302770A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- modifying
- tube catalyst
- oxygen
- plasma
- 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.)
- Pending
Links
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/18—Carbon
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Nanotechnology (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
This case discloses a kind of method of modifying of carbon nano-tube catalyst, includes the following steps: that 1) carbon nanotube is put into quartz boat, and quartz boat is placed in the high-field electrode and grounding electrode region of discharge of apparatus for processing plasma；2) it is filled with initiation gas in apparatus for processing plasma, and applies voltage between two electrodes, adjusts plasma device pressure, electric discharge handles 1~30min, obtains modified carbon nano-tube catalyst.Catalyst provided by the invention, increase the C=O functional group that surface has catalytic activity using the high energy active specy of plasma and the interaction of carbon nanotube, it is harsh to avoid traditional wet chemistry method of modifying process conditions, the problems such as period is long, pollutes environment, operating process are simple, controllable, the catalyst is in the reaction of dehydrogenating propane system, conversion of propane is preferable, and Propylene Selectivity is preferable, shows excellent catalytic activity.
Description
Technical field
The present invention relates to a kind of catalyst preparation technologies in Industrial Catalysis field, more particularly to a kind of carbon nanometer pipe catalytic
The method of modifying of agent and its application.
Background technique
Preparing propylene by dehydrogenating propane becomes one of the important channel for increasing propylene source.The activity of platinum-tin catalyst is high, selection
Property it is good, more harsh process conditions can be born, but noble metal platinum is expensive, leads to catalyst higher cost.Chromium system
Although catalyst price is relatively cheap, such catalyst easily causes carbon distribution inactivation, will regenerate one every 15-30 minutes
It is secondary, and the use of chromium can also cause environment seriously to pollute.C N101972640A discloses a kind of non-loaded order mesoporous
Carbon material is the catalyst of preparing propylene by dehydrogenating propane, shows high catalytic activity, Propylene Selectivity and reaction stability.But
It is that the carbon material surface group content after high temperature cabonization is lower, reduces catalyst performance, it is therefore desirable to change to carbon material
Sex modification increases surface oxygen functional group.The most commonly used is being handled by chemical reagent, defect is nitric acid treatment, it is time-consuming compared with
It grows and easily causes environmental pollution；Liquor potassic permanganate processing has metal ion residual, influences the performance of catalyst.
Summary of the invention
In view of the above shortcomings, the purpose of the present invention is to provide a kind of method of modifying of carbon nano-tube catalyst.
Technical solution of the present invention is summarized as follows:
A kind of method of modifying of carbon nano-tube catalyst, wherein include the following steps:
1) carbon nanotube is put into quartz boat, and by quartz boat be placed on the high-field electrode of apparatus for processing plasma with
In grounding electrode region of discharge；
2) be filled with initiation gas in apparatus for processing plasma, and apply voltage between two electrodes, adjust etc. from
Daughter device pressure discharges in 5~10kHz high voltage power supply, handles 1~30min, obtains modified carbon nano-tube catalysis
Agent.
Plasma is that the gases such as argon gas, nitrogen are applied with certain voltage to generate its ionization.It contain electronics, from
The high energy active specy such as son, free radical, these high energy active specy temperature are up to 104~105K, but the behaviour of cold plasma
Make temperature and but maintain room temperature, the active specy of plasma carries high energy, can using these high energy active species
To realize the physical and chemical process for needing high temperature to be just able to achieve under normal condition, such as the decomposition reaction of substance, plasma by
In can be operated at room temperature, therefore the reunion for being easy to the material occurred in pyroreaction, duct can be effectively avoided
The problems such as collapsing.Carbon nanotube has good mechanical property, and big specific surface area has as adsorbent and catalyst carrier
Very big superiority.The type and quantity of the functional group of carbon nano tube surface are directly related to the application performance of material.The present invention
Catalyst based on carbon nanotube, be modified processing to it using plasma, increase surface C=O oxygen-containing functional group,
For being catalyzed preparing propylene by dehydrogenating propane.The modification method for preparing avoids traditional wet chemistry method of modifying process conditions harshness,
Period is long, pollutes environment, and the problems such as metal residual, operating process is simple, controllable, safety and environmental protection.Preferably, the carbon is received
The method of modifying of mitron catalyst, wherein the initiation gas of the step 1) is oxygen, in argon gas/oxygen, nitrogen/oxygen
It is a kind of.
Preferably, the method for modifying of the carbon nano-tube catalyst, wherein step 2) the corona treatment pressure
Power is 0.1~0.5MPa, and gas flow rate is 20~100sccm.
Preferably, the method for modifying of the carbon nano-tube catalyst, wherein the voltage that the step 2) applies is
220V~1000V.
Preferably, the method for modifying of the carbon nano-tube catalyst, wherein the step 2) plasma discharge is adopted
With one of glow discharge, corona discharge, dielectric barrier discharge, radio frequency discharge, microwave-excitation.
Preferably, the method for modifying of the carbon nano-tube catalyst, wherein the mixed gas of the argon gas and oxygen
The volume ratio of middle argon gas and oxygen is 95:5.
Preferably, the method for modifying of the carbon nano-tube catalyst, wherein the mixed gas of the nitrogen and oxygen
The volume ratio of middle nitrogen and oxygen is 75:25.
A kind of application of modified carbon nano-tube catalyst, wherein for being catalyzed preparing propylene by dehydrogenating propane, catalytic dehydrogenation
Process conditions are as follows: 600~650 DEG C of temperature, 0.05~0.2MPa of reaction pressure, 2000~5000h of propane mass space velocity-1。
The beneficial effects of the present invention are:
(1) catalyst provided by the invention is compared with the traditional method method with the obvious advantage, of the invention and utilizes plasma
High energy active specy and carbon nanotube interaction increase surface oxygen functional group, prepare the catalysis of preparing propylene by dehydrogenating propane
The problems such as agent, avoids that traditional wet chemistry method of modifying process conditions are harsh, and the period is long, pollutes environment, operating process is simple,
Confined plasma prepares modified carbon nano-tube process without using any acid, alkali, organic solvent, toxic reagent, only uses argon
The cheap initiation gas of the free of contamination gas as plasma such as gas, nitrogen, oxygen, therefore preparation process is environmentally protective；Deng
The modified carbon nano-tube catalyst particle size that gas ions prepare is uniformly, good dispersion, catalyst activity are high, stability is good, fits
Close batch production.
(2) carbon nano-tube modification catalyst of the invention, for improving propane in propane direct dehydrogenation olefine reaction
Conversion ratio, Propylene Selectivity is preferable, shows excellent catalytic performance.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification
Text can be implemented accordingly.
Embodiment 1:
A kind of method of modifying of carbon nano-tube catalyst, includes the following steps:
1) carbon nanotube is put into quartz boat, the high-field electrode and grounding electrode for being placed on apparatus for processing plasma are put
In electric region；
2) it is filled in apparatus for processing plasma and causes gas oxygen, and apply voltage 220V between two electrodes,
Adjust plasma device pressure, plasma treatment pressure 0.1MPa, gas flow rate 20sccm, in 5kHz high voltage power supply
Glow discharge is carried out, 10min is handled, obtains modified carbon nano-tube catalyst.
The application of carbon nano-tube catalyst is used for Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane, the process conditions of catalytic dehydrogenation are as follows: temperature
600 DEG C, reaction pressure 0.05MPa of degree, propane mass space velocity 3000h-1, catalyst amount 0.2g.
Embodiment 2:
A kind of method of modifying of carbon nano-tube catalyst, includes the following steps:
1) carbon nanotube is put into quartz boat, the high-field electrode and grounding electrode for being placed on apparatus for processing plasma are put
In electric region；
2) it is filled with initiation argon gas/oxygen gas in apparatus for processing plasma, argon in the mixed gas of argon gas and oxygen
The volume ratio of gas and oxygen be 95:5, and between two electrodes apply 500V voltage, adjust plasma device pressure, wait from
Daughter processing pressure is 0.3MPa, gas flow rate 50sccm, carries out corona discharge in 8kHz high voltage power supply, handles 30min, i.e.,
Modified carbon nano-tube catalyst is made.
The application of carbon nano-tube catalyst is used for Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane, the process conditions of catalytic dehydrogenation are as follows: temperature
600 DEG C, reaction pressure 0.05MPa of degree, propane mass space velocity 3000h-1, catalyst amount 0.2g.
Embodiment 3:
A kind of method of modifying of carbon nano-tube catalyst, includes the following steps:
1) carbon nanotube is put into quartz boat, the high-field electrode and grounding electrode for being placed on apparatus for processing plasma are put
In electric region；
2) it is filled in apparatus for processing plasma and causes nitrogen/oxygen gas, nitrogen in the mixed gas of nitrogen and oxygen
The volume ratio of gas and oxygen is 75:25, and applies 1000V voltage between two electrodes, carries out radio frequency in 10kHz high voltage power supply
Electric discharge, plasma treatment pressure 0.2MPa, gas flow rate 60sccm handle 30min, obtain modified carbon nano-tube and urge
Agent.
The application of carbon nano-tube catalyst is used for Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane, the process conditions of catalytic dehydrogenation are as follows: temperature
600 DEG C, reaction pressure 0.05MPa of degree, propane mass space velocity 3000h-1, catalyst amount 0.2g.
Embodiment 4:
A kind of method of modifying of carbon nano-tube catalyst, includes the following steps:
1) carbon nanotube is put into quartz boat, the high-field electrode and grounding electrode for being placed on apparatus for processing plasma are put
In electric region；
2) it is filled with nitrogen/oxygen in apparatus for processing plasma and causes gas, nitrogen in the mixed gas of nitrogen and oxygen
The volume ratio of gas and oxygen is 75:25, and applies 700V voltage between two electrodes, adjusts plasma device pressure,
8kHz high voltage power supply carries out microwave excited discharge, handles 20min, obtains modified carbon nano-tube catalyst.
The application of carbon nano-tube catalyst is used for Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane, the process conditions of catalytic dehydrogenation are as follows: temperature
600 DEG C, reaction pressure 0.05MPa of degree, propane mass space velocity 3000h-1, catalyst amount 0.2g.
Embodiment 5:
A kind of method of modifying of carbon nano-tube catalyst, includes the following steps:
1) carbon nanotube is put into quartz boat, the high-field electrode and grounding electrode for being placed on apparatus for processing plasma are put
In electric region；
2) it is filled with nitrogen/oxygen in apparatus for processing plasma and causes gas, nitrogen in the mixed gas of nitrogen and oxygen
The volume ratio of gas and oxygen is 75:25, and applies 800V voltage between two electrodes, adjusts plasma device pressure, etc.
Gas ions processing pressure is 0.4MPa, gas flow rate 70sccm, carries out dielectric barrier discharge, processing in 9kHz high voltage power supply
20min obtains modified carbon nano-tube catalyst.
The application of carbon nano-tube catalyst is used for Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane, the process conditions of catalytic dehydrogenation are as follows: temperature
600 DEG C, reaction pressure 0.05MPa of degree, propane mass space velocity 3000h-1, catalyst amount 0.2g.
Following table is the catalysis reaction result of Examples 1 to 5:
Table one
By the test data in table 1 it is found that embodiment 1~implementation 5, conversion of propane of the invention is preferable, propylene selection
Property it is preferable, catalyst propane direct dehydrogenation reaction in have excellent reactivity worth.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (8)
1. a kind of method of modifying of carbon nano-tube catalyst, which comprises the steps of:
1) carbon nanotube is put into quartz boat, and quartz boat is placed on to high-field electrode and the ground connection of apparatus for processing plasma
In electrode discharge region；
2) it is filled with initiation gas in apparatus for processing plasma, and applies voltage between two electrodes, adjusts plasma
Device pressure discharges in 5~10kHz high voltage power supply, handles 1~30min, obtains modified carbon nano-tube catalyst.
2. the method for modifying of carbon nano-tube catalyst according to claim 1, which is characterized in that the initiation of the step 1)
Gas is one of oxygen, argon gas/oxygen, nitrogen/oxygen.
3. the method for modifying of carbon nano-tube catalyst according to claim 1, which is characterized in that the step 2) plasma
Body processing pressure is 0.1~0.5MPa, and gas flow rate is 20~100sccm.
4. the method for modifying of carbon nano-tube catalyst according to claim 1, which is characterized in that the step 2) applied
Voltage is 220V~1000V.
5. the method for modifying of carbon nano-tube catalyst according to claim 1, which is characterized in that the step 2) plasma
Body electric discharge uses one of glow discharge, corona discharge, dielectric barrier discharge, radio frequency discharge, microwave-excitation.
6. the method for modifying of carbon nano-tube catalyst according to claim 2, which is characterized in that the argon gas and oxygen
The volume ratio of argon gas and oxygen is 95:5 in mixed gas.
7. the method for modifying of carbon nano-tube catalyst according to claim 2, which is characterized in that the nitrogen and oxygen
The volume ratio of nitrogen and oxygen is 75:25 in mixed gas.
8. a kind of application of the modified carbon nano-tube catalyst of any one of claim 1~7, which is characterized in that for being catalyzed third
Alkane dehydrogenation producing propylene, the process conditions of catalytic dehydrogenation are as follows: 600~650 DEG C of temperature, 0.05~0.2MPa of reaction pressure, propane
2000~5000h of mass space velocity-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910449094.3A CN110302770A (en) | 2019-05-28 | 2019-05-28 | A kind of method of modifying of carbon nano-tube catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910449094.3A CN110302770A (en) | 2019-05-28 | 2019-05-28 | A kind of method of modifying of carbon nano-tube catalyst and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110302770A true CN110302770A (en) | 2019-10-08 |
Family
ID=68075118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910449094.3A Pending CN110302770A (en) | 2019-05-28 | 2019-05-28 | A kind of method of modifying of carbon nano-tube catalyst and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110302770A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169757A (en) * | 2020-09-29 | 2021-01-05 | 上海交通大学 | Low-temperature plasma modified carbon nanotube and application thereof in water treatment |
| CN113828344A (en) * | 2021-11-02 | 2021-12-24 | 安徽工业技术创新研究院六安院 | Preparation method of nitrogen plasma modified platinum carbon |
| CN114806420A (en) * | 2022-05-19 | 2022-07-29 | 广州华德汽车弹簧有限公司 | Processing method of stabilizer bar bushing assembly |
| CN116328751A (en) * | 2023-03-28 | 2023-06-27 | 浙江大学 | Modified carbon catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428789A (en) * | 2008-12-04 | 2009-05-13 | 东华大学 | Method for processing barometric pressure, normal-temperature plasma modification on carbon nano-tube surface |
| CN106607019A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst and preparation method thereof |
-
2019
- 2019-05-28 CN CN201910449094.3A patent/CN110302770A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428789A (en) * | 2008-12-04 | 2009-05-13 | 东华大学 | Method for processing barometric pressure, normal-temperature plasma modification on carbon nano-tube surface |
| CN106607019A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZHONG-PAN HU ETAL.: "Direct dehydrogenation of propane to propylene on surface-oxidized multiwall carbon nanotubes", 《APPLIED CATALYSIS A, GENERAL》 * |
| 张宝艳: "《先进复合材料界面技术》", 31 July 2017 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169757A (en) * | 2020-09-29 | 2021-01-05 | 上海交通大学 | Low-temperature plasma modified carbon nanotube and application thereof in water treatment |
| CN113828344A (en) * | 2021-11-02 | 2021-12-24 | 安徽工业技术创新研究院六安院 | Preparation method of nitrogen plasma modified platinum carbon |
| CN114806420A (en) * | 2022-05-19 | 2022-07-29 | 广州华德汽车弹簧有限公司 | Processing method of stabilizer bar bushing assembly |
| CN116328751A (en) * | 2023-03-28 | 2023-06-27 | 浙江大学 | Modified carbon catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110302770A (en) | A kind of method of modifying of carbon nano-tube catalyst and its application | |
| CN104028293B (en) | A kind of preparation method of cryogenic nitrogen doped graphene load nano Pd particle hydrogenation catalyst | |
| Cai et al. | Decolorization of azo dye Orange G by aluminum powder enhanced by ultrasonic irradiation | |
| CN111547681B (en) | Method and device for preparing synthesis gas by dry reforming of methane under catalysis of plasma | |
| CN112624893B (en) | Catalytic coupling method of light alkane | |
| Berenblyum et al. | Supported palladium nanomaterials as catalysts for petroleum chemistry: 2. Kinetics and specific features of the mechanism of selective hydrogenation of phenylacetylene in the presence of carbon-supported palladium nanocatalyst | |
| Dinh et al. | Reducing energy cost of in situ nitrogen fixation in water using an arc-DBD combination | |
| CN104307523B (en) | A kind of method being prepared year Fischer-Tropsch synthesis by rice husk thermal decomposition charcoal one step | |
| Khoshtinat et al. | A review of methanol production from methane oxidation via non-thermal plasma reactor | |
| CN109420493A (en) | The method that carbon supported noble metal catalyst catalysis phenylacetylene hydrogenation prepares styrene | |
| CN107011120A (en) | A kind of method of recycling treatment carbon dioxide and water high selectivity ethanol | |
| CN201742637U (en) | Atmospheric pressure medium blocking-air cold plasma fluidizing device | |
| Weidong et al. | Study of selective hydrogenation of biodiesel in a DBD plasma reactor | |
| Lu et al. | Mechanism in chlorine‐enhanced Pd catalyst for H2O2 in situ synthesis in electro‐Fenton system | |
| CN113072426B (en) | Method and device for synthesizing methanol by using carbon dioxide and methane | |
| CN111484028B (en) | Porous zirconium boride material, preparation method thereof and application of porous zirconium boride material in preparation of vinyl chloride through hydrochlorination of acetylene | |
| CN110576177B (en) | Method for changing shape of nano-particles | |
| CN113648993A (en) | Method for preparing graphene oxide supported palladium by using liquid-phase atmospheric pressure cold plasma | |
| CN111203266A (en) | Regeneration method of non-metal catalyst | |
| CN203346306U (en) | Experimental system for producing methanol by converting coal-mine gas under synergistic effect of plasmas and catalyst | |
| CN209968113U (en) | Heterogeneous discharge system for removing VOCs with different solubilities through catalysis and synergy | |
| CN203564814U (en) | Liquid acrylamide refining device | |
| CN106215943A (en) | Ester through hydrogenation catalyst and its preparation method and application | |
| Wang et al. | Conversion of natural gas to C 2 hydrocarbons through dielectric-barrier discharge plasma catalysis | |
| CN108101024A (en) | A kind of method for mixing source of the gas and preparing carbon nanotubes |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191008 |
|
| RJ01 | Rejection of invention patent application after publication |