CN106865498B - A method of using Carbon Materials as catalyst preparation hydrogen and fibrous carbon - Google Patents
A method of using Carbon Materials as catalyst preparation hydrogen and fibrous carbon Download PDFInfo
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- CN106865498B CN106865498B CN201710150860.7A CN201710150860A CN106865498B CN 106865498 B CN106865498 B CN 106865498B CN 201710150860 A CN201710150860 A CN 201710150860A CN 106865498 B CN106865498 B CN 106865498B
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- carbon
- hydrogen
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- methane
- gaseous mixture
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1271—Alkanes or cycloalkanes
- D01F9/1272—Methane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
Abstract
The present invention relates to a kind of using Carbon Materials as the method for catalyst preparation hydrogen and fibrous carbon, belongs to catalyst technical field.A method of using Carbon Materials as catalyst preparation hydrogen and fibrous carbon, it is characterized by: the method using the gaseous mixture containing methane and hydrogen as raw material, using Carbon Materials as catalyst, is reacted under 600~1200 DEG C, normal pressure, wherein, hydrogen accounts for the 1%~90% of gaseous mixture total flow.This method effectively improves the stability of Carbon Materials catalytic methane cracking hydrogen production, and obtains fibrous carbon distribution, has important application value to charcoal catalytic methane cracking hydrogen production industrial application and the economic benefit etc. for promoting Carbon Materials and methane cracking generation carbon distribution.
Description
Technical field
The present invention relates to a kind of using Carbon Materials as the method for catalyst preparation hydrogen and fibrous carbon, belongs to catalyst technology neck
Domain.
Background technique
With the development and application of fuel cell, preparation is free of CO2Or the high-purity hydrogen of CO becomes a big demand.Catalysis
Methane cracking produces the advantages that high hydrogen is easily isolated due to its process is simple, product only has hydrogen and two kinds of solid carbon, has
Wide prospect.
Compared with metallic catalyst, although required reaction temperature is higher for carbon material catalyst, but the wide, valence with raw material sources
The many advantages such as objectionable impurities and high temperature resistant such as cheap, sulfur resistive of lattice, thus by extensive in methane catalytic decomposition hydrogen production process
Concern.Carbon material catalyst initial activity with higher, but stability is relatively poor, and the carbon being cracked to form is usually nothing
Sizing carbon, restricts its application to a certain extent.
Summary of the invention
Based on above-mentioned theory and understanding, the present invention provides one kind both to have improved the steady of charcoal catalytic methane cracking hydrogen production catalyst
Qualitative, rich production fibrous carbon again new method.
A method of using Carbon Materials as catalyst preparation hydrogen and fibrous carbon, the method is with containing methane and hydrogen
Gaseous mixture is raw material, using Carbon Materials as catalyst, is reacted under 600~1200 DEG C, normal pressure,
Wherein, hydrogen accounts for the 1%~90% of gaseous mixture total flow.
Above-mentioned technical proposal be using the gaseous mixture containing methane and hydrogen as raw material, using Carbon Materials as catalyst, in 600~
It is reacted under 1200 DEG C of normal pressures, obtaining product is hydrogen and fibrous carbon.
In above-mentioned technical proposal, the gaseous mixture is the gaseous mixture containing hydrogen and methane, can be for only by hydrogen and first
The gaseous mixture of alkane composition, and the preferably gaseous mixture is the gaseous mixture being made of hydrogen and methane.The gaseous mixture can also serve as reasons
The gaseous mixture of hydrogen, methane and nitrogen composition, wherein nitrogen is as internal standard compound, for calculating conversion ratio.
In above-mentioned technical proposal, the preferably described hydrogen accounts for the 5%~50% of gaseous mixture total flow;Further, it is preferable to be
10%~40%;Further, most preferably 20%~30%.
In above-mentioned technical proposal, the air speed of the preferably described gaseous mixture is 1~100L/ (hgcat);Further preferably 10
~40L/ (hgcat)。
In above-mentioned technical proposal, the reaction temperature of the preferably described reaction is 800~1000 DEG C.
In above-mentioned technical proposal, the carbon source of the preferably described carbon material catalyst be coal, direct liquefaction residue, semicoke, coconut husk,
One of pitch, shell, petroleum coke, lignin are several.
Further, it is preferable to which the carbon material catalyst is made as follows: by carbon source take activator quality 1/5~
1/1 with activator mechanical mixture, then after 750 DEG C~950 DEG C activation 0.5h~4h, successively progress pickling, suction filtration, washing,
Activated-carbon catalyst is made after drying.
In above-mentioned technical proposal, the activator is preferably KOH.
It is of the present invention can be in the prior art by method the method for catalyst preparation hydrogen and fibrous carbon of Carbon Materials
Disclosed in be suitable for using solid as catalyst, gas be reaction raw materials any reactor in carry out, it is anti-to be preferable over fixed bed
It answers in device and carries out.
The invention has the benefit that on fixed bed reactors, by the control to hydrogen content in methane feed gas,
Methane catalytic decomposition hydrogen manufacturing is carried out on carbon material catalyst, improves the stability of catalyst, while generates methane cracking
Carbon is fibrous carbon distribution.This method effectively improves the stability of Carbon Materials catalytic methane cracking hydrogen production, and obtains fiber
Shape carbon distribution generates the economic benefit etc. of carbon distribution to charcoal catalytic methane cracking hydrogen production industrial application and promotion Carbon Materials and methane cracking
With important application value.
Detailed description of the invention
Fig. 1 a is the stereoscan photograph of activated-carbon catalyst SM-AC in embodiment 1;
Fig. 1 b is the stereoscan photograph for the carbon distribution that activated-carbon catalyst SM-AC is generated in embodiment 2;
Fig. 1 c is the stereoscan photograph for the carbon distribution that activated-carbon catalyst SM-AC is generated in embodiment 4;
Fig. 1 d is the stereoscan photograph for the carbon distribution that activated-carbon catalyst SM-AC is generated in comparative example 1;
Fig. 2 is the methane conversion under the conditions of embodiment 1,2,3,4 and comparative example 1.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method;The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
5g Shenmu Coal (SM) and 10g KOH mechanical mixture are taken, then after 850 DEG C of activation 2h, pickling is successively carried out, takes out
Activated-carbon catalyst is made after filter, washing, drying, is denoted as SM-AC, stereoscan photograph is shown in Fig. 1 a.
Take 0.2g SM-AC sample as the catalyst of reaction of the present invention, normal pressure, 850 DEG C, total air speed is 30L/
(h·gcat), under the conditions of total flow is 100mL/min (methane/hydrogen/nitrogen flow is 40/6/54mL/min), it is in internal diameter
It is reacted in the stainless steel tube fixed bed reactors of 8mm.Exit gas composition is analyzed by gas-chromatography on-line checking.It works off one's feeling vent one's spleen
Body is mainly made of methane, hydrogen and nitrogen.
The calculation formula of methane conversion is as follows:Wherein, FCH4,inAnd FCH4,outRespectively
Indicate methane inlet flow rate and methane outlet flow.
The result shows that methane conversion is reduced to by initial 5.7% after reacting 390min when hydrogen flowing quantity is 6mL/min
1.5%.
Embodiment 2
It takes 0.2g SM-AC sample as the catalyst of reaction of the present invention, is distinguished with embodiment 1 are as follows: keep total tolerance
Under the conditions of 100mL/min, hydrogen flowing quantity 10mL/min, nitrogen flow 50mL/min, methane flow 40mL/min.
After reacting 370min, methane conversion is being reduced to 2.7% (see Fig. 2) by initial 5.6%.Although methane initial conversion
Rate is slightly below embodiment 1, but after reacting for a long time, methane conversion reduces amplitude and is obviously reduced, illustrate when hydrogen methane with
When content in hydrogen mixed gas increases to 20% by 13%, the cracking reaction of methane is promoted, the stability of catalyst is improved.
Catalyst sample after reaction is denoted as SM-AC-10H2, stereoscan photograph is shown in Fig. 1 b.Find out from photo, is urged in active carbon
Obviously there is the carbon distribution of threadiness in agent surface.
Embodiment 3
It takes 0.2g SM-AC sample as the catalyst of reaction of the present invention, is distinguished with embodiment 1 are as follows: keep total tolerance
Under the conditions of 100mL/min, hydrogen flowing quantity 15mL/min, nitrogen flow 45mL/min, methane flow 40mL/min.
When hydrogen flowing quantity is 15mL/min, that is, when accounting for the 27% of methane and hydrogen mixed gas total flow, methane conversion
It is reduced to 2.4% by 4.5% after reacting 410min, sees Fig. 2.It can be seen from the figure that methane conversion is slightly below embodiment 2,
But catalyst shows preferable stability.
Embodiment 4
It takes 0.2g SM-AC sample as the catalyst of reaction of the present invention, is distinguished with embodiment 1 are as follows: keep total gas
Under the conditions of amount is 100mL/min, hydrogen flowing quantity 25mL/min, nitrogen flow 35mL/min, methane flow 40mL/min.
When hydrogen flowing quantity is 25mL/min, that is, when accounting for the 38% of methane and hydrogen mixed gas total flow, methane conversion
It is reduced to 1.8% (see Fig. 2) by 3.3% after reacting 410min, catalyst shows higher stability, but methane under this condition
Conversion ratio lower than embodiment 2 and embodiment 3, show that methane can be inhibited while improving stability when hydrogen content is higher
Cracking.Sample after reaction is denoted as SM-AC-25H2, corresponding stereoscan photograph such as Fig. 1 c.As can be seen that being urged in active carbon
Obviously there is the carbon distribution of threadiness in agent surface.
Comparative example 1
The catalyst for taking 0.2g SM-AC sample to crack as catalytic methane is distinguished are as follows: keep total tolerance to be with embodiment 1
Under the conditions of 100mL/min, hydrogen flowing quantity 0mL/min, nitrogen flow 60mL/min, methane flow 40mL/min.
The results show that methane conversion is reduced to 0.6% (Fig. 2) by 6.6% after reaction 340min.With embodiment 1,2,3,4
It compares, when not adding hydrogen, although methane initial conversion is higher, stability is obviously poor, and 340min rear catalyst is complete
Full inactivation, illustrates to add a certain amount of hydrogen in methane gas, can significantly improve the stability of catalyst.After reaction
Sample (is denoted as SM-AC-0H2) it is scanned electron microscope analysis (Fig. 1 d).Compared with embodiment 1,2,3,4, when not adding hydrogen, first
The carbon that alkane cracking hydrogen production generates is unformed carbon material;And a certain amount of hydrogen is added in methane gas, Pd/carbon catalyst table
What face primarily formed is fibrous carbon, shows that the introducing of hydrogen changes the generation type of methane cracking hydrogen production process carbon, is promoted fine
It ties up the formation of shape carbon and inhibits the generation of agraphitic carbon.
Claims (6)
1. a kind of using Carbon Materials as the method for catalyst preparation hydrogen and fibrous carbon, it is characterised in that: the method is to contain first
The gaseous mixture of alkane and hydrogen is that raw material reacts under 600~1200 DEG C, normal pressure using Carbon Materials as catalyst, and acquisition product is hydrogen
Gas and fibrous carbon,
Wherein, hydrogen accounts for the 10%~40% of gaseous mixture total flow.
2. according to the method described in claim 1, it is characterized by: the air speed of the gaseous mixture is 1~100L/ (hgcat)。
3. according to the method described in claim 2, it is characterized by: the air speed of the gaseous mixture is 10~40L/ (hgcat)。
4. according to the method described in claim 1, it is characterized by: the reaction temperature of the reaction is 800~1000 DEG C.
5. according to the method described in claim 1, it is characterized by: the gaseous mixture is made of hydrogen and methane.
6. according to the method described in claim 1, it is characterized by: the carbon source of the carbon material catalyst is coal, direct liquefaction
One of residue, semicoke, pitch, shell, petroleum coke, lignin are several.
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CN111689467B (en) * | 2020-06-16 | 2022-02-15 | 中国矿业大学 | Method for preparing hydrogen by catalyzing methane cracking with activated carbon as catalyst |
CN113307225B (en) * | 2021-05-31 | 2023-08-22 | 中国矿业大学 | Method for preparing hydrogen by stable catalytic methane pyrolysis by using carbon black enhanced active carbon and application |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1291165A (en) * | 1998-02-24 | 2001-04-11 | 尼亚加拉莫霍克能量公司 | Hydrogen production via the direct cracking of hydrocarbons |
CN1632198A (en) * | 2004-12-07 | 2005-06-29 | 中国科学院山西煤炭化学研究所 | Process for preparing knitting wool form vapor-grown carbon fibers |
CN102583242A (en) * | 2012-03-09 | 2012-07-18 | 大连理工大学 | Method for preparing hydrogen gas through catalytic cracking of methane |
CN106283272A (en) * | 2016-10-25 | 2017-01-04 | 西北大学 | A kind of method that lower carbon number hydrocarbons catalytic pyrolysis prepares carbon fiber and hydrogen |
-
2017
- 2017-03-14 CN CN201710150860.7A patent/CN106865498B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1291165A (en) * | 1998-02-24 | 2001-04-11 | 尼亚加拉莫霍克能量公司 | Hydrogen production via the direct cracking of hydrocarbons |
CN1632198A (en) * | 2004-12-07 | 2005-06-29 | 中国科学院山西煤炭化学研究所 | Process for preparing knitting wool form vapor-grown carbon fibers |
CN102583242A (en) * | 2012-03-09 | 2012-07-18 | 大连理工大学 | Method for preparing hydrogen gas through catalytic cracking of methane |
CN106283272A (en) * | 2016-10-25 | 2017-01-04 | 西北大学 | A kind of method that lower carbon number hydrocarbons catalytic pyrolysis prepares carbon fiber and hydrogen |
Non-Patent Citations (1)
Title |
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