CN111689467A - Method for preparing hydrogen by catalyzing methane cracking with activated carbon as catalyst - Google Patents
Method for preparing hydrogen by catalyzing methane cracking with activated carbon as catalyst Download PDFInfo
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- CN111689467A CN111689467A CN202010548015.7A CN202010548015A CN111689467A CN 111689467 A CN111689467 A CN 111689467A CN 202010548015 A CN202010548015 A CN 202010548015A CN 111689467 A CN111689467 A CN 111689467A
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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
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- 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
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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
- 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
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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
- 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
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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
- 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 invention discloses a method for preparing hydrogen by catalyzing methane cracking by using activated carbon as a catalyst, which adopts a gas-solid phase catalytic reaction fixed bed reactor, takes methane as a raw material, adds trace hydrogen sulfide, takes the activated carbon as the catalyst, and reacts at the temperature of 900-950 ℃ under normal pressure to obtain products of hydrogen and carbon, wherein the concentration of the hydrogen sulfide is 100ppm-300 ppm. According to the invention, trace hydrogen sulfide is added into the methane raw material gas, so that the activity of the activated carbon for catalyzing the methane cracking for hydrogen production is improved, the inactivation time of the activated carbon catalyst is prolonged, and the method has an important industrial application value for improving the conversion efficiency of the activated carbon for catalyzing the methane cracking for hydrogen production.
Description
Technical Field
The invention relates to the technical field of hydrogen production by methane cracking, in particular to a method for producing hydrogen by catalyzing methane cracking by using activated carbon as a catalyst.
Background
The direct cracking of methane to produce hydrogen is one clean hydrogen producing process, and methane is decomposed into hydrogen and carbon at high temperature without producing CO2The method is a transition process for connecting fossil fuel and renewable energy. The methane cracking reaction is an endothermic reaction to produce hydrogenThe energy to be consumed is 37.8kJ/mol, C-H in methane molecules is very stable, the cracking rate of non-catalytic methane cracking reaction is very low below 1000 ℃, and the reaction temperature can be greatly reduced and the hydrogen yield can be improved during catalytic cracking.
At present, the research of hydrogen production by methane cracking mainly focuses on the aspects of developing catalysts which are efficient and easy to obtain, low in price and strong in stability. The metal catalyst has high catalytic activity and good stability, but the metal catalyst can form carbon nanotubes (CNTs or CNFs) in the catalytic process, the carbon tubes push away metal particles with catalytic activity from the surface of a carrier, and the carbon deposition is usually removed by using steam in the regeneration process, so that the metal particles fall off, the catalyst structure is damaged, and the metal catalyst is difficult to regenerate. The carbon-based catalyst does not generate metal carbide in the process of catalyzing methane cracking, and carbon deposition generated on the surface can be removed by using high-temperature steam, so that the catalyst is regenerated; and the carbon material catalyst has low price, wide raw material source, high temperature resistance, sulfur resistance and other toxic impurities resistance. The activated carbon catalyst is one of the most common carbon-based catalysts, the initial catalytic activity of the activated carbon catalyst is high, but the activated carbon catalyst is quickly deactivated, and the catalytic efficiency is low after the activated carbon catalyst is deactivated, so that the popularization and the application of the activated carbon catalyst are influenced.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen by catalyzing methane cracking by using activated carbon as a catalyst, which can delay the inactivation process of the activated carbon catalyst and improve the catalytic efficiency.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for preparing hydrogen by catalyzing methane cracking by using activated carbon as a catalyst adopts a gas-solid phase catalytic reaction fixed bed reactor, uses methane as a raw material, adds a trace amount of hydrogen sulfide, uses the activated carbon as the catalyst, and reacts at the temperature of 900-.
Preferably, the space velocity of methane in the hydrogen production by catalytic cracking of methane is 20 ml/min-g.
Preferably, the concentration of hydrogen sulfide is 200 ppm.
Preferably, the activated carbon is coconut shell activated carbon, and the particle size is 8-16 meshes.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, ppm-level trace hydrogen sulfide gas is added into the feed gas, so that the activity of the activated carbon for catalyzing the methane cracking for hydrogen production is improved, the inactivation time of the activated carbon catalyst is prolonged, and the method has an important industrial application value for improving the conversion efficiency of the activated carbon for catalyzing the methane cracking for hydrogen production;
2. the method adopts the activated carbon as the catalyst, is cheap and easy to obtain, has low production cost and high economy, and the carbon deposit generated by the reaction does not need to be separated and can be directly used as the precursor of the carbon material to realize the recycling of the catalyst.
Drawings
FIG. 1 is a graph showing the conversion of catalytic methane cracking to produce hydrogen at 900 ℃ for examples 1-3 and comparative example 1;
FIG. 2 is a graph of the catalytic methane cracking hydrogen production conversion rate at 950 ℃ for examples 4-6 and comparative example 2;
FIG. 3a is a scanning electron micrograph of the morphology of the activated carbon catalyst surface prior to reaction in example 1;
FIG. 3b is a scanning electron micrograph of the morphology of the activated carbon catalyst surface after 10min of reaction in example 1;
FIG. 3c is a scanning electron micrograph of the morphology of the activated carbon catalyst surface after 10min of reaction in comparative example 1;
FIG. 3d is a scanning electron micrograph of the morphology of the activated carbon catalyst surface after 90min of reaction in example 1;
FIG. 3e is a scanning electron micrograph of the morphology of the activated carbon catalyst surface after 90min of reaction in comparative example 1.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
Taking a proper amount of 8-16 mesh coconut shell activated carbon catalyst in N2Calcining at 900 deg.C for 3h in the atmosphere to remove ash and volatile components in the activated carbon, activating, and adding N2Naturally cooling to room temperature in the atmosphere for later use.
Uniformly filling 2g of activated coconut shell activated carbon into a quartz tube with the inner diameter of 20mm, fixing two sides of the activated coconut shell activated carbon by quartz cotton, then placing the activated coconut shell activated carbon into a normal-pressure gas-solid phase catalytic fixed bed reactor, connecting the reactor and a gas analyzer, then performing leak detection, introducing nitrogen, wherein the space velocity is 20ml/min g, the heating rate is 30 ℃/min, closing the nitrogen when the temperature is raised to the cracking temperature of 900 +/-5 ℃ and the reaction temperature is reached, switching to methane gas to perform methane catalytic cracking hydrogen production, and simultaneously introducing hydrogen sulfide gas with the concentration of 200 ppm; the mass flow meter is adjusted to make the methane flow rate be 40ml/min constantly, namely the space velocity be 20ml/min g. And after reaction, the gas is discharged from the right end of the quartz tube, enters a gas analyzer for on-line gas component analysis, and starts to record data when the gas analyzer detects hydrogen. The change curve of the methane conversion rate of the hydrogen production by methane catalytic cracking along with the time is shown in figure 1.
The methane conversion efficiency (see the following formula) was calculated from the ratio of outlet hydrogen to methane as a basis for determining the catalyst activity.
CH4,％＝100*(([H2]out/2)/([CH4]out+[H2]out/2))
Example 2
The process was substantially the same as in example 1 except that the hydrogen sulfide gas was introduced at a concentration of 100 ppm. The change curve of the methane conversion rate of the hydrogen production by methane catalytic cracking along with the time is shown in figure 1.
Example 3
The process was substantially the same as in example 1 except that the hydrogen sulfide gas was introduced at a concentration of 300 ppm. The change curve of the methane conversion rate of the hydrogen production by methane catalytic cracking along with the time is shown in figure 1.
Example 4
Substantially the same procedure as in example 1 was conducted for catalytic cracking of methane, except that the reaction temperature was 950 ℃. The change curve of the methane conversion rate of the hydrogen production by methane catalytic cracking along with the time is shown in figure 2.
Example 5
The process was substantially the same as in the catalytic cracking of methane of example 2, except that the reaction temperature was 950 ℃. The change curve of the methane conversion rate of the hydrogen production by methane catalytic cracking along with the time is shown in figure 2.
Example 6
Substantially the same procedure as in example 3 was conducted for catalytic cracking of methane, except that the reaction temperature was 950 ℃. The change curve of the methane conversion rate of the hydrogen production by methane catalytic cracking along with the time is shown in figure 2.
Comparative example 1
The process was substantially the same as the catalytic cracking process of methane in example 1, except that hydrogen sulfide gas was not introduced. The change curve of the methane conversion rate of the hydrogen production by methane catalytic cracking along with the time is shown in figure 1.
Comparative example 2
Substantially the same as in comparative example 1 except that the reaction temperature was 950 ℃. The change curve of the methane conversion rate of the hydrogen production by methane catalytic cracking along with the time is shown in figure 2.
As can be seen from FIGS. 1 and 2, the initial stage of the reaction shows a high conversion rate of methane, and as the reaction proceeds, the carbon generated by the reaction adheres to the activated carbon and covers the active sites, so that the catalytic effect of the activated carbon is reduced, and particularly, the activated carbon is completely inactivated only 15min at 950 ℃. But with addition of H2After S, in H2And under the action of S, the inactivation speed of the activated carbon is slowed down. Adding trace amount of H2S can greatly improve the conversion efficiency of methane in the inactivation stage of the activated carbon, the maximum improvement efficiency can reach about 20 percent, and trace H2S can prolong the complete inactivation time of the activated carbon by about one time, and has obvious effect.
In examples 1 to 6, 200ppm H showed no significant difference in the effect of increasing the methane conversion when the hydrogen sulfide concentrations were 100ppm, 200ppm and 300ppm2The concentration of S is the preferred reaction condition.
Fig. 3 is a scanning electron microscope image of the surface morphology of activated carbon, and it can be seen that unreacted fresh activated carbon (a) has a smooth surface, has the characteristics of rich pore structure and large specific surface area, and can effectively adsorb methane molecules, and methane contacts with an active center through the pore structure of activated carbon to perform a cracking reaction.
After the reaction of pure methane for 10min (c), the surface of the activated carbon is quickly covered by the generated carbon deposition, and the activated carbon is quickly and completely deactivated by combining the conversion rate of methane. Pure methane and H2And (b) after the S mixed gas reacts for 10min, the small pores on the surface of the activated carbon are clearly visible, the carbon deposition attached to the surface is far less than that of a pure methane working condition, but the surface of the activated carbon is not as smooth as that of fresh activated carbon, and powdery carbon deposition is attached to the surface. After the pure methane reacts for 90min (e), the hole shape of the activated carbon is covered by deposited carbon, the hole edge is difficult to distinguish and completely inactivated, but the pure methane and H2After the S mixed gas reacts for 90min (d), small holes of the activated carbon are still visible, but compared with the unreacted activated carbon, edges and corners of edges of the small holes are not clear any more, the holes are also much smaller than those of the fresh activated carbon, and the surface of the activated carbon can be obviously covered by powdery carbon deposition.
Research shows that the morphology of deposited carbon is influenced by various factors such as reaction temperature, catalyst type, catalyst size, airspeed, raw materials and the like, and various deposition forms such as amorphous carbon, carbon fiber, carbon nano tube and the like can be presented. In this experiment, H2The addition of S just changes the morphology of deposited carbon, thereby improving the activity of the catalyst and improving the conversion rate of methane. As is apparent from FIG. 3, the deposited carbon generated by the reaction of pure methane is in the form of spherical or blocky protrusions, and the pores of the activated carbon are blocked by the deposited carbon, so that the pore diameter of the activated carbon is rapidly reduced and the activated carbon is rapidly inactivated. But with addition of H2In the reaction of S, the deposited carbon on the surface of the activated carbon does not plug the pores in a protruding shape, but the powdered carbon gradually and uniformly covers the activated carbon to gradually reduce the pores of the activated carbon, and the deposited carbon form does not rapidly plug the pores of the activated carbon like the pure methane reaction, only covers the active sites, and finally completely inactivates the activated carbon. Therefore, the carbon deposition mode of the pure methane reaction ensures that the active sites of the activated carbon are covered more quickly and the inactivation is quicker, and H2The addition of S changes the deposition morphology of the carbon deposit, so that the inactivation speed of the activated carbon is slowed down, and the addition of H is the same2S may increase the methane conversion.
Claims (4)
1. A method for preparing hydrogen by catalyzing methane cracking by using activated carbon as a catalyst adopts a gas-solid phase catalytic reaction fixed bed reactor, and is characterized in that methane is used as a raw material, a trace amount of hydrogen sulfide is added, the activated carbon is used as the catalyst, and the reaction is carried out at the temperature of 900-950 ℃ and under normal pressure to obtain products of hydrogen and carbon, wherein the concentration of the hydrogen sulfide is 100ppm-300 ppm.
2. The method for preparing hydrogen by catalytic cracking of methane by using activated carbon as a catalyst according to claim 1, wherein the space velocity of methane in the hydrogen preparation by catalytic cracking of methane is 20 ml/min-g.
3. The method for preparing hydrogen by cracking methane by using activated carbon as a catalyst according to claim 1, wherein the concentration of the hydrogen sulfide is 200 ppm.
4. The method for preparing hydrogen by cracking methane by using activated carbon as a catalyst according to claim 1, wherein the activated carbon is coconut shell activated carbon with a particle size of 8-16 meshes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307225A (en) * | 2021-05-31 | 2021-08-27 | 中国矿业大学 | Method for preparing hydrogen by stably catalyzing methane cracking through carbon black enhanced activated carbon and application |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113307225A (en) * | 2021-05-31 | 2021-08-27 | 中国矿业大学 | Method for preparing hydrogen by stably catalyzing methane cracking through carbon black enhanced activated carbon and application |
| 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 |
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