LU102649B1 - A method for producing hydrogen by catalytic reforming of biogas slurry - Google Patents
A method for producing hydrogen by catalytic reforming of biogas slurry Download PDFInfo
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- LU102649B1 LU102649B1 LU102649A LU102649A LU102649B1 LU 102649 B1 LU102649 B1 LU 102649B1 LU 102649 A LU102649 A LU 102649A LU 102649 A LU102649 A LU 102649A LU 102649 B1 LU102649 B1 LU 102649B1
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- biogas slurry
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- biogas
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- hydrogen production
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- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents 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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel 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
- 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
- C01B2203/1082—Composition of support materials
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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
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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
- C01B2203/1258—Pre-treatment of the feed
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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
- C01B2203/1288—Evaporation of one or more of the different feed components
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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a method for producing hydrogen by catalytic reforming of biogas slurry. The biogas slurry in liquid phase is used as a raw material, which becomes gas phase after preheating, and then passes into a high temperature reactor equipped with a supported nickel-based catalyst at a certain flow rate. The tail gas of the reactor is condensed and collected to obtain a gas-phase product dominated by hydrogen. The application and method provided by the present invention provide a new solution for the treatment and utilization of biogas slurry, and realize the process of efficiently producing hydrogen from renewable biogas slurry raw materials. This enriches the form of gas products in the biogas production industrial chain and enhances the value of gas products in the biogas production industrial chain.
Description
oe LU102649 Description A method for producing hydrogen by catalytic reforming of biogas slurry
TECHNICAL FIELD The invention relates to the cross field of energy and environment, in particular to a method for producing hydrogen by catalytic reforming of biogas slurry.
BACKGROUND As a traditional agricultural country, China produces a large amount of agricultural waste every year, which needs to be treated and utilized effectively. Biogas production technology using agricultural waste fermentation is very popular in China, and related technology research is also more advanced. The products and by-products of biogas production include biogas in the gas phase, biogas liquid in the liquid phase and biogas residue in the solid phase. The main component of biogas is methane, which is the main product of the process, while the biogas liquid and digestate are the by-products of the process.
Biogas is the liquid phase by-product of the agricultural waste fermentation process, which contains a large amount of water, soluble small molecule organic matter and a large number of bacterial microorganisms produced after fermentation. At present, the main way to treat and utilize the biogas waste from agricultural waste fermentation process is to put it back into the agricultural production process as feed or fertilizer. On the one hand, there are two problems with this treatment and utilization method: on the one hand, there are a lot of bacterial microorganisms produced during the fermentation process, so using it as HU102649 agricultural fertilizer or feed has certain health risks; on the other hand, introducing a production chain of feed or agricultural fertilizer in a large-scale biogas production process will greatly increase the cost of the whole process management, transportation and sales.
In fact, the above problems can be solved if the soluble organic matter in these biogas streams can be produced and converted into gas with better combustion performance for utilization. However, the high moisture content of biogas, the conventional gasification technology and devices use solid raw materials as reactants, and if the biogas is dried and then gasified for utilization, its energy utilization efficiency and economic benefits will be greatly reduced.
Based on the above background, it is a promising method to generate hydrogen by reforming organic matter in methane with water (ChHmOr + (2n-k)H,O — nCO, + (2n+m/2-k)H>) under the action of high temperature and nickel-based catalysts using the high water content of methane. The hydrogen-based gas-phase product generated is a gas product with good combustion performance, and can also be purified by certain separation means and used as a chemical raw material.
SUMMARY The present invention provides a method for producing hydrogen by catalytic reforming of biogas slurry, which solves the problems of single way of biogas utilization and poor utilization benefits in existing biogas production technologies and processes.
The invention is realized by the following technical scheme:
. . . LU102649 (1) Preparation of catalyst. The hydrogen production catalyst is prepared by the following methods: a. Placing the catalyst carrier (à-Al>O3, y-Al>O;, ZSM-5, etc.) in a certain concentration of nickel nitrate solution by impregnation and stirring to obtain a suspension, in which the loading of Ni on the catalyst 1s ensured to be 10-20 wt%.
b. Placing the suspension as described in a. in an oven and drying it at 110°C to obtain a solid.
c. Placing the solid obtained in b. in a muffle furnace and roasting at 600-700°C for 3-5h to obtain a coral-like solid d. Reducing the coral-like solid obtained in c. under H2 atmosphere at 600-700°C to obtain a powdered solid e. The powdered solid obtained in d. is pressed, crushed and sieved to obtain 20-40 mesh particles, which is the desired loaded nickel-based catalyst.
(2) Biogas filtration. In order to ensure the safety of using the hydrogen production equipment, the residual digestate in the methane liquid is filtered out. The residue in the methane that is not completely fermented is filtered out by a 20~100 mesh sieve to obtain a light brown liquid, which is used as the raw material for catalytic hydrogen production, and the catalytic hydrogen production reaction is carried out on a heating reaction device including but not limited to the one shown in the attached Figure 1.
(3) Equipment preheating. In order to ensure that it is the gas phase reactant on the catalyst for the reaction, the preheater temperature is set to 300°C in order to vaporize the liquid phase reactant. The high temperature reactor temperature is set to 500-800°C to HU102649 allow for catalytic hydrogen production reaction. Preferably, the high temperature reactor temperature of 650°C is more conducive to achieve higher hydrogen selectivity while saving electrical and thermal energy. The preheater is brought up to the set temperature with the high temperature reactor prior to the introduction of the methane reactant in order to carry out the hydrogen production reaction.
(4) Hydrogen production reaction. The methane is first passed through the preheater and then into the high temperature reactor, so that the reforming reaction occurs under the action of catalyst and high temperature, and the tail gas with non-condensable gas phase products and gaseous reactants and intermediate products as the main components is obtained.
(5) Product collection. The gas-phase products are passed through a circulating water condenser and a gas-liquid separator, and the non-condensable gas obtained is the gas- phase products mainly consisting of hydrogen.
Generally speaking, the invention can achieve the following beneficial effects: (1) It provides a hydrogen production application of biogas slurry and its related chemical method, which provides a new solution for the treatment and utilization of biogas slurry.
(2) It provides a method for efficiently preparing hydrogen from renewable biogas slurry, which can achieve more than 80% hydrogen content in detectable components under the optimal implementation conditions.
. . . . . LU102649 (3) With the method of the invention to prepare hydrogen from biogas slurry, it can enrich the forms of gas products in the biogas production industry chain and enhance the value of products.
BRIEF DESCRIPTION OF THE FIGURES Fig. 1 is the equipment flow chart of a fixed bed reaction system which can realize the biogas slurry hydrogen production method of the invention.
DESCRIPTION OF THE INVENTION In order to make the technical scheme and characteristics of the present invention clearer, the present invention will be further explained with reference to the drawings and specific embodiments. The specific embodiments described here are only used to explain the present invention, but do not limit the scope of protection of the present invention.
Example 1 1 g of Ni/a-Al»O; catalyst was placed in the fixed-bed reactor shown in the attached Figure 1, and the reactor temperature was set to 550°C and the preheater temperature was set to 300°C. After the temperatures of both the fixed-bed reactor and the preheater reached the set values, the filtered methane was passed into the preheater at a flow rate of 0.2 mL/min to convert the liquid-phase reactants into the gas phase, and then the gas-phase reactants were passed into the fixed-bed through a N» carryover of 50 mL/min for the reaction. The gas phase products of the reaction were collected at 0.5h, 1h and 1.5h, and the composition of the product gas was detected by gas chromatography. The gas composition was measured by external standard method, and the concentrations of the above components in the product gas were analyzed by using the standard gas containing
. . LU102649 eight components of Hz, CO», CoH4, CzHe, CsHs, CsHe, CH4 and CO with known concentrations as external standards. The product gas components were obtained as shown in Table 1. Table 1 Reaction H, Mole CO, CH, CH C3Hs C3H6 N, Mole CH, CO Mole time/h ratio /% Mole Mole Mole Mole Mole ratio /% Mole ratio /% ratio /% | ratio /% | ratio /% | ratio/% | ratio /% ratio /% CE | ST [BOLO | 09 | IT LOC I | 00
EEE EEE | PP fees fe fe | 00 fee] Example 2 The same method and steps as in example 1 were adopted, but the fixed bed reactor temperature was set at 650 °C, and the product gas components were obtained as shown in Table 2. Table 2 Reaction H, Mole CO, CH, CH C3Hs C3H6 N, Mole CH, CO Mole time/h ratio /% Mole Mole Mole Mole Mole ratio /% Mole ratio /% ratio /% | ratio /% | ratio /% | ratio/% | ratio /% ratio /% (or [rw er fw [we wo wf | | Te [me | 08 | 09 | 00 | 00 | 00] | oF (Tw ww [ww [we Example 3
. LU102649 The same method and steps as in example 1 were adopted, but the fixed bed reactor temperature was set at 750 °C, and the product gas components were obtained as shown in Table 3. Table 3 Reaction H, Mole CO, CH, CH C3Hs C3H6 N, Mole CH, CO Mole time/h ratio /% Mole Mole Mole Mole Mole ratio /% Mole ratio /% ratio /% | ratio /% | ratio /% | ratio/% | ratio /% ratio /% oe ee fe ww |e | PS [M00 | 09 00 00 | 00 0) m 115 | ME me | 08 J fe ef]
Claims (8)
1. The invention relates to a method for producing hydrogen by catalytic reforming of biogas slurry, which is characterized in that the liquid-phase biogas slurry is used as a raw material, which is preheated and then changed into a gas phase, and then is introduced into a high-temperature reactor filled with a supported nickel-based catalyst at a certain flow rate; the tail gas of the reactor can be collected to obtain a gas-phase product mainly containing hydrogen after being condensed.
2. The method for hydrogen production by catalytic reforming of biogas slurry according to claim 1, which is characterized in that the biogas slurry used can be a liquid product obtained by anaerobic digestion of crop straws such as wheat and corn or animal feces such as cow dung and rabbit dung in the process of producing biogas by fermentation.
3. The method for hydrogen production by catalytic reforming of biogas slurry according to claim 1, which is characterized in that the temperature of the preheating step is 300°C, but it can be adjusted in the actual use process as long as the biogas slurry can be preheated from liquid phase to gas phase.
4. The method for producing hydrogen by catalytic reforming of biogas slurry according to claim 1 is characterized in that the supported nickel-based catalyst is prepared by the following method: (1) impregnating and stirring the catalyst carrier in a certain concentration of nickel nitrate solution to obtain a suspension; (2) place the suspension described in (1) in an oven and dry it at 110°C to obtain a solid;
. . . . . LL. LU102649 (3) placing the solid obtained in (2) in a muffle furnace and roasting it at 600-700°C for 3-5h to obtain a coral-like solid (4) reducing the coral-like solid obtained in (3) in H2 atmosphere at 600-700°C to obtain a powdered solid (5) the powdered solid obtained in (4) is pressed, crushed and sieved to obtain 20-40 mesh particles, which is the desired loaded nickel-based catalyst.
5. The method for hydrogen production by catalytic reforming of biogas slurry according to claim 1 is characterized in that the carrier of the supported catalyst includes but is not limited to a-Al>O3, y-Al»O3, ZSM-5, etc.
6. The method for hydrogen production by catalytic reforming of biogas slurry according to claim 1 is characterized in that the loading amount of Ni in the supported catalyst is 10-20wt%.
7. The method for hydrogen production by catalytic reforming of biogas slurry according to claim 1 is characterized in that the high-temperature reactor includes but is not limited to a fixed bed, a tubular furnace, and the like.
8. The method for hydrogen production by catalytic reforming of biogas slurry according to claim 1 is characterized in that, in the hydrogen production method, the temperature range of the high temperature reactor is controlled to be 500-800 °C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU102649A LU102649B1 (en) | 2021-03-11 | 2021-03-11 | A method for producing hydrogen by catalytic reforming of biogas slurry |
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| Application Number | Priority Date | Filing Date | Title |
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| LU102649A LU102649B1 (en) | 2021-03-11 | 2021-03-11 | A method for producing hydrogen by catalytic reforming of biogas slurry |
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| LU102649B1 true LU102649B1 (en) | 2021-09-13 |
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| LU102649A LU102649B1 (en) | 2021-03-11 | 2021-03-11 | A method for producing hydrogen by catalytic reforming of biogas slurry |
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| LU (1) | LU102649B1 (en) |
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2021
- 2021-03-11 LU LU102649A patent/LU102649B1/en active IP Right Grant
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Effective date: 20210913 |