CN118045592B - Application of high-activity nickel-based catalyst in hydrogen production by glycerin aqueous phase reforming - Google Patents

Application of high-activity nickel-based catalyst in hydrogen production by glycerin aqueous phase reforming Download PDF

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CN118045592B
CN118045592B CN202410357706.7A CN202410357706A CN118045592B CN 118045592 B CN118045592 B CN 118045592B CN 202410357706 A CN202410357706 A CN 202410357706A CN 118045592 B CN118045592 B CN 118045592B
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nickel
based catalyst
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CN118045592A (en
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刘天龙
李中宏
冯晓博
李琦
杨沛燕
赵小燕
曹景沛
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China University of Mining and Technology CUMT
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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
    • 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
    • B01J37/08—Heat treatment
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • B01J37/30—Ion-exchange
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • 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
    • 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
    • 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
    • C01B2203/1217—Alcohols
    • 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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses an application of a high-activity nickel-based catalyst in hydrogen production by glycerin water phase reforming, wherein the nickel-based catalyst is prepared by mixing S950 ion exchange resin, basic nickel carbonate and ammonia water solution, performing ion exchange, and then sequentially performing neutral washing, drying and carbonization; the aqueous glycerol solution was passed into a fixed bed reactor containing a nickel-based catalyst for reforming reaction, and the results showed that: the method provided by the invention has the advantages that the organic carbon conversion rate on Ni/S950 is up to more than 99%, meanwhile, the volume percentage of H 2 is kept to be more than 50%, and the activity can be kept to be more than 50 hours. The Ni/S950 catalyst provided by the invention has the advantages of low price, high dispersion, high activity and the like, and achieves higher hydrogen selectivity and organic carbon conversion rate under the condition of less metal loading.

Description

Application of high-activity nickel-based catalyst in hydrogen production by glycerin aqueous phase reforming
Technical Field
The invention relates to the technical field of catalysts, in particular to an application of a high-activity nickel-based catalyst in hydrogen production by glycerin water phase reforming.
Background
Hydrogen energy is an ideal energy source in the 21 st century. The main industrial process for hydrogen production is the high temperature reforming of hydrocarbons derived from fossil fuels. In addition, hydrogen can be produced from more sustainable sources, such as biomass, using catalytic processes under mild temperature and pressure conditions.
The method for preparing hydrogen by biomass and its derivatives mainly comprises steam reforming, supercritical water reforming, autothermal reforming, dry gas reforming, water phase reforming, etc. Reforming hydrogen production is a relatively sophisticated technology. In 2002, a new hydrogen production method is proposed by the Dumesic subject group in the United states, biomass, derivatives and water are used as main raw materials in the process, and H 2 is prepared through aqueous phase reforming reaction under the action of a proper reaction condition and a catalyst. The technology has the main advantages of mild reaction conditions, high yield, no pollution, low energy consumption and strong adaptability. Aqueous phase reforming can produce products with low CO content and high hydrogen yield in a single reactor under mild conditions.
To achieve higher reforming activity and hydrogen selectivity, it is critical to break the c—c bonds in the molecules of biomass and its derivatives, while at the same time being able to promote the water shift reaction while minimizing the break of the c—o bonds and methanation reactions. Therefore, the active species and the carrier of the selected catalyst are important, and various noble metal supported catalysts have been used in the aqueous phase reforming hydrogen production reaction, such as noble metal catalysts of Pt, pd, ru, ir and the like, which have high reforming activity, but the high price limits industrial application; the non-noble metal supported catalyst is also lack of an inexpensive metal catalyst with high activity, high selectivity and high stability, which is one of the technical bottlenecks for developing the green new process.
Disclosure of Invention
The invention aims to provide an application of a high-activity nickel-based catalyst in glycerin aqueous phase reforming hydrogen production, the nickel-based catalyst has high activity and good stability, and almost no carbon monoxide is contained in gas, so that the technical problem of poor stability of the non-noble metal catalyst in high-efficiency catalytic glycerin aqueous phase reforming hydrogen production is solved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: use of a high activity nickel-based catalyst in hydrogen production by aqueous phase reforming of glycerol, the nickel-based catalyst being prepared by the steps of: mixing a nickel-containing precursor compound in water, performing ultrasonic treatment, adjusting the pH of the solution to be alkaline by using ammonia water, performing ultrasonic treatment, adding S950 ion exchange resin into the solution, placing the solution into a constant temperature oscillating bed for overnight, washing the obtained solid particles to be neutral after ion exchange, drying, and carbonizing to obtain the nickel-based catalyst Ni/S950.
Preferably, the nickel-containing precursor compound is basic nickel carbonate.
Preferably, the nickel-based catalyst has a nickel loading of 8 to 14wt%.
Preferably, the aqueous ammonia adjusts the pH of the solution to >13.
Preferably, the conditions of the constant temperature oscillating bed are as follows: the ion exchange temperature is 30 ℃, the oscillation speed is 170rpm, and the oscillation time is more than 12 hours.
Preferably, the carbonization conditions are as follows: the carbonization temperature is 500 ℃, the heating program is 10 ℃/min, and the carbonization time is 1h.
Preferably, the specific step of the application is to introduce the glycerol aqueous solution into a fixed bed reactor filled with a nickel-based catalyst Ni/S950, and carry out reforming reaction at 300 ℃ and 90bar to obtain hydrogen.
Preferably, the concentration of the glycerol aqueous solution is 5000ppm.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention successfully realizes that the low-cost metallic nickel catalyst is utilized to obtain higher hydrogen selectivity and organic carbon conversion rate under the condition of less metal loading.
(2) The catalyst has excellent stability, so that the production cost of hydrogen production by glycerin aqueous phase reforming can be effectively reduced in practical application.
(3) The heterogeneous catalyst Ni/S950 selected by the invention is a solid catalyst which is granular and has magnetism, which is convenient for recycling the catalyst.
Drawings
FIG. 1 is an SEM spectrum of a catalyst prepared according to example 3 of the invention;
FIG. 2 shows XRD spectra of catalysts prepared in examples 1,2, 3 and 4 according to the present invention;
FIG. 3 is a graph showing the stability test of the catalyst prepared in example 3 of the present invention in a continuous reaction at 300℃and 90 bar.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
The invention will be further described in detail with reference to the drawings and examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, and that the particular amounts of materials, reaction times and temperatures, process parameters, etc. shown are but one example of a suitable range, and that some insubstantial modifications and adaptations of the invention to those skilled in the art are within the scope of the invention.
The invention provides a preparation method of a nickel-based catalyst, which comprises the following steps:
Mixing a nickel-containing precursor compound in water, performing ultrasonic treatment, adjusting the pH of the solution to be alkaline by using ammonia water, performing ultrasonic treatment, adding S950 ion exchange resin into the solution, placing the solution into a constant temperature oscillating bed for overnight, washing the obtained solid particles to be neutral after ion exchange, drying, and carbonizing to obtain the catalyst which is named Ni/S950.
In the present invention, the nickel-containing precursor compound is basic nickel carbonate.
In the invention, the mass ratio of the nickel-containing precursor to the water is 1:500.
In the invention, the ultrasonic time is 5 minutes.
In the present invention, the alkalinity adjustment is to adjust the pH of the solution to be more than 13 by ammonia water.
In the present invention, the theoretical nickel loading is 5 to 15wt%, more preferably 8.0 to 14.0wt%, still more preferably 12.0wt%.
In the invention, the conditions in the constant temperature oscillating bed overnight are as follows: the ion exchange temperature is 30 ℃, the oscillation speed is 170rpm, and the oscillation time is more than 12 hours.
The washing is not particularly limited in the present invention, and the washing may be performed to be neutral by a scheme well known to those skilled in the art. Specifically, in the examples of the present invention, deionized water was used for washing 6 to 8 times.
In the present invention, the drying temperature is preferably 100 to 120 ℃.
In the present invention, the carbonization conditions are as follows: the carbonization temperature is 500 ℃, the heating program is 10 ℃/min, and the carbonization time is 1h.
The invention also provides application of the nickel-based catalyst in the scheme in hydrogen production by glycerin aqueous phase reforming.
In the present invention, the application preferably includes:
And (3) introducing the glycerol aqueous solution into a fixed bed reactor filled with a nickel-based catalyst Ni/S950 for reforming reaction to obtain hydrogen.
In the present invention, the concentration of the aqueous glycerin solution is preferably 5000ppm.
In the invention, the granularity of the catalyst is preferably 16-32 meshes, and the feeding speed of the glycerol aqueous solution is preferably 0.5mL/min; the reaction temperature is preferably 300℃and the pressure is preferably 90bar.
The nickel-based catalyst and the use thereof in hydrogen production by aqueous reforming of glycerol are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
Preparation of nickel-based catalyst:
basic nickel carbonate and water are mixed according to the mass ratio of 1:500 to prepare a solution, wherein the nickel loading is 8.0wt% and the ultrasonic treatment is carried out for 5min.
Adding ammonia water into the basic nickel carbonate solution, adjusting the pH to 13-14, and performing ultrasonic treatment for 5min.
Adding S950 ion exchange resin into basic nickel carbonate solution, and oscillating under the conditions of constant temperature: the ion exchange temperature is 30 ℃, the oscillation speed is 170rpm, and the oscillation time is more than 12 hours.
Washing the obtained solid particles to be neutral, washing the solid particles with deionized water for 6 to 8 times, putting the washed solid particles into an oven, and drying the solid particles at 110 ℃ for 3 to 4 hours.
And (3) placing the catalyst into a tubular furnace for carbonization, wherein the carbonization temperature is 500 ℃, the heating program is 10 ℃/min, and the carbonization time is 1h, thus obtaining the catalyst.
Performance evaluation of nickel-based catalyst:
1.0g of Ni/S950 catalyst was charged into the constant temperature section of the fixed bed reactor. Deionized water was continuously pumped at a rate of 0.5mL/min and after the entire flow path was filled with liquid, the pressure was slowly adjusted to 90bar by a back pressure valve. After confirming that the system was well airtight, the temperature was raised from room temperature to 300℃at a heating rate of 10℃per minute, starting to pump the raw material (5000 ppm aqueous glycerol solution), then maintaining the temperature at the target temperature, collecting the liquid effluent and the gas product every 1-2 hours, and calculating the organic carbon conversion and the hydrogen selectivity. And cooling and releasing pressure after the reaction is finished, collecting catalysis, drying and weighing.
Example 2
The only differences from example 1 are: the nickel loading was 10.0wt%.
Example 3
The only differences from example 1 are: the nickel loading was 12.0wt%.
FIG. 1 is an SEM spectrum of the catalyst prepared in this example. From the graph, the S950 resin has a rough surface and a narrow pore size distribution, which is caused by shrinkage of the S950 resin after carbonization at high temperature, ni particles are uniformly dispersed, and no obvious agglomeration phenomenon is caused. Thus, well-dispersed Ni particles are beneficial for exposing more active sites on S950.
FIG. 2 shows XRD spectra of catalysts prepared in examples 1,2,3 and 4 according to the present invention. As shown in fig. 2, XRD characterization showed that diffraction peaks of metallic nickel appear at positions of 44.6 °, 52.1 ° and 76.5 ° in terms of the crystal planes (111), (200), (220) of Ni, respectively, the intensities of which are very low and hardly observable, indicating that the nickel metal is highly dispersed.
Example 4
The only differences from example 1 are: the nickel loading was 14.0wt%.
Comparative example 1
The only differences from example 3 are: the reaction temperature was 250℃and the reaction pressure was 45bar.
Comparative example 2
The only differences from example 3 are: the reaction temperature was 275℃and the reaction pressure was 68bar.
The catalytic performances of the obtained catalysts with different nickel loadings and different reaction conditions are shown in table 1, and it can be seen that: with increasing nickel loading, the activity of the catalyst increased, with an optimum at a loading of 12 wt%; as the reaction temperature increases, the activity of the catalyst increases, and the catalytic performance at 300 ℃ is the best.
TABLE 1
The catalytic performance of the obtained 12Ni/S950 is shown in FIG. 3 at 300℃and 90bar, and it can be seen that: as the reaction time increases, the activity of the catalyst is kept unchanged, the organic carbon conversion rate is kept at 100%, the volume percentage of hydrogen is kept at about 50%, and the hydrogen increases with time, and the data in the figure also show that the catalyst 12Ni/S950 used in the invention has high stability and is not easy to deactivate.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.

Claims (7)

1. The application of the high-activity nickel-based catalyst in the hydrogen production by glycerin water phase reforming is characterized in that the specific steps are that glycerin water solution is introduced into a fixed bed reactor filled with nickel-based catalyst Ni/S950, and reforming reaction is carried out at 300 ℃ and 90bar to obtain hydrogen; wherein the nickel-based catalyst Ni/S950 is prepared by the steps of: mixing a nickel-containing precursor compound in water, performing ultrasonic treatment, adjusting the pH of the solution to be alkaline by using ammonia water, performing ultrasonic treatment, adding S950 ion exchange resin into the solution, placing the solution into a constant temperature oscillating bed for overnight, washing the obtained solid particles to be neutral after ion exchange, drying, and carbonizing to obtain the nickel-based catalyst Ni/S950.
2. Use according to claim 1, wherein the nickel-containing precursor compound is basic nickel carbonate.
3. The use according to claim 1, wherein the nickel-based catalyst has a nickel loading of 8 to 14wt%.
4. The use according to claim 1, wherein the aqueous ammonia adjusts the pH of the solution to >13.
5. The use according to claim 1, wherein the conditions of the thermostatically oscillating bed are: the ion exchange temperature is 30 ℃, the oscillation speed is 170rpm, and the oscillation time is more than 12 hours.
6. The use according to claim 1, wherein the carbonization conditions are: the carbonization temperature is 500 ℃, the heating program is 10 ℃/min, and the carbonization time is 1h.
7. The use according to claim 1, wherein the aqueous glycerol solution has a concentration of 5000ppm.
CN202410357706.7A 2024-03-27 2024-03-27 Application of high-activity nickel-based catalyst in hydrogen production by glycerin aqueous phase reforming Active CN118045592B (en)

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GB926235A (en) * 1959-10-01 1963-05-15 Chemetron Corp Catalyst and the production thereof
EP4223730A3 (en) * 2010-12-30 2023-10-04 Virent, Inc. Organo-catalytic biomass deconstruction
CN110711584B (en) * 2019-10-08 2022-03-25 宁夏大学 Semicoke-loaded coke oil steam reforming catalyst and preparation method and application thereof
CN111111675A (en) * 2020-01-17 2020-05-08 昆明理工大学 Ni-CeO2Process for preparing catalyst
CN114570372B (en) * 2022-03-29 2023-06-09 中国石油大学(华东) Methane carbon dioxide dry reforming nickel-based catalyst and preparation method and application thereof

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CN114653373A (en) * 2022-05-10 2022-06-24 中国矿业大学 High-selectivity nickel resin carbon catalyst and preparation method and application thereof

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