CN112452329B - Synthesis method of reforming catalyst - Google Patents

Synthesis method of reforming catalyst Download PDF

Info

Publication number
CN112452329B
CN112452329B CN202011230361.7A CN202011230361A CN112452329B CN 112452329 B CN112452329 B CN 112452329B CN 202011230361 A CN202011230361 A CN 202011230361A CN 112452329 B CN112452329 B CN 112452329B
Authority
CN
China
Prior art keywords
calixarene
chloroform
solution
precursor
roasting
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.)
Active
Application number
CN202011230361.7A
Other languages
Chinese (zh)
Other versions
CN112452329A (en
Inventor
孙予罕
王慧
杜洋
马春辉
张磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Original Assignee
Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Cluster Rui Low Carbon Energy Technology Co ltd filed Critical Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Priority to CN202011230361.7A priority Critical patent/CN112452329B/en
Publication of CN112452329A publication Critical patent/CN112452329A/en
Application granted granted Critical
Publication of CN112452329B publication Critical patent/CN112452329B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • 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
    • C01B3/40—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 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
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • 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
    • C01B2203/1094—Promotors or activators
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a synthesis method of a reforming catalyst, which is characterized in that nickel nitrate, calixarene, chloroform and methanol are prepared into a solution, and the solution is vigorously stirred to fully dissolve the nickel nitrate; adding an alkaline substance into the obtained solution, and removing the solvent through rotary evaporation after reaction to obtain a precursor complex formed by calixarene and Ni; preparing a solution from the precursor complex, an auxiliary agent precursor, chloroform and methanol, performing equal-volume impregnation on the obtained solution and a carrier, and drying and roasting the obtained solid sample to obtain the catalyst. According to the invention, Ni and calixarene form a small-size precursor complex, other active metal elements are jointly impregnated on a carrier according to a certain proportion, and finally the catalyst is obtained after filtration, washing, drying and roasting.

Description

Synthesis method of reforming catalyst
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a method for synthesizing a reforming catalyst by controlling synthesis of calixarene and application thereof.
Background
Methane and carbon dioxide are two greenhouse gases, and large amounts of emissions have an adverse effect on the environment. Since the first report of reforming and converting methane and carbon dioxide into synthesis gas in 1888, people have developed a great deal of research on the reaction, and the methane and carbon dioxide reforming reaction reduces the emission of methane and carbon dioxide and has environmental protection significance; and meanwhile, the generated synthesis gas can be used for further industrial application, and has economic benefit.
Catalysts for catalytic reforming of methane and carbon dioxide can be classified into two types: noble metals and non-noble metals. Among them, the noble metals Rh, Ru and Ir have the best catalytic activity. Although the noble metal catalyst has good catalytic activity and carbon deposit resistance, the industrial application of the noble metal catalyst is poor in economic benefit due to limited resources and high price. On the contrary, although the catalytic activity and the carbon deposit resistance of the non-noble metal are not as good as those of noble metals, the non-noble metal is low in price and rich in resources, so that the main research content is still the non-noble metal catalyst. Wherein the catalytic activity sequence of the non-noble metal is Ni & gt Co & gt Cu & gt Fe. Therefore, nickel-based catalysts have become the focus of research in methane and carbon dioxide reforming reactions.
Currently, the preparation methods for preparing reforming catalysts for methane and carbon dioxide include impregnation, sol-gel, and coprecipitation. Among them, the impregnation method and the coprecipitation method are relatively simple and easy to operate, and are the catalyst preparation methods mainly adopted at present.
Chinese patent CN102389801B discloses a nickel-based catalyst for reforming methane with carbon dioxide to obtain synthesis gas and a preparation method thereof, the method comprises the steps of preparing a mixed solution of metal salts in the first step, and treating treated gamma-Al in the second step under the condition of vacuumizing 2 O 3 Placing the mixture into the mixed solution for impregnation, and finally roasting to obtain the catalyst. Although the method has good conversion rate, the preparation process has high requirement, and the method is not beneficial to popularization and application.
Chinese patent CN105413734B discloses a nickel-based catalyst for methane-carbon dioxide reforming to produce reducing gas and a preparation method thereof, wherein the first step is the preparation of a modified molecular sieve carrier, and the second step is the impregnation of an active component and an auxiliary agent, and then the catalyst is obtained by roasting. Although the method has good conversion rate, the preparation process is more complicated, and the carbon deposit amount is more, so that the method is not suitable for large-scale production.
Therefore, the preparation of the methane and carbon dioxide reforming catalyst with high dispersity, small particle size and good stability is the key content of the current research. The addition of the auxiliary agent in the catalyst can improve the catalytic performance of the catalyst. The effect on the auxiliaries is currently roughly considered to be the following: changing the acidity and alkalinity of the surface of the catalyst, improving the dispersion degree of the active metal, modulating the interaction force between the active component and the carrier and changing the electron density of the active component to influence the catalyst on CH 4 And CO 2 Dissociation of (3). The assistant for methane-carbon dioxide reforming catalyst is divided intoAlkali metal (Na) 2 O、K 2 O), alkaline earth metal oxides (MgO, CaO), and rare earth oxides (CeO) 2 、La 2 O 3 ) And the like. The calixarene serving as a macrocyclic ligand has a good threshold effect and strong coordination capacity with metal, and can effectively control the dispersion degree and particle size of the metal by coordination with the metal.
Disclosure of Invention
The technical problem solved by the invention is as follows: the catalyst in the prior art has the defects of large particle size, easy Ni agglomeration and growth in the reaction process to inactivate, easy carbon accumulation and inactivation and the like.
In order to solve the above technical problem, the present invention provides a method for synthesizing a reforming catalyst, comprising the steps of:
step 1): preparing nickel nitrate, calixarene, chloroform and methanol into a solution, and violently stirring to fully dissolve the nickel nitrate;
step 2): adding an alkaline substance into the solution obtained in the step 1), and removing the solvent through rotary evaporation after reaction to obtain a precursor complex formed by calixarene and Ni;
step 3): preparing the precursor complex obtained in the step 2) with an auxiliary agent precursor, chloroform and methanol into a solution, performing equal-volume impregnation on the obtained solution and a carrier, and drying and roasting the obtained solid sample to obtain the catalyst.
Preferably, the structure of the calixarene in step 1) is as follows:
Figure BDA0002764997820000031
wherein n is 1, 3 or 5; r 1 ～R n+2 is-H, C 1 -C 5 Alkyl radical, C 1 -C 5 Any one or more of alkoxy and nitro; all A are the same group and are-CH 2 or-S.
Preferably, the molar ratio of the calixarene to the nickel nitrate in the step 1) is 1: (1-15), preferably 1 (3-9); the volume ratio of chloroform to methanol is 1: (1-5); dissolving 0.01mol of calixarene in 5-20 mL of chloroform.
Preferably, in the step 2), the alkaline substance is any one of urea, ammonium bicarbonate, triethylamine and ammonia water, and the pH value of the solution is controlled to be 7-7.5.
Preferably, the reaction time in the step 2) is 4-24 h, and preferably 8-12 h; the rotary evaporation temperature is controlled to be 30-60 ℃;
preferably, the molar ratio of the precursor complex to the auxiliary agent precursor in the step 3) is 1 (5-20), and preferably 1 (8-15); the volume ratio of chloroform to methanol is 1: (1-10); dissolving every 0.01mol of precursor complex in 2-5 mL of chloroform; the precursor of the auxiliary agent is at least one of nitrates of Zn, La, Ce, Mg and Ca.
Preferably, the dipping temperature in the step 3) is 30-90 ℃, preferably 40-60 ℃, and the time is 12-48 hours, preferably 12-24 hours; the drying temperature is 70-120 ℃, preferably 80-100 ℃, and the drying time is 4-24 hours, preferably 6-12 hours; the roasting temperature is 400-700 ℃, preferably 500-650 ℃, and the roasting time is 2-12 hours, preferably 4-6 hours.
Preferably, the catalyst obtained in the step 3) comprises an active component Ni, an auxiliary agent and a carrier, wherein the mass content of Ni is 2-15%, the mass content of the auxiliary agent is 2-15%, and the balance is the carrier.
More preferably, the auxiliary agent is any one or more of Zn, La, Ce, Mg and Ca; the carrier is gamma-Al 2 O 3 And ZrO 2 Any one of them.
The catalyst preparation method provided by the invention can effectively control the size and dispersion degree of Ni, can avoid inactivation caused by rapid agglomeration and growth of Ni particles in the reaction process, and meanwhile, the small-sized Ni has higher specific surface area and better catalytic activity.
Compared with the prior art, the invention has the following advantages:
(1) by utilizing the threshold effect of calixarene and through coordination of a non-metal element and a Ni element, the removal of a calixarene framework in the roasting process is ensured, and meanwhile, the high dispersity, small size, large specific surface area and high catalytic activity of Ni particles can be effectively ensured, and meanwhile, Ni atoms are not easy to agglomerate in the reaction process to cause catalyst inactivation;
(2) the preparation process is simple, and the traditional impregnation method is adopted, so that the complexity of operation is reduced.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
The evaluation procedure for the reforming reaction using the catalyst prepared in the example was as follows:
mixing the oxidation precursor catalyst (0.1g, 80-100 mesh) with analytically pure quartz sand (0.9g, 80-100 mesh), and adding into H 2 /N 2 Atmosphere (50% each by volume, flow rate 120mL/min), 700 ℃ pre-reduction for 1 h. After reduction is complete, at 50% H 2 /N 2 Raising the reaction temperature to 850 ℃ in the atmosphere, and switching to CO after raising the temperature to 850 DEG C 2 /CH 4 The mixed gas (molar ratio 1:1, GHSV: 30000 mL/g.h) undergoes the reforming reaction. After the reaction was stable, the composition of the product was measured on-line by gas chromatography.
Example 1
The calixarene is selected from p-tert-butyl thiacalix [6 ]]Aromatic hydrocarbons (n ═ 3, R) 1 ～R 4 T-butyl, a ═ S);
calixarene (0.01mol, 7.44g) was weighed and dissolved in 15mL of chloroform, nickel nitrate hexahydrate (0.15mol, 43.62g) was weighed and dissolved in 45mL of a mixed solution of methanol, the chloroform solution of calixarene was added with vigorous stirring while adding 50. mu.L of ammonia water, the reaction was carried out for 18h, and all the solution was removed by rotary evaporation (50 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, lanthanum nitrate (0.1mol, 32.49g), was dissolved in a mixed solution of 5mL of chloroform and 40mL of methanol, and then mixed with γ -Al 2 O 3 (0.66mol, 67.32g), soaking at the temperature of 60 ℃ for 36h, taking out, drying at the temperature of 100 ℃ for 12h, taking out the dried solid, roasting at the roasting temperature of 600 ℃ for 4h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO 2 Conversion 81.27%, CH 4 Conversion rate 85.61%, H in output 2 The ratio of/CO is 0.84, the reaction lasts for 300h, CO 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 2
The calixarene is selected from p-tert-butyl thiacalix [4 ]]Aromatic hydrocarbons (n ═ 1, R) 1 ～R 4 T-butyl, a ═ S);
calixarene (0.01mol, 7.21g) was weighed and dissolved in 10mL of chloroform, nickel nitrate hexahydrate (0.1mol, 29.08g) was weighed and dissolved in 30mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 12h, and all the solution was removed by rotary evaporation (50 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.2mol, 51.28g) was dissolved in a mixed solution of 5mL of chloroform and 30mL of methanol and then mixed with gamma-Al 2 O 3 (0.3mol, 30.59g), soaking at 50 ℃ for 12h, taking out, drying at 100 ℃ for 12h, taking out the dried solid, roasting at 650 ℃, roasting for 4h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO 2 Conversion 82.77%, CH 4 Conversion of 87.25%, H in the product 2 The ratio of/CO is 0.85, the reaction lasts for 300h, CO 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 3
The calixarene is selected from p-tert-butyl thiacalix [4 ]]Aromatic hydrocarbons (n ═ 1, R) 1 ～R 4 T-butyl, a ═ S);
calixarene (0.01mol, 7.21g) was weighed and dissolved in 10mL of chloroform, nickel nitrate hexahydrate (0.05mol, 14.54g) was weighed and dissolved in 30mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 12h, and all the solution was removed by rotary evaporation (50 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.1mol, 25.64g) was dissolved in a mixed solution of 5mL of chloroform and 25mL of methanol and then mixed with gamma-Al 2 O 3 (0.012mol, 12.24g), soaking at 50 ℃ for 24h, taking out, drying at 90 ℃ for 12h, taking out the dried solid, roasting at 650 ℃ for 4h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO 2 Conversion 86.02%, CH 4 Conversion rate of 90.16%, H in output 2 The ratio of/CO is 0.9, the reaction lasts for 300h, CO 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 4
The calixarene is selected from p-nitrothiacalix [4 ]]Aromatic hydrocarbons (n ═ 1, R) 1 ～R 4 ＝-NO 2 ，A＝-S)；
Calixarene (0.01mol, 6.04g) was weighed and dissolved in 20mL of chloroform, nickel nitrate hexahydrate (0.15mol, 43.62g) was weighed and dissolved in 100mL of a mixed solution of methanol, the chloroform solution of calixarene was added with vigorous stirring while 100. mu.L of triethylamine was added, the reaction was carried out for 24h, and all the solution was removed by rotary evaporation (60 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.2mol, 51.28g) was dissolved in a mixed solution of 5mL of chloroform and 50mL of methanol and then mixed with gamma-Al 2 O 3 (0.4mol, 40.81g) soaking, keeping the temperature at 80 ℃ for 48h, taking out, drying at 120 ℃ for 12h, taking out the dried solid, roasting at 650 ℃, roasting for 12h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO 2 Conversion 74.41%, CH 4 Conversion 79.86%, H in the effluent 2 The ratio of/CO was 0.82, reaction time 300h, CO 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 5
The calixarene is selected from p-tert-butyl thiacalix [4 ]]Aromatic hydrocarbons (n ═ 1, R) 1 ～R 4 T-butyl, a ═ S);
calixarene (0.01mol, 7.21g) was weighed out and dissolved in 5mL of chloroform, nickel nitrate hexahydrate (0.01mol, 2.91g) was weighed out and dissolved in 5mL of a mixed solution of methanol, and the chloroform solution of calixarene was dissolved in 5mL of chloroformAdding while stirring vigorously, adding 100 mu L of triethylamine, reacting for 4h, and removing all the solution by rotary evaporation (40 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, lanthanum nitrate (0.05mol, 16.25g), was dissolved in a mixed solution of 2mL of chloroform and 2mL of methanol, and then mixed with ZrO 2 (0.15mol, 18.48g) soaking, keeping the temperature at 60 ℃ for 24h, taking out, drying at 80 ℃ for 12h, taking out the dried solid, roasting at 700 ℃, roasting for 6h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO 2 Conversion 75.44%, CH 4 Conversion of 81.94%, H in the output 2 The ratio of/CO is 0.82, the reaction lasts for 300h, CO 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 6
The calixarene is selected from p-tert-butyl calix [8 ]]Aromatic hydrocarbons (n ═ 5, R) 1 ～R 4 Is tert-butyl, A is-CH 2 )；
Calixarene (0.01mol, 12.98g) was weighed and dissolved in 5mL of chloroform, nickel nitrate hexahydrate (0.05mol, 14.54g) was weighed and dissolved in 10mL of a mixed solution of methanol, the chloroform solution of calixarene was added with vigorous stirring while adding 50. mu.L of ammonia water, the reaction was carried out for 10h, and all the solution was removed by rotary evaporation (60 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, cerium nitrate (0.1mol, 43.42g), was dissolved in a mixed solution of 3mL of chloroform and 15mL of methanol, and then mixed with ZrO 2 (0.6mol, 73.93g) is soaked, the temperature is kept at 70 ℃ for soaking for 12h, the obtained product is taken out and dried at 120 ℃ for 24h, the dried solid is taken out and roasted, the roasting temperature is 600 ℃, the roasting time is 4h, and the oxidation precursor state catalyst is obtained after the roasting is finished.
Calculating to obtain CO 2 Conversion 83.28%, CH 4 Conversion rate is 87.65%, and H in output 2 The ratio of/CO is 0.86, the reaction lasts for 300h, CO 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 7
The calixarene adopts p-isopropyl cup [8 ]]Aromatic hydrocarbons(n＝5，R 1 ～R 4 Is isopropyl, A is-CH 2 )；
Calixarene (0.01mol, 11.86g) was weighed and dissolved in 20mL of chloroform, nickel nitrate hexahydrate (0.12mol, 34.90g) was weighed and dissolved in 80mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 4h, and all the solution was removed by rotary evaporation (60 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.15mol, 38.46g) was dissolved in a mixed solution of 4mL of chloroform and 40mL of methanol and then mixed with gamma-Al 2 O 3 (0.45mol, 45.90g) soaking, keeping the temperature at 30 ℃ for 48h, taking out, drying at 100 ℃ for 8h, taking out the dried solid, roasting at 550 ℃, and roasting for 12h to obtain the oxidized precursor catalyst after roasting.
Calculating to obtain CO 2 Conversion 74.62%, CH 4 Conversion 76.51%, H in the output 2 The ratio of/CO is 0.81, the reaction lasts for 300h, CO 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Example 8
The calixarene is selected from p-tert-butyl calix [6 ]]Aromatic hydrocarbons (n ═ 3, R) 1 ～R 4 Is tert-butyl, A is-CH 2 )；
Calixarene (0.01mol, 9.73g) was weighed and dissolved in 10mL of chloroform, nickel nitrate hexahydrate (0.08mol, 23.26g) was weighed and dissolved in 30mL of a mixed solution of methanol, the chloroform solution of calixarene was added while stirring vigorously and 100. mu.L of triethylamine was added, the reaction was carried out for 24h, and all the solution was removed by rotary evaporation (30 ℃) to obtain a precursor complex solid formed by calixarene and Ni. This solid, magnesium nitrate hexahydrate (0.1mol, 25.64g) was dissolved in a mixed solution of 2mL of chloroform and 20mL of methanol and then mixed with ZrO 2 (0.35mol, 43.13g) soaking, keeping the temperature at 90 ℃ for 12h, taking out, drying at 70 ℃ for 4h, taking out the dried solid, roasting at 400 ℃, roasting for 2h, and obtaining the oxidized precursor catalyst after roasting.
Calculating to obtain CO 2 Conversion 79.52%, CH 4 Conversion of 82.46%, H in the effluent 2 The ratio of/CO is 0.85, the reaction lasts for 300h, CO 2 、CH 4 Conversion and H 2 the/CO ratio remains substantially unchanged.
Comparative example 1
Nickel nitrate hexahydrate (0.05mol, 14.54g) and magnesium nitrate hexahydrate (0.1mol, 25.64g) were weighed, dissolved in 30mL of aqueous solution, and mixed with gamma-Al 2 O 3 (0.012mol, 12.24g) is soaked, the temperature is kept at 50 ℃ for 24h, the mixture is taken out and dried at 90 ℃ for 12h, the dried solid is taken out and roasted, the roasting temperature is 650 ℃, the roasting time is 4h, and the oxidized precursor catalyst is obtained after the roasting is finished.
Calculating to obtain CO 2 Conversion 62.02%, CH 4 Conversion 64.16%, H in the output 2 The ratio of/CO is 0.72, the obvious inactivation phenomenon appears after the reaction is carried out for 300h, and the carbon deposition is serious in the thermogravimetric analysis of the catalyst.
Table 1 shows a comparison of the performance of the catalysts of examples 1 to 8 and comparative example 1. As can be seen from Table 1, in examples 1-8, the addition of the calixarene ligand during the synthesis of the precursor complex effectively reduced the particle size of the finally formed oxidized precursor catalyst, and the average particle size was 6.4nm, while the catalyst had a larger specific surface area, which was 151.24m 2 In g, CO with higher catalytic activity, catalysts of examples 1 to 8 2 The conversion rate is 74.41-86.02%, CH 4 The conversion rate is 76.51% -90.16%, and the catalyst can stably run for more than 300H, the activity of the catalyst is maintained stable, and H is 2 The ratio of/CO is 0.81 to 0.9. In contrast, in comparative example 1, no calixarene is added in the synthesis process, the particle size of the finally formed oxidation precursor catalyst is 2.2 times of the average particle size of examples 1-8, and the specific surface area is reduced to 71.6% of the average specific surface area of the oxidation precursor catalysts of examples 1-8, when the reforming catalytic reaction is carried out, the initial 24h catalytic activity is similar to that of the catalysts of examples 1-8, but after the continuous operation for 300h, the catalytic activity is greatly reduced, CO is greatly reduced, and 2 the conversion rate is reduced to 62.02 percent, and CH 4 The conversion rate is reduced to 64.16%, H 2 the/CO was reduced to 0.72. It can thus be seen that the control of synthetic precursor complexation by using calixarenesThe dispersion degree of metal Ni in the precursor complex can be effectively controlled, and the precursor oxidation state catalyst can be obtained by impregnation, drying and roasting, and the particle size of the catalyst can be effectively reduced, so that high CO can be obtained 2 And CH 4 The reforming catalyst with high conversion rate and high stability has simple and easy operation in the synthesis process and industrial application prospect.
The performance versus ratio for the catalysts of examples 1-8 and comparative example 1 run for 300h is shown in table 1.
TABLE 1
Figure BDA0002764997820000091

Claims (5)

1. A method of synthesizing a reforming catalyst, comprising the steps of:
step 1): preparing nickel nitrate, calixarene, chloroform and methanol into a solution, and violently stirring to fully dissolve the nickel nitrate; the molar ratio of calixarene to nickel nitrate is 1: (1-15); the volume ratio of chloroform to methanol is 1: (1-5); dissolving 0.01mol of calixarene in 5-20 mL of chloroform; the structure of the calixarene is as follows:
Figure 692883DEST_PATH_IMAGE001
；
wherein n is 1, 3 or 5; r 1 ~R n+2 is-H, C 1 -C 5 Alkyl radical, C 1 -C 5 Any one or more of alkoxy and nitro; all A are the same group and are-CH 2 or-S;
step 2): adding an alkaline substance into the solution obtained in the step 1), and removing the solvent through rotary evaporation after reaction to obtain a precursor complex formed by calixarene and Ni; the alkaline substance is any one of urea, ammonium bicarbonate, triethylamine and ammonia water, and the pH value of the solution is controlled to be 7-7.5;
step 3): mixing the precursor complex obtained in the step 2) with an auxiliary agent precursor, chloroform andpreparing methanol into solution, wherein the precursor of the auxiliary agent is at least one of nitrates of Zn, La, Ce, Mg and Ca, impregnating the obtained solution and a carrier in equal volume, and the carrier is gamma-Al 2 O 3 And ZrO 2 Drying and roasting the obtained solid sample to obtain the catalyst.
2. The method for synthesizing a reforming catalyst according to claim 1, wherein the reaction time in the step 2) is 4-24 h; the rotary evaporation temperature is controlled to be 30-60 ℃.
3. The synthesis method of the reforming catalyst according to claim 1, wherein the molar ratio of the precursor complex to the auxiliary precursor in the step 3) is 1 (5-20); the volume ratio of chloroform to methanol is 1: (1-10); dissolving 0.01mol of the precursor complex in 2-5 mL of chloroform.
4. The method for synthesizing the reforming catalyst according to claim 1, wherein the temperature for impregnation in the step 3) is 30 to 90 ℃ and the time is 12 to 48 hours; the drying temperature is 70-120 ℃, and the drying time is 4-24 hours; the roasting temperature is 400-700 ℃, and the roasting time is 2-12 h.
5. The method for synthesizing a reforming catalyst according to claim 1, wherein the catalyst obtained in step 3) comprises an active component Ni, an auxiliary agent and a carrier, wherein the mass content of Ni is 2-15%, the mass content of the auxiliary agent is 2-15%, and the balance is the carrier.
CN202011230361.7A 2020-11-06 2020-11-06 Synthesis method of reforming catalyst Active CN112452329B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011230361.7A CN112452329B (en) 2020-11-06 2020-11-06 Synthesis method of reforming catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011230361.7A CN112452329B (en) 2020-11-06 2020-11-06 Synthesis method of reforming catalyst

Publications (2)

Publication Number Publication Date
CN112452329A CN112452329A (en) 2021-03-09
CN112452329B true CN112452329B (en) 2022-09-20

Family

ID=74826417

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011230361.7A Active CN112452329B (en) 2020-11-06 2020-11-06 Synthesis method of reforming catalyst

Country Status (1)

Country Link
CN (1) CN112452329B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004011335A1 (en) * 2004-03-09 2005-09-22 Süd-Chemie AG Preparation of supported metal / metal oxide catalysts by precursor chemical nanometallurgy in defined reaction spaces of porous supports by means of organometallic and / or inorganic precursors and metal-containing reducing agents
CN1751789A (en) * 2005-09-02 2006-03-29 浙江大学 Prepn. method and application of high-dispersion loading type nickel-based catalyst
CN102659821B (en) * 2012-04-20 2016-02-17 陕西师范大学 To metal-salt title complex of nitro calixarene and preparation method thereof
CN106944082B (en) * 2016-01-07 2019-07-12 中国石油化工股份有限公司 A kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst
CN107376919B (en) * 2017-07-19 2020-03-10 太原理工大学 Promoting CO2Catalyst for activation and dissociation and preparation method and application thereof
CN108499568B (en) * 2018-05-02 2019-12-20 陕西师范大学 Nickel-based catalyst for reforming methane by pressurizing carbon dioxide
CN108620079B (en) * 2018-05-10 2020-02-21 陕西师范大学 Nickel-based composite catalyst for preparing synthesis gas by reforming methane with pressurized carbon dioxide
CN111574548B (en) * 2020-06-05 2021-05-28 中国科学院长春应用化学研究所 Preparation method of macrocyclic carrier multi-center metalloporphyrin complex and polycarbonate

Also Published As

Publication number Publication date
CN112452329A (en) 2021-03-09

Similar Documents

Publication Publication Date Title
CN112871198B (en) Catalyst for synthesizing formic acid by carbon dioxide hydrogenation, preparation method and application thereof
CN108479834B (en) Fischer-Tropsch synthesis catalyst and preparation method thereof
CN101992089A (en) Three-dimensional ordered porous-mesoporous iron-based perovskite oxide catalyst and preparation method thereof
CN113019383A (en) Nickel/lanthanum oxide catalyst and preparation method and application thereof
CN110787789A (en) Preparation and application of catalyst for preparing methanol by carbon dioxide hydrogenation
CN113663707A (en) Method for macro-preparation of multiple formaldehyde decomposition catalysts
CN104437501B (en) A kind of cobalt-base catalyst and the preparation method and application thereof
CN111992213A (en) Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN113058613B (en) Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof
CN106268856A (en) Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application
CN112452329B (en) Synthesis method of reforming catalyst
CN110329992B (en) Catalyst for preparing hydrogen by reforming methanol with low temperature water vapor and preparation method thereof
CN115646500B (en) Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof
CN113441140A (en) Hydrodeoxygenation catalyst and preparation method and application thereof
CN102441387B (en) Method for preparing high-activity cobalt-based Fischer-Tropsch synthetic catalyst
CN114471555A (en) Low-temperature high-efficiency bimetallic synergetic catalytic purification catalyst for VOCs and preparation method thereof
CN105727969B (en) A kind of preparation method of synthesis gas methanation catalyst
CN115739090B (en) Preparation method and application of transition metal oxide catalyst with high surface oxygen vacancy density
CN115212885B (en) Cobalt silicate derived cobalt-based catalyst for directly preparing low-carbon alcohol from synthesis gas, preparation method and pretreatment method
CN113441151B (en) Metal oxide modified MOx-CoMnOx nano-catalyst, preparation method and use method
CN103372451B (en) Preparation method of supported catalyst
CN116510732A (en) Alloy carbide catalyst, preparation method and application thereof
CN116726946A (en) Supported alloy catalyst based on interaction of metal and carrier, and preparation method and application thereof
CN117696073A (en) Limited domain type catalyst capable of being used for direct dehydrogenation and oxidative dehydrogenation of propane at same time, and preparation method and application thereof
CN114797816A (en) Preparation method of polyhydroxy nano aluminum oxide with transition metal replacing Al framework

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
GR01 Patent grant
GR01 Patent grant