CN114177912B - Perovskite sulfur-resistant shift catalyst and preparation method and application thereof - Google Patents

Perovskite sulfur-resistant shift catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114177912B
CN114177912B CN202010958239.5A CN202010958239A CN114177912B CN 114177912 B CN114177912 B CN 114177912B CN 202010958239 A CN202010958239 A CN 202010958239A CN 114177912 B CN114177912 B CN 114177912B
Authority
CN
China
Prior art keywords
catalyst
equal
sulfur
perovskite
less
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
CN202010958239.5A
Other languages
Chinese (zh)
Other versions
CN114177912A (en
Inventor
王民
余汉涛
赵庆鲁
白志敏
王昊
姜建波
薛红霞
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.)
China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
Original Assignee
China Petroleum and Chemical Corp
Qilu Petrochemical Co of Sinopec
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 China Petroleum and Chemical Corp, Qilu Petrochemical Co of Sinopec filed Critical China Petroleum and Chemical Corp
Priority to CN202010958239.5A priority Critical patent/CN114177912B/en
Publication of CN114177912A publication Critical patent/CN114177912A/en
Application granted granted Critical
Publication of CN114177912B publication Critical patent/CN114177912B/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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous 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
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • 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)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Disclosed is a perovskite sulfur shift-resistant catalyst having a composition represented by chemical formula 1 and having a perovskite structure: ABO (anaerobic-anoxic-oxic) 3 Formula 1; wherein A represents one or more of rare earth metal elements, alkali metal elements and/or alkaline earth metal elements; b represents molybdenum and/or cobalt. When the catalyst is used for sulfur-tolerant shift reaction, particularly under the severe working conditions of low water-vapor ratio, low sulfur content and the like, the catalyst has higher stability and catalyst life, and has higher catalytic activity.

Description

Perovskite sulfur-resistant shift catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of coal chemical industry; relates to a sulfur-tolerant shift catalyst for coal chemical industry and a preparation method and application thereof; more particularly, relates to a perovskite sulfur-tolerant shift catalyst and a preparation method and application thereof.
Background
Sulfur tolerant shift is an important approach for efficient utilization of coal and is also the current primary mode of hydrogen production, and catalysts are the core technology of sulfur tolerant shift processes.
Compared with other types of catalysts, the cobalt-molybdenum-based catalyst has the advantages of sulfur resistance, wide reaction temperature range, low cost, simple preparation process and the like, and is most widely applied to domestic and foreign devices. As a cobalt-molybdenum-based sulfur-tolerant shift catalyst, the catalyst should have high activity and high stability. However, the existing cobalt-molybdenum-based catalyst has the problems of obviously reduced catalyst activity and stability, obviously shortened service life and the like under the severe conditions of low sulfur, low water vapor ratio and the like.
In recent years, perovskite catalysts have attracted attention because of their excellent properties such as conductivity, magnetism, thermopaticity, piezoelectricity, etc., low production cost, thermodynamic and mechanical stability at high temperatures, and excellent oxygen ion and electron conductors at high temperatures. The perovskite type metal oxide catalyst has a general formula of ABO 3 . Typically, element a is a relatively low catalytic activity but stabilizing element, while element B is a transition metal element, which plays a major active role. The catalytic activity can be further enhanced by replacing the atoms of the moieties a and B. However, the specific surface area of the current prepared perovskite sulfur-tolerant shift catalyst is low, and the promotion of the catalytic activity of the catalyst is severely limited.
The inventors have not found a literature report of preparing a perovskite type cobalt-molybdenum sulfur-tolerant shift catalyst from a cobalt-molybdenum based catalyst by fully searching the prior art. The inventors have surprisingly found that when a perovskite type cobalt-molybdenum sulfur-tolerant shift catalyst is prepared by doping a cobalt-molybdenum based catalyst with a suitable element, the catalytic activity and stability of the conventional cobalt-molybdenum based catalyst are improved under severe conditions such as low sulfur, low water-vapor ratio and the like.
On the other hand, the perovskite type cobalt-molybdenum sulfur shift catalyst is further coated on a conventional high specific surface area carrier (for example, al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 Etc.), not only can the advantages of the perovskite type catalyst be exerted, but also the characteristic of high specific surface of the traditional carrier can be fully utilized, thereby further improving the activity and stability of the catalyst.
Disclosure of Invention
The invention aims at providing a perovskite sulfur-tolerant shift catalyst. The catalyst improves the activity and stability of the traditional cobalt-molybdenum-based catalyst under the severe conditions of low sulfur, low water vapor ratio and the like.
The second object of the present invention is to provide a method for producing the perovskite sulfur shift catalyst. The preparation method is simple in process, easy to operate and suitable for large-scale industrial application.
The invention further aims to provide a perovskite sulfur-tolerant shift catalyst with high specific surface area, which is coated on the surface of a traditional carrier. The perovskite sulfur-tolerant shift catalyst with high specific surface area has the advantages of high thermal stability, long service life, low cost, strong capability of adapting to severe working conditions and the like, and has higher specific surface area, so that the catalytic activity of the perovskite catalyst is effectively improved.
The fourth object of the present invention is to provide a method for producing the perovskite sulfur-tolerant shift catalyst having a high specific surface area. The preparation method is simple in process, easy to operate and suitable for large-scale industrial application.
The fifth object of the present invention is to provide the perovskite sulfur shift-resistant catalyst or the use of the perovskite sulfur shift-resistant catalyst with a high specific surface area. When the catalyst is used for sulfur-tolerant shift reaction, particularly under the severe working conditions of low water-vapor ratio, low sulfur content and the like, the catalyst has higher stability and catalyst life, and has higher catalytic activity.
To achieve the above object, in one aspect, the present invention provides a perovskite sulfur shift-resistant catalyst having a composition represented by chemical formula 1 and having a perovskite structure:
ABO 3 1 (1)
Wherein A represents one or more of rare earth metal elements, alkali metal elements and/or alkaline earth metal elements; b represents molybdenum and/or cobalt.
As the rare earth metal element, lanthanum (La), cerium (Ce), scandium (Sc), yttrium (Y), praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd), terbium (Tb), dysprosium (Dy), ytterbium (Yb), lutetium (Lu), and the like are included, but not limited thereto. Lanthanum (La), cerium (Ce), neodymium (Nd), gadolinium (Gd) are preferred from the standpoint of economic cost and/or catalytic activity.
Examples of the alkali metal element include, but are not limited to, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). Sodium (Na) and potassium (K) are preferred from the standpoint of economic cost and/or catalytic activity.
As the alkaline earth metal element, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra) are included, but not limited thereto. Magnesium (Mg), calcium (Ca), strontium (Sr) are preferred from the viewpoint of economic cost and/or catalytic activity.
The foregoing perovskite sulfur shift resistant catalyst according to the present invention, wherein the catalyst has a composition represented by chemical formula 2 and has a perovskite structure:
(A 1 ) x (A 2 ) 1-x BO 3 2, 2
Wherein A is 1 Represents a rare earth metal element; a is that 2 Represents one or more of alkali metal elements and/or alkaline earth metal elements; b represents one or two of molybdenum and/or cobalt; x is more than or equal to 0 and less than or equal to 1.
Preferably, at least one element of B is molybdenum.
Preferably, 0.01.ltoreq.x.ltoreq.0.99; further, the method comprises the steps of, x is more than or equal to 0.02 and less than or equal to 0.98,0.03 and less than or equal to 0.97,0.05 and less than or equal to 0.95,0.08 and less than or equal to 0.92,0.1 and less than or equal to 0.9,0.15 and less than or equal to 0.85,0.2 and less than or equal to 0.8,0.25 and less than or equal to 0.75,0.3 and less than or equal to 0.7,0.35 and less than or equal to 0.65,0.4 and less than or equal to 0.6,0.45 and less than or equal to 0.55.
The foregoing perovskite sulfur shift resistant catalyst according to the present invention, wherein the catalyst has a composition represented by chemical formula 3 and has a perovskite structure:
(A 1 ) x (A 2 ) 1-x (B 1 ) y (B 2 ) 1-y O 3 3
Wherein A is 1 Represents a rare earth metal element; a is that 2 Represents one or more of alkali metal elements and/or alkaline earth metal elements; b (B) 1 Represents molybdenum; b (B) 2 Represents cobalt; x is more than or equal to 0 and less than or equal to 1; y is more than or equal to 0.2 and less than or equal to 1.
Preferably, 0.01.ltoreq.x.ltoreq.0.99; further, x is more than or equal to 0.02 and less than or equal to 0.98,0.03, x is more than or equal to 0.97,0.05 and less than or equal to 0.95,0.08 and less than or equal to 0.92; further, the method comprises the steps of, x is more than or equal to 0.1 and less than or equal to 0.9,0.15 and less than or equal to 0.85,0.2 and less than or equal to 0.8,0.25 and less than or equal to 0.75,0.3 and less than or equal to 0.7,0.35, x is more than or equal to 0.65,0.4 and less than or equal to 0.6,0.45 and less than or equal to 0.55.
In one embodiment, 0.45.ltoreq.x.ltoreq.0.55. In a more specific embodiment, x=0.5.
Preferably, y is 0.25.ltoreq.y.ltoreq.1; further, y is more than or equal to 0.3 and less than or equal to 1,0.35 and y is more than or equal to 1; further, y is more than or equal to 0.4 and less than or equal to 1,0.45 and less than or equal to 1, y is more than or equal to 0.5 and less than or equal to 1,0.55 and less than or equal to 1,0.6 and less than or equal to 1,0.65 and less than or equal to 1, y is more than or equal to 0.7 and less than or equal to 1,0.75 and less than or equal to 1,0.8 and less than or equal to 1,0.85 and less than or equal to 1, and y is more than or equal to 0.9 and less than or equal to 1,0.95 and less than or equal to 1.
Or, y is more than or equal to 0.4 and less than or equal to 0.9,0.4 and less than or equal to 0.9,0.4 and less than or equal to 0.7,0.4 and less than or equal to 0.6,0.4 and less than or equal to 0.5, y is more than or equal to 0.5 and less than or equal to 0.9,0.5 and less than or equal to 0.8,0.5 and less than or equal to 0.7,0.5 and less than or equal to 0.6,0.6 and y is more than or equal to 0.9,0.6 and less than or equal to 0.8,0.6 and less than or equal to 0.7,0.7 and less than or equal to 0.9,0.7 and less than or equal to 0.8,0.8 and less than or equal to 0.9.
In one embodiment, 0.4.ltoreq.y.ltoreq.0.6. In a more specific embodiment, 0.45.ltoreq.y.ltoreq.0.55. In a more specific embodiment, y=0.45 or 0.55.
In another aspect, the present invention provides a method for preparing the perovskite sulfur tolerant shift catalyst, the method comprising:
(1) Obtaining an aqueous solution/dispersion comprising a hydroxycarboxylic acid, an a-element salt, and a B-element salt;
(2) The aqueous solution/dispersion is gelled at an elevated temperature to obtain a gel;
(3) And roasting the dried gel to obtain the perovskite sulfur-tolerant shift catalyst.
As the hydroxycarboxylic acid, citric acid, lactic acid, tartaric acid, hydroxybutyric acid, and the like are included, but not limited thereto. Citric acid is preferred from the standpoint of economic cost and/or catalytic activity.
As salts, including, but not limited to, nitrate, chloride, sulfate, acetate, and salts of oxyacids of the metal itself.
According to the preparation process of the present invention, the temperature is 40 to 200 ℃, preferably 50 to 190 ℃, more preferably 60 to 180 ℃, and most preferably 70 to 160 ℃.
In a specific embodiment, the temperature is 80 ℃.
According to the preparation method of the present invention, the calcination is performed at 200 to 1000 ℃, preferably 300 to 900 ℃, more preferably 400 to 800 ℃, and most preferably 500 to 700 ℃.
In a specific embodiment, the firing is performed at 600 ℃.
In yet another aspect, the present invention provides a high specific surface area perovskite sulfur shift resistant catalyst having a composition represented by chemical formula 4:
M/C type 4
Wherein M represents the perovskite sulfur tolerant shift catalyst according to the invention as previously described; c represents an inert carrier.
The perovskite sulfur shift catalyst preferably has a composition represented by chemical formula 1, more preferably has a composition represented by chemical formula 2, and most preferably has a composition represented by chemical formula 3.
As inert supports, include, but are not limited to, alumina (Al 2 O 3 ) Silicon dioxide (SiO) 2 ) Titanium dioxide (TiO) 2 ) Zirconium dioxide (ZrO) 2 ) Magnesium oxide (MgO), nickel oxide (NiO) and carbon-based supports. From the viewpoint of economic cost and/or catalytic activity, alumina (Al 2 O 3 ) Silicon dioxide (SiO) 2 ) Titanium dioxide (TiO) 2 ) Zirconium dioxide (ZrO) 2 )。
In still another aspect, the present invention provides a method for preparing the above perovskite sulfur shift catalyst with high specific surface area, which comprises:
(1) Obtaining an aqueous solution/dispersion comprising hydroxycarboxylic acid, an element a salt, and an element B salt, and C;
(2) The aqueous solution/dispersion is gelled at an elevated temperature to obtain a gel;
(3) And roasting the dried gel to obtain the perovskite sulfur-tolerant shift catalyst.
As the hydroxycarboxylic acid, citric acid, lactic acid, tartaric acid, hydroxybutyric acid, and the like are included, but not limited thereto. Citric acid is preferred from the standpoint of economic cost and/or catalytic activity.
As salts, including, but not limited to, nitrate, chloride, sulfate, acetate, and salts of oxyacids of the metal itself.
According to the preparation process of the present invention, the temperature is 40 to 200 ℃, preferably 50 to 190 ℃, more preferably 60 to 180 ℃, and most preferably 70 to 160 ℃.
In a specific embodiment, the temperature is 80 ℃.
According to the preparation method of the present invention, the calcination is performed at 200 to 1000 ℃, preferably 300 to 900 ℃, more preferably 400 to 800 ℃, and most preferably 500 to 700 ℃.
In a specific embodiment, the firing is performed at 600 ℃.
In a final aspect, the present invention provides the use of a perovskite sulfur shift resistant catalyst as described above or a perovskite sulfur shift resistant catalyst of high specific surface area as described above for sulfur shift resistant reactions, in particular low water to vapor ratio, low sulfur content sulfur shift resistant reactions.
The beneficial effects of the invention are as follows:
(1) The perovskite sulfur tolerant shift catalyst of the present invention. The catalyst improves the activity and stability of the traditional cobalt-molybdenum-based catalyst under the severe conditions of low sulfur, low water vapor ratio and the like.
(2) The perovskite sulfur-tolerant shift catalyst with high specific surface area has the advantages of high thermal stability, long service life, low cost, strong capability of adapting to severe working conditions and the like, and has higher specific surface area, so that the catalytic activity of the perovskite catalyst is effectively improved.
(3) The preparation method of the invention has simple process and easy operation, and is suitable for large-scale industrialized application
(4) The perovskite catalyst is used for sulfur tolerant shift reaction. The catalyst has higher stability and service life under the harsh working conditions of low water-vapor ratio, low sulfur content and the like, and has higher catalytic activity.
Drawings
FIG. 1 shows specific surface areas of catalysts according to various embodiments.
Detailed Description
The invention is further illustrated below with reference to examples, which are not intended to limit the applicability of the invention. Unless otherwise indicated, the percentages in the examples are by mass.
Perovskite sulfur tolerant shift catalyst-example P1
And pouring a certain amount of citric acid into deionized water, uniformly mixing, and then respectively dripping a certain amount of metal salt aqueous solution of lanthanum nitrate and magnesium nitrate into the solution, and uniformly mixing. And respectively dripping a certain amount of aqueous solution of ammonium molybdate and cobalt nitrate into the solution, uniformly mixing, and heating to 80 ℃ to evaporate water so as to gradually change the aqueous solution into gel. The gel obtained was dried at 120 degrees. And roasting the solid obtained by drying at 600 ℃. The catalyst is obtained. Wherein the mol ratio of lanthanum nitrate to magnesium nitrate is 0.5:0.5, and the atomic ratio of molybdenum atoms to Co atoms is 0.45:0.55. The catalyst obtained was designated La 0.5 Mg 0.5 Mo 0.45 Co 0.55 O 3 。
Perovskite sulfur tolerant shift catalyst-example P2
And pouring a certain amount of citric acid into deionized water, uniformly mixing, and then respectively dripping a certain amount of metal salt aqueous solutions of lanthanum nitrate and calcium nitrate into the solutions, and uniformly mixing. And respectively dripping a certain amount of aqueous solution of ammonium molybdate and cobalt nitrate into the solution, uniformly mixing, and heating to 80 ℃ to evaporate water so as to gradually change the aqueous solution into gel. The gel obtained was dried at 120 degrees. And roasting the solid obtained by drying at 600 ℃. The catalyst is obtained. Wherein the mol ratio of lanthanum nitrate to calcium nitrate is 0.5:0.5, and the atomic ratio of molybdenum atoms to Co atoms is 0.45:0.55. The catalyst obtained was designated La 0.5 Ca 0.5 Mo 0.45 Co 0.55 O 3 。
Perovskite sulfur shift catalyst-comparative example C1
And pouring a certain amount of citric acid into deionized water, uniformly mixing, and then respectively dripping a certain amount of metal salt aqueous solution of lanthanum nitrate into the solution, and uniformly mixing. And respectively dripping a certain amount of aqueous solution of ammonium molybdate and cobalt nitrate into the solution, uniformly mixing, and heating to 80 ℃ to evaporate water so as to gradually change the aqueous solution into gel. The gel obtained was dried at 120 degrees. And roasting the solid obtained by drying at 600 ℃. The catalyst is obtained. Wherein the atomic ratio of molybdenum atoms to cobalt atoms is 0.45:0.55. The catalyst obtained was designated as LaMo 0.45 Co 0.55 O 3 。
High specific surface area perovskite sulfur tolerant shift catalyst-example H1
Taking a certain amount of commercially available Al 2 O 3 Pouring the carrier and the citric acid into deionized water, uniformly mixing, then taking a certain amount of aqueous solutions of cerium nitrate and magnesium nitrate metal salt, respectively dripping the aqueous solutions into the solution, and uniformly mixing. And respectively dripping a certain amount of aqueous solution of ammonium molybdate and cobalt nitrate into the solutions, uniformly mixing, and heating to 120 ℃ to evaporate water so as to gradually change the aqueous solution into gel. The gel obtained was dried at 120 degrees. And roasting the solid obtained by drying at 600 ℃. The catalyst is obtained. Wherein the molar ratio of cerium nitrate to magnesium nitrate is 0.5:0.5, and the atomic ratio of molybdenum atoms to Co atoms is 0.45:0.55. A1A 1 2 O 3 The carrier accounts for 70% of the total mass of the catalyst, and the catalyst is named Ce 0.9 Mg 0.1 Mo 0.45 Co 0.55 O 3 /Al 2 O 3 。
High specific surface area perovskite sulfur tolerant shift catalyst-example H2
Taking a certain amount of commercially available SiO 2 Pouring the carrier and the citric acid into deionized water, uniformly mixing, then taking a certain amount of gadolinium nitrate and sodium nitrate metal salt aqueous solution, respectively dripping into the solutions, and uniformly mixing. Respectively dripping a certain amount of aqueous solution of ammonium molybdate and cobalt nitrate into the solution, uniformly mixing, and heating to 150 ℃ to evaporate waterAnd gradually changing the gel into gel. The gel obtained was dried at 150 degrees. And roasting the solid obtained by drying at the temperature of 1000 ℃. The catalyst is obtained. Wherein the molar ratio of gadolinium nitrate to sodium nitrate is 0.5:0.5, and the atomic ratio of molybdenum atoms to Co atoms is 0.55:0.45.SiO (SiO) 2 The carrier accounts for 60% of the total mass of the catalyst, and the obtained catalyst is named Gd 0.1 Mg 0.9 Mo 0.45 Co 0.55 O 3 /SiO 2 。
High specific surface area perovskite sulfur tolerant shift catalyst-example H3
Taking a certain amount of commercial TiO 2 Pouring the carrier and the citric acid into deionized water, uniformly mixing, then taking a certain amount of metal salt aqueous solution of lanthanum nitrate and calcium nitrate, respectively dripping into the solutions, and uniformly mixing. And respectively dripping a certain amount of aqueous solution of ammonium molybdate and cobalt nitrate into the solutions, uniformly mixing, and heating to 120 ℃ to evaporate water so as to gradually change the aqueous solution into gel. The gel obtained was dried at 120 degrees. And roasting the solid obtained by drying at the temperature of 800 ℃. The catalyst is obtained. Wherein the mol ratio of lanthanum nitrate to calcium nitrate is 0.5:0.5, and the atomic ratio of molybdenum atoms to Co atoms is 0.55:0.45.SiO (SiO) 2 The carrier accounts for 60% of the total mass of the catalyst, and the obtained catalyst is named La 0.5 Ca 0.5 Mo 0.55 Co 0.45 O 3 /SiO 2 。
High specific surface area perovskite sulfur tolerant shift catalyst-example H4
Taking a certain amount of commercial ZrO 2 Pouring the carrier and the citric acid into deionized water, uniformly mixing, then taking a certain amount of metal salt aqueous solution of lanthanum nitrate and potassium nitrate, respectively dripping into the solutions, and uniformly mixing. And respectively dripping a certain amount of aqueous solution of ammonium molybdate and cobalt nitrate into the solution, uniformly mixing, and heating to 80 ℃ to evaporate water so as to gradually change the aqueous solution into gel. The gel obtained was dried at 80 degrees. And roasting the solid obtained by drying at the temperature of 400 ℃. The catalyst is obtained. Wherein the mol ratio of lanthanum nitrate to potassium nitrate is 0.5:0.5, and the atomic ratio of molybdenum atoms to Co atoms is 0.55:0.45.SiO (SiO) 2 The carrier accounts for 50% of the total mass of the catalyst, and the obtained catalyst is named La 0.5 Ca 0.5 Mo 0.55 Co 0.45 O 3 /ZrO 2 。
The pressurizing activity evaluating device in the prior art is used for simulating industrial conditions and comparing the performances of the catalyst, such as conversion activity, stability and the like, the reaction tube is a stainless steel tube with the diameter of phi 45 multiplied by 5mm, and the center is provided with a thermocouple tube with the diameter of phi 8 multiplied by 2 mm. A certain amount of water is added according to the requirements of different water-gas ratios, and the water is gasified at high temperature and then enters a reaction tube together with raw material gas to carry out water gas shift reaction, and the tail gas after the reaction is analyzed by chromatography.
Table 1 shows the results of evaluating the catalytic activity of the catalyst finished products of each of examples and comparative examples under normal conditions and severe conditions.
TABLE 1
It should be understood that the description of the specific embodiments is merely illustrative of the principles and spirit of the invention, and not in limitation thereof. Further, it should be understood that various changes, substitutions, omissions, modifications, or adaptations to the present invention may be made by those skilled in the art after having read the present disclosure, and such equivalent embodiments are within the scope of the present invention as defined in the appended claims.

Claims (5)

1. Use of a high specific surface area perovskite catalyst in sulfur tolerant shift reactions, the catalyst having a composition represented by chemical formula 4:
M/C type 4
Wherein M is a composition represented by chemical formula 3 and has a perovskite type structure:
(A 1 ) x (A 2 ) 1-x (B 1 ) y (B 2 ) 1-y O 3 3
Wherein A is 1 Represents a rare earth metal element; a is that 2 Represents one or more of alkali metal elements and/or alkaline earth metal elements; b (B) 1 Represents molybdenum; b (B) 2 Represents cobalt; x is more than or equal to 0 and less than or equal to 1; y is more than or equal to 0.2 and less than or equal to 1; c represents an inert carrier;
the inert support includes alumina, silica, titania, zirconia, magnesia, nickel oxide, and carbon-based supports.
2. A process for the preparation of a high specific surface area perovskite catalyst for use according to claim 1, said process comprising:
(1) Obtaining an aqueous solution/dispersion comprising hydroxycarboxylic acid, a group a element salt and a group B element salt, and C;
(2) The aqueous solution/dispersion is gelled at an elevated temperature to obtain a gel;
(3) And roasting the dried gel to obtain the perovskite catalyst with high specific surface area.
3. The preparation method according to claim 2, wherein the temperature is 40-200 ℃.
4. The preparation method according to claim 2, wherein the firing is performed at 200 to 1000 ℃.
5. The use according to claim 1, wherein the sulfur tolerant shift reaction is a low water to vapor ratio, low sulfur content sulfur tolerant shift reaction.
CN202010958239.5A 2020-09-14 2020-09-14 Perovskite sulfur-resistant shift catalyst and preparation method and application thereof Active CN114177912B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010958239.5A CN114177912B (en) 2020-09-14 2020-09-14 Perovskite sulfur-resistant shift catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010958239.5A CN114177912B (en) 2020-09-14 2020-09-14 Perovskite sulfur-resistant shift catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114177912A CN114177912A (en) 2022-03-15
CN114177912B true CN114177912B (en) 2024-02-13

Family

ID=80600691

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010958239.5A Active CN114177912B (en) 2020-09-14 2020-09-14 Perovskite sulfur-resistant shift catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114177912B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1154271A (en) * 1996-01-11 1997-07-16 中国石化齐鲁石油化工公司 Preparation method of novel CO sulfur-tolerant shift catalyst
CN1559679A (en) * 2004-02-16 2005-01-05 厦门大学 Carbon monoxide sulfur resisting transform catalyst and its preparation method
JP2006116370A (en) * 2004-10-19 2006-05-11 Seimi Chem Co Ltd Carbon monoxide shift reaction catalyst
KR20110075323A (en) * 2009-12-28 2011-07-06 주식회사 포스코 Method of water gas shift reaction and method for producing hydrogen using the same
CN102515096A (en) * 2011-11-22 2012-06-27 中国科学院广州能源研究所 Application of three-dimensional ordered macro-porous perovskite type oxide in preparing hydrogen through carbonic fuel chemical chain
CN104888798A (en) * 2015-06-10 2015-09-09 西南化工研究设计院有限公司 High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087192C (en) * 1998-07-15 2002-07-10 中国石化齐鲁石油化工公司 Hydration-resisting and sulfur-resisting conversion catalyst and its preparation
GB201109376D0 (en) * 2011-06-06 2011-07-20 Johnson Matthey Plc Water-gas shift catalyst

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1154271A (en) * 1996-01-11 1997-07-16 中国石化齐鲁石油化工公司 Preparation method of novel CO sulfur-tolerant shift catalyst
CN1559679A (en) * 2004-02-16 2005-01-05 厦门大学 Carbon monoxide sulfur resisting transform catalyst and its preparation method
JP2006116370A (en) * 2004-10-19 2006-05-11 Seimi Chem Co Ltd Carbon monoxide shift reaction catalyst
KR20110075323A (en) * 2009-12-28 2011-07-06 주식회사 포스코 Method of water gas shift reaction and method for producing hydrogen using the same
CN102515096A (en) * 2011-11-22 2012-06-27 中国科学院广州能源研究所 Application of three-dimensional ordered macro-porous perovskite type oxide in preparing hydrogen through carbonic fuel chemical chain
CN104888798A (en) * 2015-06-10 2015-09-09 西南化工研究设计院有限公司 High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst

Also Published As

Publication number Publication date
CN114177912A (en) 2022-03-15

Similar Documents

Publication Publication Date Title
CN103752319B (en) Anti-carbon Ni methylmethane vapor reforming hydrogen production catalyst and preparation method thereof
CN109126787B (en) Rare earth metal oxide supported ruthenium catalyst for ammonia synthesis and application thereof
CN108246300A (en) With rutile TiO2Methanation catalyst for carrier and preparation method thereof
JP2017050180A (en) Fuel electrode material, cell for solid oxide fuel battery, catalyst for hydrogen production, and method for producing hydrogen
CN104971727A (en) Preparation method of high-efficiency nickel-based catalyst for producing hydrogen in methanol-steam reforming
CN108126762A (en) One kind manufactures for producing undersaturated cobalt-base catalyst and preparing with carboxylate
JP2002336702A (en) Autothermal reforming catalyst and method for manufacturing fuel gas for fuel cell
CN102302931A (en) Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof
CN114177912B (en) Perovskite sulfur-resistant shift catalyst and preparation method and application thereof
CN113332863B (en) Preparation method of biphase oxygen permeable membrane with high surface catalytic activity
JP5969632B2 (en) Method for synthesizing air electrode powder for medium- and low-temperature solid oxide fuel cells by sol-gel method
JP2023550204A (en) Catalyst and sulfur-resistant conversion catalyst method
KR20150067253A (en) Method for producing composite oxide and composite oxide catalyst
CN106966728B (en) Anion-doped K2NiF4Oxygen permeable membrane material of mixed conductor, preparation method and application thereof
Chen et al. Chemical compatibility between boron oxides and electrolyte and cathode materials of solid oxide fuel cells
Fu et al. Effective Macroporous Core–Shell Structure of Alumina‐Supported Spinel Ferrite for Carbon Dioxide Splitting Based on Chemical Looping
CN109437882B (en) BaFeO doped with La element and Cu element3-Ceramic-based oxygen-permeable membrane material and preparation method thereof
CN111482181A (en) Reforming hydrogen production composite catalyst and preparation method and application thereof
CN114100625B (en) Cobalt-molybdenum-based perovskite sulfur-tolerant shift reaction catalyst and preparation method thereof
CN108573815B (en) Preparation method of porous spherical NiO serving as electrode material of super capacitor
CN101775610B (en) Solid electrochemical oxygen pump and carbon dioxide decomposition method thereof
CN110813302A (en) Preparation method of Ni-based catalyst
CN109382113B (en) Perovskite type oxide catalyst, preparation method and application thereof
CN113582133A (en) Ammonia catalysis and hydrogen separation integrated membrane, preparation method and application
CN114425395B (en) Porous perovskite sulfur-resistant shift catalyst and preparation method and application thereof

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