CN114939435A - Integral type bifunctional catalyst and preparation method and application thereof - Google Patents

Integral type bifunctional catalyst and preparation method and application thereof Download PDF

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Publication number
CN114939435A
CN114939435A CN202210756393.3A CN202210756393A CN114939435A CN 114939435 A CN114939435 A CN 114939435A CN 202210756393 A CN202210756393 A CN 202210756393A CN 114939435 A CN114939435 A CN 114939435A
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China
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molecular sieve
printing
metal oxide
ink
bifunctional catalyst
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Chinese (zh)
Inventor
王阳
刘涛
林世源
夏水林
胡涵
王荟钦
王文行
李智
李梦
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China University of Petroleum East China
Shandong Energy Group Co Ltd
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China University of Petroleum East China
Shandong Energy Group Co Ltd
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Priority to CN202210756393.3A priority Critical patent/CN114939435A/en
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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

Abstract

The invention belongs to the technical field of chemical catalysis, and particularly relates to an integral bifunctional catalyst, and a preparation method and application thereof. The integral bifunctional catalyst provided by the invention is prepared by 3D printing of metal oxide ink and molecular sieve ink, and then drying and sintering; the metal oxide and the molecular sieve in the integral bifunctional catalyst are orderly arranged according to a preset 3D printing geometric structure. The invention utilizes 3D printing technology to arrange metal oxide and molecular sieve in order to form the catalyst with a certain geometric structure, optimizes the mass transfer and heat transfer performance of the catalyst, improves the selectivity of the catalyst to a target product in the catalytic conversion process of carbon dioxide, and has higher economic value and environmental benefit.

Description

Integral type bifunctional catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to an integral type bifunctional catalyst, and a preparation method and application thereof.
Background
With the rapid development of human society, a large amount of carbon dioxide is discharged into the atmosphere, which directly causes a series of ecological environmental problems such as global warming, sea level rising and the like, and seriously threatens the survival development of human beings. The direct conversion of carbon dioxide into value-added chemicals not only reduces the level of greenhouse gases in the atmosphere, but also provides a promising strategy for the production of high value-added chemicals.
Bifunctional catalysts are those having multiple catalytic functionsActive center, catalyst for multiple different catalytic reactions in one reaction process. With CO 2 For the hydrogenation reaction, the metal oxide is responsible for CO 2 The activation is carried out and then selective C-C coupling is carried out by a molecular sieve, and the activation and the selective C-C coupling are combined to realize CO 2 To high added value products such as olefin aromatic hydrocarbon in one step.
In the traditional dual-function catalyst, different active ingredients are mixed together in a form of powder or granules, and the mass and heat transfer processes in the catalyst are disordered, so that the selectivity of a target product is influenced.
Disclosure of Invention
In view of this, the present invention aims to provide an integral bifunctional catalyst, and a preparation method and an application thereof, and the catalyst provided by the present invention has good mass transfer and heat transfer, and is favorable for improving the selectivity of a target product.
The invention provides an integral bifunctional catalyst, which is prepared by 3D printing of metal oxide ink and molecular sieve ink, drying and sintering;
the metal oxide and the molecular sieve in the integral bifunctional catalyst are orderly arranged according to a preset 3D printing geometric structure.
In the monolithic bifunctional catalyst provided by the invention, the metal oxide ink contains metal oxide and solvent, and preferably also contains a binder and a dispersant; the metal oxide is a compound having CO 2 Metal oxides with activating properties, preferably one or more of oxides of indium, iron and chromium; the oxide of indium is preferably indium oxide or MOF precursor derived indium oxide; the solvent is not particularly limited, and may be a solvent well known to those skilled in the art, and is preferably water; the binder is not particularly limited, and may be a binder well known to those skilled in the art, preferably bentonite; the dispersant is not particularly limited, and may be a dispersant well known to those skilled in the art, and is preferably hydroxypropylmethylcellulose.
In the monolithic bifunctional catalyst provided by the present invention, the mass ratio of the metal oxide to the binder in the metal oxide ink is preferably (9:1) - (1:9), and more preferably 1: 1; the mass ratio of the total amount of the metal oxide and the binder to the solvent is preferably (1:2) to (2:1), more preferably 1: 2; the mass of the dispersant accounts for 1-15 wt% of the mass of the solvent, and the mass of the dispersant is 2.5 wt% preferably.
In the monolithic bifunctional catalyst provided by the invention, the molecular sieve ink contains a molecular sieve and a solvent, and preferably also contains a binder and a dispersant; the molecular sieve is preferably a ZSM-5 molecular sieve and/or a SAPO-34 molecular sieve, and is more preferably a SAPO-34 molecular sieve; the solvent is not particularly limited, and may be a solvent well known to those skilled in the art, and is preferably water; the binder is not particularly limited, and may be a binder well known to those skilled in the art, preferably bentonite; the dispersant is not particularly limited, and may be a dispersant well known to those skilled in the art, and is preferably hydroxypropylmethylcellulose.
In the monolithic bifunctional catalyst provided by the invention, in the molecular sieve ink, the mass ratio of the molecular sieve to the binder is preferably (9:1) - (1:9), and more preferably 1: 1; the mass ratio of the total amount of the molecular sieve and the binder to the solvent is preferably (1:2) to (2:1), more preferably 1: 2; the mass of the dispersant accounts for 1-15 wt% of the mass of the solvent, and the mass of the dispersant is 2.5 wt% preferably.
In the monolithic bifunctional catalyst provided by the present invention, the ratio of the metal oxide ink by mass of metal oxide to the molecular sieve ink by mass of molecular sieve is preferably (1:18) to (18:1), more preferably (1:2) to (2:1), and most preferably 1: 2.
In the integral bifunctional catalyst provided by the invention, the metal oxide ink and the molecular sieve ink are subjected to 3D printing, so that the metal oxide and the molecular sieve are orderly arranged into a certain geometric structure; the 3D printing mode is preferably direct-writing 3D printing; the geometric shape of the outer contour of the 3D printing is not specially limited, and the outer contour can be any geometric shape, preferably a cylinder shape; the filling mode of the 3D printing is not particularly limited, and may be linear filling or nonlinear filling, and is preferably linear filling; the inner diameter of the needle head for 3D printing is preferably 0.1-1 mm, and more preferably 0.21 mm; the air pressure of the 3D printing nozzle is preferably 0.01-0.6 MPa, more preferably 0.1-0.4 MPa, and most preferably 0.1-0.3 MPa.
In the monolithic bifunctional catalyst provided in the present invention, the drying manner is not particularly limited, and may be a drying manner well known to those skilled in the art, and preferably freeze-drying; the freeze drying time is preferably 12-48 h, and more preferably 24 h.
In the monolithic bifunctional catalyst provided by the present invention, the binder may be sintered and the dispersant removed by the calcination; the calcination mode is preferably calcination in air; the calcination temperature is preferably 300-600 ℃, and more preferably 550 ℃; the heating rate before reaching the calcination temperature is preferably 1-10 ℃/min, and more preferably 5 ℃/min; the calcination time is preferably 1-6 h, more preferably 5h, and the calcination time does not include the time spent on heating to the calcination temperature.
The invention also provides a preparation method of the integral type bifunctional catalyst, which comprises the following steps:
and 3D printing, drying and calcining the metal oxide ink and the molecular sieve ink to obtain the integral bifunctional catalyst.
In the preparation method provided by the invention, the metal oxide ink contains metal oxide and solvent, and preferably also contains a binder and a dispersant; the metal oxide is a compound having CO 2 A metal oxide having an activating property, preferably one or more of indium oxide, iron oxide and chromium oxide, more preferably indium oxide; the solvent is not particularly limited, and may be a solvent well known to those skilled in the art, and is preferably water; the binder is not particularly limited, and may be a binder well known to those skilled in the art, preferably bentonite; the dispersant is not particularly limited, and may be a dispersant well known to those skilled in the art, and is preferably hydroxypropylmethylcellulose.
In the preparation method provided by the invention, in the metal oxide ink, the mass ratio of the metal oxide to the binder is preferably (9:1) - (1:9), and more preferably 1: 1; the mass ratio of the total amount of the metal oxide and the binder to the solvent is preferably (1:2) to (2:1), more preferably 1: 2; the mass of the dispersant accounts for 1-15 wt% of the mass of the solvent, and the mass of the dispersant is 2.5 wt% preferably.
In the preparation method provided by the invention, the molecular sieve ink contains a molecular sieve and a solvent, and preferably also contains a binder and a dispersant; the molecular sieve is preferably a ZSM-5 molecular sieve and/or a SAPO-34 molecular sieve, and is more preferably a SAPO-34 molecular sieve; the solvent is not particularly limited, and may be a solvent well known to those skilled in the art, and is preferably water; the binder is not particularly limited, and may be a binder well known to those skilled in the art, preferably bentonite; the dispersant is not particularly limited, and may be a dispersant well known to those skilled in the art, and is preferably hydroxypropylmethylcellulose.
In the preparation method provided by the invention, in the molecular sieve ink, the mass ratio of the molecular sieve to the binder is preferably (9:1) - (1:9), and more preferably 1: 1; the mass ratio of the total amount of the molecular sieve and the binder to the solvent is preferably (1:2) to (2:1), more preferably 1: 2; the mass of the dispersing agent accounts for 1-15 wt% of the mass of the solvent, and 2.5 wt% is more preferable.
In the production method provided by the present invention, the ratio of the metal oxide ink by mass of the metal oxide to the molecular sieve ink by mass of the molecular sieve is preferably (1:18) to (18:1), more preferably (1:2) to (2:1), and most preferably 1: 2.
In the preparation method provided by the invention, the metal oxide ink and the molecular sieve ink are preferably prepared by mixing corresponding raw material components, and the equipment used for mixing is preferably a planetary centrifugal mixer.
In the preparation method provided by the invention, the metal oxide ink and the molecular sieve ink are subjected to 3D printing, so that the metal oxide and the molecular sieve are orderly arranged into a certain geometric structure; the 3D printing mode is preferably direct-writing 3D printing; the geometric shape of the outer contour of the 3D printing is not specially limited, and the outer contour can be any geometric shape, preferably a cylinder shape; the filling mode of the 3D printing is not particularly limited, and may be linear filling or nonlinear filling, and is preferably linear filling; the inner diameter of the needle head for 3D printing is preferably 0.1-1 mm, and more preferably 0.21 mm; the air pressure of the 3D printing is preferably 0.01-0.6 MPa, and more preferably 0.1-0.4 MPa.
In the preparation method provided by the present invention, the drying manner is not particularly limited, and may be a drying manner well known to those skilled in the art, and is preferably freeze-drying; the freeze drying time is preferably 12-48 h, and more preferably 24 h.
In the preparation method provided by the invention, the calcination mode is preferably calcination in air; the calcination temperature is preferably 300-600 ℃, and more preferably 550 ℃; the heating rate before reaching the calcination temperature is preferably 1-10 ℃/min, and more preferably 5 ℃/min; the calcination time is preferably 1-6 h, and more preferably 5 h.
The invention also provides a method for catalytic hydrogenation of carbon dioxide, wherein the catalyst adopted in the catalytic hydrogenation process is the integral bifunctional catalyst prepared by the technical scheme or the preparation method of the technical scheme. The method specifically comprises the following steps:
in the presence of said catalyst, CO 2 Hydrogenation reaction is carried out to obtain a hydrogenation product.
In the catalytic hydrogenation process provided by the invention, the catalyst is preferably subjected to H before use 2 Reduction treatment and activation; said H 2 The reduction treatment activation is preferably carried out in a fixed bed reactor; said H 2 The temperature for reduction treatment activation is preferably 150-300 ℃, and more preferably 200 ℃; said H 2 The time for the reduction treatment activation is preferably 1 to 4 hours, and more preferably 1 hour.
In the catalytic hydrogenation method provided by the invention, CO is used for carrying out the hydrogenation reaction 2 And H 2 Is preferably 1: (2-5), more preferably 1: 3.2; the hydrogenation reaction is preferably carried out in the presence of argon; the argon preferably accounts for argon and CO 2 And H 2 2-8% of the volume of the mixed gas, more preferably 5.07%.
In the catalytic hydrogenation method provided by the invention, the hydrogenation reaction is preferably carried out in a fixed bed reactor; the temperature of the hydrogenation reaction is preferably 300-550 ℃, and more preferably 380 ℃; the pressure intensity of the hydrogenation reaction is preferably 2-10 MPa, and more preferably 3 MPa; the total gas flow of the hydrogenation reaction is preferably 5-100 mL/min, and specifically can be 20mL/min, 60mL/min or 100 mL/min; the preferred space velocity of the hydrogenation reaction is 2000-30000 mL/g cat –1 ·h –1 Specifically, 4000 mL/g cat –1 ·h –1 、12000mL·g cat –1 ·h –1 Or 20000mL g cat –1 ·h –1 。
Compared with the prior art, the invention provides an integral bifunctional catalyst and a preparation method and application thereof. The technical scheme provided by the invention utilizes a 3D printing technology to orderly arrange the metal oxide and the molecular sieve into the catalyst with a certain geometric structure, optimizes the mass transfer and heat transfer performance of the catalyst, improves the selectivity of the catalyst to a target product in the catalytic conversion process of carbon dioxide, and has higher economic value and environmental benefit.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a structural design drawing of a monolithic bifunctional catalyst prepared according to an example provided by the present invention;
FIG. 2 is a digital photograph of a monolithic bifunctional catalyst prepared according to an example provided by the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the metal oxide 3D printing ink comprises the following steps:
respectively grinding 0.5g of indium oxide and 0.5g of bentonite in a mortar for 20-30 min, and putting the ground indium oxide and bentonite (purchased from Mecanum reagent, product number B802110), 2g of deionized water and 0.05g of hydroxypropyl methyl cellulose (purchased from Mecanum reagent, product number H811098) into a planetary centrifugal mixer for fully and uniformly mixing; and transferring the mixed slurry into a 3D printing material barrel, putting the material barrel filled with the slurry into a centrifugal machine for centrifugation, and defoaming the slurry to obtain the indium oxide 3D printing ink.
Example 2
The preparation method of the molecular sieve 3D printing ink comprises the following steps:
respectively grinding 0.5g of SAPO-34 molecular sieve and 0.5g of bentonite in a mortar for 20-30 min, and putting the ground molecular sieve and bentonite (purchased from Mecanum reagent, product number B802110), 2g of deionized water and 0.05g of hydroxypropyl methyl cellulose (purchased from Mecanum reagent, product number H811098) into a planetary centrifugal mixer for fully and uniformly mixing; and transferring the mixed slurry into a 3D printing material barrel, putting the material barrel filled with the slurry into a centrifugal machine for centrifugation, and defoaming the slurry to obtain the SAPO-34 molecular sieve 3D printing ink.
Example 3
The preparation of the integral bifunctional catalyst comprises the following steps:
designing a 3D printing model and a printing path in computer software, wherein the specific model is shown in FIGS. 1(a) - (b), FIG. 1(a) is a single-layer schematic diagram of the model, FIG. 1(b) is a multilayer disassembled structure schematic diagram of the model, in the diagram, a solid line represents the printing path of indium oxide 3D printing ink, a dotted line represents the printing path of SAPO-34 molecular sieve 3D printing ink, the outer diameter of the model is 10mm, the diameter of a monofilament is 0.21mm, and the distance between filaments is 0.4 mm; it can be seen that in the same layer, the indium oxide 3D printing ink and the SAPO-34 molecular sieve 3D printing ink are alternately arranged from filament to filament, and the filaments between the two adjacent layers are perpendicular to each other.
Carefully transferring the printing inks formulated in examples 1 and 2 to 5cm 3 In the syringe of (1); in a direct-writing 3D printing system, printing ink is printed layer by layer at room temperature through a needle head according to the movement of a computer in the directions of x, y and z, the inner diameter of the printing needle head is 0.21mm, and the printing air pressure is 0.1-0.3 MPa; in the printing process, the mass ratio of the total consumption of the indium oxide 3D printing ink to the total consumption of the SAPO-34 molecular sieve 3D printing ink is 1: 2; after printing is finished, In order to prevent collapse and cracking of the catalyst, the catalyst is placed In a freeze dryer for 24 hours, then the temperature is raised to 550 ℃ In the air at the temperature rise rate of 5 ℃/min, and the catalyst is subjected to heat preservation and calcination for 5 hours to obtain the integral bifunctional catalyst named In 2 O 3 The physical appearance of the/SAPO-34-3D-S is shown in figure 2 (a).
Example 4
The preparation of the integral bifunctional catalyst comprises the following steps:
designing a 3D printing model and a printing path in computer software, wherein the specific model is shown in FIGS. 1(c) to (D), FIG. 1(c) is a schematic view of a top view structure of the model, FIG. 1(D) is a schematic view of a multilayer disassembled structure of the model, in the figure, a solid line represents the printing path of indium oxide 3D printing ink, a dotted line represents the printing path of SAPO-34 molecular sieve 3D printing ink, the outer diameter of the model is 10mm, the diameter of a monofilament is 0.21mm, and the distance between filaments is 0.4 mm; it can be seen that in the same layer, the same ink is used; different inks are used between two adjacent layers, and the directions of the filaments are mutually vertical.
Carefully transferring the printing inks formulated in examples 1 and 2 to 5cm 3 In the syringe of (1); in a direct-writing 3D printing system, printing ink is printed layer by layer at room temperature through a needle head according to the movement of a computer in the directions of x, y and z, the inner diameter of the printing needle head is 0.21mm, and the printing air pressure is 0.1-0.3 MPa; in the printing process, the mass ratio of the total consumption of the indium oxide 3D printing ink to the total consumption of the SAPO-34 molecular sieve 3D printing ink is 1: 2; after printing, to prevent collapse and crack, it is placed in a freeze dryer24h, heating to 550 ℃ at the heating rate of 5 ℃/min In the air, and carrying out heat preservation and calcination for 5h to obtain the integral bifunctional catalyst named In 2 O 3 The physical appearance of the/SAPO-34-3D-C is shown in figure 2 (b).
Example 5
The preparation of the integral bifunctional catalyst comprises the following steps:
designing a 3D printing model and a printing path in computer software, wherein the specific model is shown in FIGS. 1(e) to (f), FIG. 1(e) is a schematic view of a top view structure of the model, FIG. 1(f) is a schematic view of a multilayer disassembled structure of the model, in the figure, a solid line represents the printing path of indium oxide 3D printing ink, a dotted line represents the printing path of SAPO-34 molecular sieve 3D printing ink, the outer diameter of the model is 10mm, and the diameter of a monofilament is 0.21 mm; in the same layer, the same ink is used to form a hexagonal pattern; different inks are used between two adjacent layers, and hexagons formed by the two layers are mutually staggered.
Carefully transferring the printing inks formulated in examples 1 and 2 to 5cm 3 In the syringe of (1); in a direct-writing 3D printing system, printing ink is printed layer by layer at room temperature through a needle head according to the movement of a computer in the directions of x, y and z, the inner diameter of the printing needle head is 0.21mm, and the printing air pressure is 0.1-0.3 MPa; in the printing process, the mass ratio of the total consumption of the indium oxide 3D printing ink to the total consumption of the SAPO-34 molecular sieve 3D printing ink is 1: 2; after printing is finished, In order to prevent collapse and cracking of the catalyst, the catalyst is placed In a freeze dryer for 24 hours, then the temperature is raised to 550 ℃ In the air at the temperature rise rate of 5 ℃/min, and the catalyst is subjected to heat preservation and calcination for 5 hours to obtain the integral bifunctional catalyst named In 2 O 3 The physical appearance of the/SAPO-34-3D-H is shown in figure 2 (c).
Example 6
The preparation method of the MOF precursor derivative indium oxide comprises the following steps:
2.11gIn (NO) 3 ) 3 Adding 1g of terephthalic acid into 25ml of DMF, uniformly mixing, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment in a 100 ℃ oven for 24 hours; centrifuging and washing with anhydrous ethanol for 3 times after water heating is finished, drying ethanol after washing, and putting the dried product into vacuum ovenDrying for 12h at 60 ℃ in a box to obtain indium oxide MOFs; heating indium oxide MOFs at 500 ℃ for 2h under a nitrogen atmosphere, and then calcining the heated indium oxide MOFs in air at 500 ℃ for 2h to obtain a product called MOF precursor derived indium oxide.
The preparation method of the metal oxide 3D printing ink comprises the following steps:
referring to the preparation method of example 1, 0.5g of indium oxide was replaced with 0.5g of MOF precursor-derived indium oxide to obtain a MOF precursor-derived indium oxide 3D printing ink.
The preparation of the integral bifunctional catalyst comprises the following steps:
designing a 3D printing model and a printing path in computer software, wherein specific models are shown in figures 1(a) - (b), the figure 1(a) is a single-layer schematic diagram of the model, the figure 1(b) is a multilayer disassembly structure schematic diagram of the model, in the figure, a solid line represents a printing path of indium oxide 3D printing ink, a dotted line represents a printing path of SAPO-34 molecular sieve 3D printing ink, the outer diameter of the model is 12mm, the diameter of a monofilament is 0.21mm, and the distance between filaments is 0.2 mm; it can be seen that in the same layer, the indium oxide 3D printing ink and the SAPO-34 molecular sieve 3D printing ink are alternately arranged from filament to filament, and the filaments between the two adjacent layers are perpendicular to each other.
Carefully transferring the formulated MOF precursor-derived indium oxide 3D printing ink and the molecular sieve 3D printing ink formulated in example 2 to 5cm 3 In the syringe of (1); in a direct-writing 3D printing system, printing ink is printed layer by layer at room temperature through a needle head according to the movement of a computer in the directions of x, y and z, the inner diameter of the printing needle head is 0.21mm, and the printing air pressure is 0.1-0.3 MPa; in the printing process, the mass ratio of the total consumption of the MOF precursor derived indium oxide 3D printing ink to the total consumption of the SAPO-34 molecular sieve 3D printing ink is 1: 2; after printing is finished, In order to prevent collapse and cracking of the catalyst, the catalyst is placed In a freeze dryer for 24 hours, then the temperature is raised to 550 ℃ In the air at the temperature rise rate of 5 ℃/min, and the catalyst is subjected to heat preservation and calcination for 5 hours to obtain the integral bifunctional catalyst named In 2 O 3 The physical appearance of the/SAPO-34-3D-M is shown in FIG. 2 (D).
Testing of catalyst Performance
Example 3 and example 6 were taken separately1.5g of each provided integral type dual-function catalyst is firstly reduced in pure hydrogen at 200 ℃ for 1h to obtain an active catalyst; placing the active catalyst in a quartz reaction tube, and respectively adding the active catalyst in the quartz reaction tube at a rate of 20 mL-min -1 、60mL·min -1 、100mL·min -1 Introducing a mixed gas containing 5.07% of argon, 23.73% of carbon dioxide and 76.27% of hydrogen, reacting for 8 hours at 380 ℃ and under the pressure of 3.0MPa, analyzing the product by gas chromatography, and obtaining the reaction results shown in Table 1:
TABLE 1 carbon dioxide conversion and reaction product selectivity test results
Figure BDA0003722638420000091
As can be seen from Table 1, In constructed by 3D printing 2 O 3 the/SAPO-34 integral type dual-function catalyst has high C 2 ～C 4 Selectivity to olefin.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. An integral bifunctional catalyst is prepared by 3D printing metal oxide ink and molecular sieve ink, and drying and sintering;
the metal oxide and the molecular sieve in the integral bifunctional catalyst are orderly arranged according to a preset 3D printing geometrical structure.
2. The monolithic bifunctional catalyst of claim 1 wherein the metal oxide in the metal oxide ink is one or more of indium oxide, iron oxide and chromium oxide.
3. Monolithic bifunctional catalyst according to claim 1, characterized in that the molecular sieve in the molecular sieve ink is a ZSM-5 molecular sieve and/or a SAPO-34 molecular sieve.
4. The monolithic bifunctional catalyst of claim 1, characterized in that the ratio of the metal oxide ink by mass of metal oxide to the molecular sieve ink by mass of molecular sieve is (1:18) - (18: 1).
5. The monolithic bifunctional catalyst of claim 1, wherein the metal oxide ink comprises a metal oxide, a binder, a dispersant and a solvent;
the adhesive is bentonite; the dispersing agent is hydroxypropyl methyl cellulose; the solvent is water;
the mass ratio of the metal oxide to the binder is (9:1) - (1: 9); the mass ratio of the total amount of the metal oxide and the adhesive to the solvent is (1:2) - (2: 1); the mass of the dispersing agent accounts for 1-15 wt% of the mass of the solvent.
6. The monolithic bifunctional catalyst of claim 1, wherein the molecular sieve ink comprises a molecular sieve, a binder, a dispersant and a solvent;
the adhesive is bentonite; the dispersing agent is hydroxypropyl methyl cellulose; the solvent is water;
the mass ratio of the molecular sieve to the adhesive is (9:1) - (1: 9); the mass ratio of the total amount of the molecular sieve and the adhesive to the solvent is (1:2) - (2: 1); the mass of the dispersing agent accounts for 1-15 wt% of the mass of the solvent.
7. A monolithic bifunctional catalyst according to claim 1 wherein the 3D printing is a direct write 3D printing.
8. A method for preparing a monolithic bifunctional catalyst according to any one of claims 1 to 7, comprising the steps of:
and 3D printing, drying and calcining the metal oxide ink and the molecular sieve ink to obtain the integral bifunctional catalyst.
9. Use of the monolithic bifunctional catalyst of any one of claims 1 to 7 or prepared by the preparation method of claim 8 as a carbon dioxide hydrogenation catalyst.
10. A method for catalytic hydrogenation of carbon dioxide is characterized in that a catalyst used in the catalytic hydrogenation process is the monolithic bifunctional catalyst of any one of claims 1 to 7 or the monolithic bifunctional catalyst prepared by the preparation method of claim 8.
CN202210756393.3A 2022-06-30 2022-06-30 Integral type bifunctional catalyst and preparation method and application thereof Pending CN114939435A (en)

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