CN114768746B - Metal catalytic reactor and preparation and use thereof in natural gas and CO 2 Application of dry gas reforming to synthesis gas - Google Patents

Metal catalytic reactor and preparation and use thereof in natural gas and CO 2 Application of dry gas reforming to synthesis gas Download PDF

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CN114768746B
CN114768746B CN202210119702.6A CN202210119702A CN114768746B CN 114768746 B CN114768746 B CN 114768746B CN 202210119702 A CN202210119702 A CN 202210119702A CN 114768746 B CN114768746 B CN 114768746B
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metal
gas
catalytic reactor
carbon dioxide
catalyst
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CN114768746A (en
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包信和
郭晓光
潘秀莲
于洪飞
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/32—Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • 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
    • 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
    • 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

Abstract

The invention relates to a metal catalytic reactor, a preparation method thereof and a catalyst for natural gas and CO 2 Application of dry gas reforming to preparation of synthesis gas, coating and doping catalyst active components on contact surface of metal tube and reaction raw material, forming catalytic dopant thin layer on contact surface of metal tube and reaction raw material to obtain the metal catalytic reactor, the metal catalytic reactor is used for natural gas and CO 2 The dry gas reforming reaction can realize the high-efficiency conversion of methane and carbon dioxide, high catalyst stability and low carbon deposition generation. The conversion rate of methane is 80-96%; the carbon dioxide conversion rate is 80-98%; the selectivity of carbon monoxide is more than 99 percent; CO/H 2 =1; low carbon deposition. The method has the characteristics of long service life of the catalyst, high methane conversion rate and product selectivity, low carbon deposition, no need of amplifying the catalyst, small industrialization difficulty, easy separation of the product, good process repeatability, safe and reliable operation and the like, and has wide industrial application prospect.

Description

Metal catalytic reactor and preparation and use thereof in natural gas and CO 2 Application of dry gas reforming to synthesis gas
Technical Field
The invention belongs to the field of catalysis, and in particular relates to a metal catalytic reactor and preparation thereof and catalytic conversion of natural gas and CO 2 Application of dry gas reforming to synthesis gas, the process realizing natural gas and CO 2 The catalyst has the characteristics of high stability and low carbon generation.
Background
Catalytic methane and carbon dioxide reforming (Dry Reforming of Methane, DRM) to produce synthesis gas (CO and H) 2 ) Is considered to be the optimal reaction path. The path can greatly improve the conversion efficiency of methane and obtain the synthesis gas H with great industrial value 2 The CO is approximately equal to 1, can be directly used as raw material gas for Fischer-Tropsch synthesis, low-carbon olefin synthesis, dimethyl ether synthesis, oxo synthesis and the like, can be conveniently combined with the related technology of coal chemical industry, and hasHas great economic and environmental benefits.
DRM reactions have attracted attention from researchers as early as 1888. In 1928, fischer and Tropsch have developed systematic studies on the performance and soot behavior of DRM reactions on Ni-based and Co-based catalysts. However, this reaction is not emphasized enough in the next few decades, and there are few related studies. Until 1991 Ashcroft et al reported on Nature that the reaction can produce lower H 2 The synthesis gas of the/CO ratio, more and more researchers have paid attention again to this reaction. During the last decades, long-felt developments have been made regarding the development of DRM reaction catalysts and the knowledge of the related scientific problems.
The methane dry gas reforming catalyst reported in the research is mainly a noble metal catalyst and a transition metal catalyst, wherein the nickel-based catalyst is widely concerned due to excellent performance, abundant reserve, low price and easy availability, and is the methane dry gas reforming catalyst with the most industrial prospect. However, particle sintering and carbon deposition are serious problems faced by nickel-based catalysts, which tend to result in catalyst deactivation, reactor plugging. For example, the dispersion and anchoring of nickel are increased by using a carrier with large specific surface area and developed pore structure; through a limited-domain strategy, the stability of nickel particles is improved through coating the nickel particles, and the catalytic activation of CO is improved through adding an auxiliary agent 2 Reducing carbon deposition, etc. (CN 104841442 A,CN 105688916A) by facilitating the carbon elimination process. However, the problems of complex preparation process, poor anti-carbon effect, difficulty in combining high activity and anti-carbon performance and the like still exist. Therefore, designing and constructing a high-temperature sintering-resistant Ni-based catalyst has become one of the most active research directions in the field of international catalysis and materials at present. The research and development of a novel anti-sintering strategy and the development of a universal anti-sintering theory have great theoretical and practical significance for the design of the catalyst.
However, no report on the industrialization success of the related technology of methane dry reforming is available at home and abroad at present, and the reason is mainly that the Ni-based catalyst used in the reaction is easy to accumulate carbon and sinter, so that the long-period operation of the catalyst is greatly limited. How to effectively solve or overcome the difficult problem of carbon deposition and sintering of the catalyst is the key of industrialization of the process.
Disclosure of Invention
The invention further researches the reasons for the problems of the catalyst in the dry reforming reaction of methane, wherein the thermodynamic analysis of the dry gas shows that the carbon deposit quantity is reduced along with the increase of the reaction temperature, and when the reaction temperature is higher than 900 ℃, the carbon deposit is not generated any more. Secondly, as can be seen from the temperature CFD simulation of the fixed bed catalyst, the temperature from the inner wall of the reactor to the center of the axial catalyst bed layer is in an inverted parabolic trend, namely the overall temperature of the catalyst bed layer is uneven and the temperature of the axial center is lowest; meanwhile, the dry gas reforming reaction is a strong heat absorption process, so that the non-uniformity of the temperature distribution of the bed layer is further aggravated, the non-uniformity can lead to less or no carbon deposition of the catalyst close to the wall surface, and the serious carbon deposition of a part far away from the catalyst.
In order to solve the problem, the invention develops an integral coating metal catalytic reactor (namely, active components are directly loaded on the inner wall of a metal pipe), so that the axial temperature difference is effectively overcome, and carbon deposition is avoided.
The technical scheme of the invention is as follows:
in one aspect, the invention provides a metal catalytic reactor, comprising a metal tube and a catalyst active component, wherein the catalyst active component is directly coated and doped on the contact surface of the metal tube and a raw material, a catalytic dopant thin layer is formed on the contact surface of the metal tube and a reaction raw material, the catalyst active component and a base metal on the contact surface of the metal tube form a catalyst, the coated and doped catalyst has a catalytic function, the metal reactor is called a catalytic reactor, and the integrated catalytic reactor has the dual functions of a reactor and a catalyst. The contact surface refers to the inner wall or the outer wall of the metal pipe.
Preferably, the thickness of the dopant-coated thin layer is 100 nm-1 mm, preferably 200 nm-0.5 mm, more preferably 500 nm-200 microns, still more preferably 1 micron-50 microns.
Preferably, the doping is lattice doping; lattice doping refers to the formation of chemical bonds between the doped metal element and some elements in the matrix metal material, such that the doped metal element is confined to the lattice of the doped matrix, resulting in specific catalytic properties.
Preferably, the active component of the catalyst is a metal element or a mixture of metal elements and non-metal elements, and the metal doping amount in the metal element doped catalyst is 0.1wt.% to 20wt.%, preferably 0.1wt.% to 15wt.%, and more preferably 0.1wt.% to 5wt.%, based on 100% of the total weight of the dopant thin layer.
Preferably, the coating doping metal exists in one or more of the group consisting of oxides, carbides, nitrides, silicides, and alloys.
Preferably, the coating doping metal element includes: one or more of magnesium, aluminum, calcium, barium, titanium, manganese, vanadium, niobium, tungsten, molybdenum, chromium, iron, cobalt, nickel, copper, zinc, tin, gallium, zirconium, lanthanum, cerium, ruthenium, gold, palladium or platinum. Preferably one or more of aluminum, barium, titanium, manganese, vanadium, niobium, tungsten, molybdenum, chromium, iron, cobalt, nickel, copper, zinc, gallium, gold, lanthanum, cerium, ruthenium, gold, palladium or platinum.
Preferably, the coating of the precursor of the doped metal element (the presence state of the pre-doped metal element) includes: one or more of nitrate, soluble chloride and soluble sulfate.
Preferably, the metal catalytic reactor, wherein the material of the base metal tube comprises: GH1015, GH1040, GH1131, GH1140, GH2018, GH2036, GH2038, GH2130, GH2132, GH2135, GH2136, GH2302, GH2696, GH3030, GH3039, GH3044, GH3028, GH3128, GH3536, GH605, GH600, GH4033, GH4037, GH4043, GH4049, GH4133B, GH4169, GH4145, hastelloy G-30, hastelloy G-35, hastelloy N, hastelloy S, incon 600, incon 601GC, incon 617, incon 622, incon 625LCF Inconel 671, inconel 672, inconel 686, inconel 690, inconel 706, inconel 718SPF, inconel 725, inconel X-750, inconel 751, inconel 754, inconel 758, inconel 783, incoloy DS, incoloy 800H, incoloy 802, incoloy 803, incoloy 804, incoloy 825, incoloy 903, incoloy 907, incoloy 909, incoloy 925, incoloy MA956, incoloy a-286, incoloy 25-6Mo, monel 400, combinations of two or more.
In another aspect, the present invention provides a method for preparing the metal catalytic reactor, wherein the metal catalytic reactor is prepared by adopting the following coating doping technology; the coating doping technology is one or more of electrochemical deposition method, conversion deposition precipitation method, electroplating, chemical plating, electrochemical deposition method, conversion deposition precipitation method, chemical vapor deposition method (CVD) and physical vapor deposition method (PVD).
The following preparation process aims to improve the dispersity and adhesion of metal elements on the surface of a metal substrate.
Preferably, the electrochemical deposition method specifically comprises the following steps:
(1) Steaming the base pipe in 10-20wt.% NaOH or KOH solution for 1-2h, deoiling, washing, and air drying at normal temperature;
(2) The matrix pipe processed in the step (1) is heated to N 2 Heating in atmosphere at 300-500 deg.c for 1-2 hr to form anticorrosive conducting film layer;
(3) Preparing an aqueous solution or an organic solution of a metal element precursor doped with a specific concentration at room temperature, preparing the pH value of the solution to 3.3-6.5, immersing a metal pipe to be doped in the precursor solution, connecting the metal pipe to be doped with the precursor solution as a cathode, taking platinum as an anode, adjusting the distance between the cathode and the anode to be 2-5cm after connecting a circuit, regulating a direct current stabilized power supply, maintaining a constant current mode, keeping the current to be 5 mA-0.5A, cleaning the surface of a substrate material with deionized water for 2-3 times after the electrodeposition time is 0.5-2 hours, and then drying and placing the substrate material at 60 ℃ for 30min to finish the electrodeposition process.
Preferably, the conversion deposition precipitation method specifically comprises the following steps:
(1) Steaming the base pipe in 10-20wt.% NaOH or KOH solution for 1-2h, deoiling, washing, and air drying at normal temperature;
(2) The matrix pipe processed in the step (1) is heated to N 2 Heating is carried out in the atmosphere, the temperature is controlled,heating at 300-500 deg.c for 1-2 hr to form anticorrosive conducting film layer;
(3) Preparing an aqueous solution or an organic solution of a metal element precursor doped with a specific concentration at room temperature, adjusting the pH value of the prepared solution to 3.8-7.2, immersing a metal pipe to be doped in the precursor solution to enable the solution to be in a flowing state in the metal pipe to be deposited, and further adding 10-20wt.% of H 2 O 2 And (3) carrying out conversion deposition precipitation, wherein the deposition time is 0.5-5 hours, and obtaining the metal reactor after the deposition is completed.
Preferably, the metal element precursor used in the electrodeposition doping technology is one or more than two of metal nitrate, soluble halide, soluble sulfate, soluble carbonate, soluble phosphate, soluble C methoxide, soluble ethoxide, soluble formate and soluble acetate.
Preferably, the metal element precursor used in the conversion deposition precipitation technology is one or more of metal chloride, methoxide, ethoxide, formate and acetate.
In yet another aspect, the present invention provides a catalytic conversion of natural gas and CO using the above metal catalytic reactor 2 A method for preparing synthesis gas by dry reforming.
Preferably, the reaction feed gas composition includes, in addition to methane and carbon dioxide, possibly one or both of an inert atmosphere gas and a non-inert atmosphere gas; the inert atmosphere gas is one or more than two of nitrogen, helium and argon, and the volume content of the inert atmosphere gas in the reaction raw material gas is 0-95%; the non-inert atmosphere gas is one or a mixture of more than two of carbon monoxide, hydrogen, carbon dioxide, water and alkane with the C number of 2-4, and the volume content ratio of the non-inert atmosphere gas to methane is 0-10%; the total volume content of methane and carbon dioxide in the reaction raw material gas is 5-100%, and the volume content ratio of methane and carbon dioxide is 0.5-2, preferably 0.9-1.1.
Preferably, the reaction process is in a continuous flow reaction mode. Continuous flow reaction mode: the reaction temperature is 600-950 ℃, preferably 700-950 ℃; the reaction pressure is 0.05-1 MPa, preferably 0.1-0.5 MPa; the flow rate of the reaction raw material gas is preferably 1-100L/min.
Advantageous effects
The invention mixes the active metal component into the special nickel-chromium alloy steel with unique shape to make the integrated catalytic reactor, so that the catalyst and the reactor are integrated. This method has some advantages:
(1) Compared with the quartz and silicon carbide doping process, the integrated metal alloy catalytic reactor has the characteristics of simple process, milder condition, more uniform dispersion of metal active components and the like;
(2) Compared with the traditional granular catalyst, the reaction process avoids the axial or radial temperature difference of the catalyst. Because the catalyst itself has poor thermal conductivity after being filled in the reactor, and the radial temperature difference of the bed layer increases (the temperature gradually decreases from the reactor wall to the center), more heat is required to be supplied to the catalyst at the center to reach the reaction temperature, and as a result, the problems of heat loss and more side reactions in the near-wall section (high temperature end) are caused.
(3) Compared with the granular catalyst, the catalyst bed layer is not provided, so that the pressure drop of the bed layer is avoided, and the reaction process is smoother.
(4) Compared with the particle catalyst, the problem of amplification is overcome.
(5) The invention catalytically converts natural gas and CO by the prepared metal catalytic reactor 2 The synthesis gas is prepared by dry reforming, and has the characteristics of high catalyst stability, high methane and carbon dioxide conversion rate, high product selectivity, low carbon deposition, good process repeatability, safe and reliable operation and the like. Wherein the conversion rate of methane is 80-96%; the carbon dioxide conversion rate is 80-98%; CO selectivity is as follows >99 percent; low carbon deposition. The method has the characteristics of long service life of the catalyst, high methane and carbon dioxide conversion rate, low carbon deposition, easy separation of products, no need of amplifying the catalyst, small industrialization difficulty, good process repeatability, safe and reliable operation and the like, and has wide industrial application prospect.
Detailed Description
The following examples are merely illustrative of the invention,the scope of the invention should be construed as including the full breadth of the claims and not only the embodiment(s). In addition, the concentration of NaOH solution, the concentration of metal precursor solution and H described in the following examples and comparative examples 2 O 2 The concentration of the solution refers to the mass percent concentration.
1. Preparation of catalytic reactor
Example 1
Selecting Inconel 601 alloy pipe (inner diameter 10, outer diameter 14, id10od 14), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Then treating for 2.5 hours in high-purity hydrogen atmosphere at 500 ℃ to obtain a blank by a blank metal catalytic reactorInconel 601 metal catalytic reactor.
Example 2
Electrochemical deposition process
Selecting GH3030 alloy pipe (15 inner diameter and 20 outer diameter, id15od 20), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Formulation of 10% RuCl 3 2L of aqueous solution, adding 20ml of 0.1mol/L citric acid, adjusting pH to 4.5 by hydrochloric acid, connecting a 0.5mm platinum wire as an anode, connecting a GH3030 alloy pipe as a cathode, and connecting a power supply, wherein the distance between the platinum wire and the alloy pipe is 2cm. And adopting a constant current mode, setting the current to be 20mA, and depositing for 0.5 hour to obtain the Ru deposited GH3030 alloy pipe. Then treating for 2 hours in high-purity hydrogen atmosphere with the temperature of 500 ℃, forming a Ru dopant thin layer with the thickness of 100nm on the contact surface of a reactor, and naturally cooling to obtain RuGH3030 metal catalytic reactor, wherein the doping amount of Ru is 0.5wt.%.
Example 3
Electrochemical deposition process
Selecting GH3030 alloy pipe (inside diameter 12, outside diameter 16, id12od 16), steaming in 15% NaOH solution for 1 hr, deoiling, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Formulation of 10% RuCl 3 And 15% FeCl 3 30ml of 0.1mol/L citric acid is added, the pH is regulated to 4.5 by hydrochloric acid, a platinum wire with the thickness of 0.5mm is connected as an anode, a GH3030 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 2cm. And adopting a constant current mode, setting the current to be 25mA, and depositing for 0.5 hour to obtain the GH3030 alloy pipe deposited by Ru and Fe. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃, forming a Ru and Fe dopant thin layer with the thickness of 110nm on the contact surface of the reactor, and then naturally cooling to obtain Ru-Fe GH3030 metal catalytic reactor, wherein the doping amounts of Ru and Fe are 0.8wt.% and 1wt.%, respectively.
Example 4
Electrochemical deposition process
Selecting Inconel 601 alloy pipe (inner diameter 10, outer diameter 14, id10od 14), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 20% Co (NO) 3 ) 2 And 15% FeCl 3 Adding 20ml of 0.1mol/L citric acid, adjusting the pH to 3.8 by hydrochloric acid, connecting a 0.5mm platinum wire as an anode, connecting an Inconel 601 alloy pipe as a cathode, connecting a power supply, and keeping the distance between the platinum wire and the alloy pipe to be 2cm. And adopting a constant current mode, setting the current to be 25mA, and depositing for 1 hour to obtain the Co and Fe deposited Inconel 601 alloy pipe. Then treating for 2.5 hours in high-purity hydrogen atmosphere at 500 ℃ to form Co and Fe dopant thin layers with the thickness of 110nm on the contact surface of the reactor, and then naturally cooling to obtain the Co-FeInconel 601 metal catalytic reactor, wherein the doping levels of Co and Fe are 1.5wt.% and 0.6wt.%, respectively.
Example 5
Electrochemical deposition process
Selecting Inconel 601 alloy pipe (inner diameter 10, outer diameter 14, id10od 14), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 20% Ni (NO) 3 ) 2 And 15% Co (NO) 3 ) 2 19ml of 0.1mol/L citric acid is added, the pH is regulated to 3.8 by nitric acid, a 0.5mm platinum wire is connected as an anode, an Inconel 601 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 2cm. And adopting a constant current mode, setting the current to be 30mA, and depositing for 1 hour to obtain the Co and Ni deposited Inconel 601 alloy pipe. Then treating for 2.5 hours in high-purity hydrogen atmosphere at 500 ℃ to form Co and Ni dopant thin layers with the thickness of 110nm on the contact surface of the reactor, and then naturally cooling to obtain the Ni-CoInconel 601 metal catalytic reactor, wherein the doping levels of Ni and Co are 1.5wt.% and 1.1wt.%, respectively.
Example 6
Electrochemical deposition process
Selecting Inconel 600 alloy tube (inner diameter 16 outer diameter 20, id16od 20), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Formulation of 10% RuCl 3 And 15% Cu (NO) 3 ) 2 Adding 32ml of 0.1mol/L citric acid, adjusting pH to 4.1 with nitric acid, connecting a 0.5mm platinum wire as an anode, connecting an Inconel 600 alloy pipe as a cathode, connecting a power supply, and keeping the distance between the platinum wire and the alloy pipe to be 2cm. Adopting a constant current mode, setting the current to 25mA, and depositing for 1 hour to obtain the Ru and Cu deposited Inconel 600 alloy tube And (3) material. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form Ru and Cu dopant thin layers with the thickness of 120nm on the contact surface of the reactor, and then naturally cooling to obtain Ru-CuInconel 600 metal catalytic reactor, wherein the doping amounts of Ru and Cu are 0.5wt.% and 0.6wt.%, respectively.
Example 7
Electrochemical deposition process
An Incoloy 800 alloy pipe (inner diameter 15 outer diameter 20, id15od 20) is selected, and is steamed in 15% NaOH solution for 1h to perform deoiling treatment, distilled water is washed clean, dried at normal temperature, and then N with continuous flow of 200ml/min at 300 DEG C 2 And treating for 2 hours in the atmosphere. Preparation of 20% Ni (NO) 3 ) 2 And 15% Co (NO) 3 ) 2 36ml of 0.1mol/L citric acid is added, the pH is regulated to 4.3 by nitric acid, a 0.5mm platinum wire is connected as an anode, an Incoloy 800 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 1cm. And adopting a constant current mode, setting the current to be 80mA, and depositing for 1 hour to obtain the Ni and Co deposited Incoloy 800 alloy pipe. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form Ni and Co dopant thin layers with thickness of 150nm on the contact surface of the reactor, and then naturally cooling to obtain Ni-Co Incoloy 800 metal catalytic reactor, wherein the doping amounts of Ni and Co are 2wt.% and 1.2wt.%, respectively.
Example 8
Electrochemical deposition process
Selecting Monel 400 alloy pipe (inner diameter 15 outer diameter 20, id15od 20), steaming in 15% NaOH solution for 1 hr, deoiling, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 20% Ni (NO) 3 ) 2 And 15% Co (NO) 3 ) 2 Is added with 41ml of 0.1mol/L lemonThe pH of the citric acid and nitric acid is adjusted to 4.3, a 0.5mm platinum wire is connected as an anode, an Incoloy 800 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 1cm. And adopting a constant current mode, setting the current to be 80mA, and depositing for 1 hour to obtain the Ni and Co deposited Monel 400 alloy pipe. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form Ni and Co dopant thin layers with thickness of 150nm on the contact surface of the reactor, and then naturally cooling to obtain Ni-CoMonel 400 metal catalytic reactor, wherein the doping amounts of Ni and Co are 2wt.% and 1.2wt.%, respectively.
Example 9
Electrochemical deposition process
Selecting Inconel X-750 alloy pipe (inner diameter 15 outer diameter 20, id15od 20), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 20% Ni (NO) 3 ) 2 And 15% Zn (NO) 3 ) 2 31ml of 0.1mol/L citric acid is added, the pH is regulated to 4.3 by nitric acid, a 0.5mm platinum wire is connected as an anode, an Incoloy 800 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 1cm. And adopting a constant-current mode, setting the current to be 100mA, and depositing for 1 hour to obtain the Ni and Zn deposited Inconel X-750 alloy pipe. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form Ni and Zn dopant thin layers with the thickness of 180nm on the contact surface of the reactor, and then naturally cooling to obtain the Ni-ZnInconel X-750 metal catalytic reactor, wherein the doping amounts of Ni and Zn are 2wt.% and 1.2wt.%, respectively.
Example 10
Electrochemical deposition process
Hastelloy G-30 alloy pipe (inner diameter 16 outer diameter 20, id16od 20) is selected, and is steamed in 15% NaOH solution for a period of timeDeoiling for 1 hr, washing with distilled water, air drying at normal temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 25% Ni (NO) 3 ) 2 And 15% La (NO) 3 ) 3 26ml of 0.1mol/L citric acid is added, the pH is regulated to 4.3 by nitric acid, a 0.5mm platinum wire is connected as an anode, a Hastelloy G-30 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 1cm. And adopting a constant current mode, setting the current to be 100mA, and depositing for 1 hour to obtain the Ni and La deposited Hastelloy G-30 alloy pipe. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form Ni and La dopant thin layers with the thickness of 180nm on the contact surface of the reactor, and then naturally cooling to obtain Ni-La Hastelloy G-30 metal catalytic reactor, wherein the doping amounts of Ni and La are 2.5wt.% and 1.6wt.%, respectively.
Example 11
Electrochemical deposition process
Selecting Inconel 600 alloy pipe (inner diameter 10, outer diameter 14, id10od 14), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 10% chloroauric acid and 15% La (NO 3 ) 3 35ml of 0.1mol/L citric acid is added, the pH is regulated to 4.1 by nitric acid, a platinum wire with the thickness of 0.5mm is connected as an anode, a GH2130 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 2cm. And adopting a constant current mode, setting the current to be 30mA, and depositing for 1 hour to obtain the deposited Inconel 600 alloy pipe with Au and La. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form Au and La dopant thin layers with the thickness of 120nm on the contact surface of the reactor, and then naturally cooling to obtain Ni-LaInconel 600 metal catalytic reactor, wherein the doping amounts of Au and La are 0.5wt.% and La, respectively0.8wt.％。
Example 12
Electrochemical deposition process
Selecting GH4169 alloy pipe (inner diameter 12 outer diameter 18, id12od 18), steaming in 15% NaOH solution for 1 hr, deoiling, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 25% Ni (NO) 3 ) 2 、16％Al(NO 3 ) 3 And 15% Fe (NO) 3 ) 3 30ml of 0.1mol/L citric acid is added, the pH is regulated to 4.0 by nitric acid, a 0.5mm platinum wire is connected as an anode, a GH4169 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 2cm. And adopting a constant current mode, setting the current to be 100mA, and depositing for 1 hour to obtain the GH4169 alloy pipe deposited by Ni, al and Fe. Then treating for 2 hours in high-purity hydrogen atmosphere with the temperature of 500 ℃, forming a thin layer of Ni, al and Fe dopant with the thickness of 160nm on the contact surface of a reactor, and then naturally cooling to obtain the Ni-Al-FeGH4169 metal catalytic reactor, wherein the doping amounts of Ni, al and Fe were 2.5wt.%, 1.5wt.% and 1.2wt.%, respectively.
Example 13
Electrochemical deposition process
An Incoloy903 alloy pipe (inner diameter 14, outer diameter 18, id14od 18) is selected, and is steamed in 15% NaOH solution for 1h to remove oil, distilled water is washed clean, dried at normal temperature, and then N with continuous flow of 200ml/min at 300 DEG C 2 And treating for 2 hours in the atmosphere. Preparation of 25% La (NO) 3 ) 3 、15％Ce(NO 3 ) 3 And 15% Fe (NO) 3 ) 3 22ml of 0.1mol/L citric acid is added, the pH is regulated to 3.6 by nitric acid, a 0.5mm platinum wire is connected as an anode, an Incoloy903 alloy pipe is connected as a cathode, a power supply is connected, and the distance between the platinum wire and the alloy pipe is 2cm. And adopting a constant current mode, setting the current to be 200mA, and depositing for 1 hour to obtain the Incoloy903 alloy pipe deposited by La, ce and Fe. Then at a temperature of Treating at 500 deg.c in high purity hydrogen atmosphere for 2 hr to form 180nm thick doped Ni, al and Fe layer, and naturally cooling to obtain La-Ce-Fe filmIncoloy 903 metal catalytic reactor, wherein the doping amounts of La, ce and Fe are 3wt.%, 2.8wt.% and 1.1wt.%, respectively.
Example 14
Deposition by conversion
An Incoloy800 alloy pipe (inner diameter 12 outer diameter 18, id12od 18) is selected, and is steamed in 15% NaOH solution for 1h to perform deoiling treatment, distilled water is washed clean, dried at normal temperature, and then N with continuous flow of 200ml/min at 300 DEG C 2 And treating for 2 hours in the atmosphere. Preparation of 10% Ce (NO) 3 ) 2 25ml of 0.1mol/L citric acid and 12ml of 10% H are added 2 O 2 . And (3) after the aqueous solution is circularly deposited for 1 hour, obtaining the Ce deposited Incoloy800 alloy pipe. Then treating for 2 hours in high-purity hydrogen atmosphere with the temperature of 500 ℃, forming a Ce dopant thin layer with the thickness of 100nm on the contact surface of a reactor, and then naturally cooling to obtain CeIncoloy800 metal catalytic reactor, wherein the doping amount of Ce was 0.8wt.% respectively.
Example 15
Deposition by conversion
Selecting GH4169 alloy pipe (inside diameter 14, outside diameter 18, id14od 18), steaming in 15% NaOH solution for 1 hr, deoiling, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 10% Ce (NO) 3 ) 2 And 20% Fe (NO) 3 ) 3 20ml of 0.1mol/L citric acid and 22ml of 10% H are added 2 O 2 . And (3) after the aqueous solution is circularly deposited for 1 hour, obtaining the Ce-deposited GH4169 alloy pipe. Then treated for 2 hours in a high-purity hydrogen atmosphere at a temperature of 500 DEG CForming a Ce and Fe dopant thin layer with the thickness of 100nm on the contact surface of the reactor, and naturally cooling to obtain the Ce-FeGH4169 metal catalytic reactor, wherein the doping amounts of Ce and Fe are 1.2wt.% and 1.1wt.%, respectively.
Example 16
Deposition by conversion
An Incoloy 800 alloy pipe (inner diameter 14 outer diameter 18, id14od 18) is selected, and is steamed in 15% NaOH solution for 1h to perform deoiling treatment, distilled water is washed clean, dried at normal temperature, and then N with continuous flow of 200ml/min at 300 DEG C 2 And treating for 2 hours in the atmosphere. Preparation of 20% La (NO) 3 ) 3 、15％Ce(NO 3 ) 3 And 20% Fe (NO) 3 ) 3 26ml of 0.1mol/L citric acid and 22ml of 10% H were added 2 O 2 . After 1.5 hours of the aqueous solution circulating deposition, the Incoloy 800 alloy pipe deposited by La, ce and Fe is obtained. Then treating for 2 hours in high-purity hydrogen atmosphere with the temperature of 500 ℃, forming a La, ce and Fe dopant thin layer with the thickness of 100nm on the contact surface of a reactor, and then naturally cooling to obtain the La-Ce-Fe Incoloy800 metal catalytic reactor, wherein the doping amounts of La, ce and Fe are 1.6wt.%, 1.0wt.% and 1.1wt.%, respectively.
Example 17
Deposition by conversion
Selecting Inconel 725 alloy pipe (inner diameter 14 outer diameter 18, id14od 18), steaming in 15% NaOH solution for 1 hr, deoiling, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 20% Al (NO) 3 ) 3 、15％Ce(NO 3 ) 3 And 20% Fe (NO) 3 ) 3 26ml of 0.1mol/L citric acid and 22ml of 10% H were added 2 O 2 . The aqueous solution was cycled to deposit 1.After 5 hours, an Inconel 725 alloy tube deposited with La, ce and Fe was obtained. Then treating for 2 hours in high-purity hydrogen atmosphere with the temperature of 500 ℃, forming a thin layer of Al, ce and Fe dopant with the thickness of 140nm on the contact surface of a reactor, and then naturally cooling to obtain the Al-Ce-FeInconel 725 metal catalytic reactor, wherein the doping amounts of Al, ce and Fe are 1.4wt.%, 1.1wt.% and 1.4wt.%, respectively.
Example 18
Deposition by conversion
Selecting Inconel 718 alloy pipe (inner diameter 21 outer diameter 25, id21od 25), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 20% Ni (NO) 3 ) 2 And 15% Zn (NO) 3 ) 2 30ml of 0.1mol/L citric acid and 50ml of 10% H were added 2 O 2 . After 1.5 hours of cyclic deposition of the aqueous solution, ni and Zn deposited Inconel 718 alloy tubing was obtained. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form 130nm thick Ni and Zn dopant thin layer on the contact surface of the reactor, and then naturally cooling to obtain Ni-ZnInconel 718 metal catalytic reactor, wherein the doping amounts of Ni and Zn are 4.5wt.% and 1.0wt.%, respectively.
Example 19
Deposition by conversion
Selecting Inconel 600 alloy pipe (inner diameter 10, outer diameter 14, id10od 14), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And treating for 2 hours in the atmosphere. Preparation of 20% La (NO) 3 ) 3 、15％Ce(NO 3 ) 3 And 20% Fe (NO) 3 ) 3 26ml of 0.1mol/L of aqueous solution 2L of (B)Citric acid, 22ml of 10% H was added 2 O 2 . After 1.5 hours of the cyclic deposition of the aqueous solution, the Inconel 600 alloy pipe deposited by La, ce and Fe is obtained. Then treating for 2 hours in high-purity hydrogen atmosphere with the temperature of 500 ℃, forming a La, ce and Fe dopant thin layer with the thickness of 100nm on the contact surface of a reactor, and then naturally cooling to obtain the La-Ce-Fe Inconel 600 metal catalytic reactor, wherein the doping amounts of La, ce and Fe were 1.6wt.%, 1.0wt.% and 1.1wt.%, respectively.
Example 20
Deposition by conversion
Selecting GH600 alloy pipe (inner diameter 10 outer diameter 14, id10od 14), steaming in 15% NaOH solution for 1 hr, deoiling, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And heating treatment is carried out for 2 hours in the atmosphere. Preparation of 20% Ni (NO) 3 ) 2 And 15% Ce (NO) 3 ) 3 100ml of 0.1mol/L citric acid was added, and 40ml of 10% H was added 2 O 2 . And (3) after the aqueous solution is circularly deposited for 2 hours, obtaining the GH600 alloy pipe deposited by Ni and Ce. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃, forming a Ni and Ce dopant thin layer with the thickness of 100nm on the contact surface of the reactor, and then naturally cooling to obtain the Ni-CeGH600 metal catalytic reactor, wherein the doping amounts of Ni and Ce are 8.5wt.% and 2.0wt.%, respectively.
Example 21
Deposition by conversion
Selecting Hastelloy G-35 alloy pipe (inner diameter of 10, outer diameter of 14, id of 10od of 14), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing at 300 deg.C and N of 200ml/min 2 And heating treatment is carried out for 2 hours in the atmosphere. Preparation of 20% Ni (NO) 3 ) 2 And 25% Fe (NO) 3 ) 3 100ml of 0.1mol/L citric acid and 35ml of 10% H are added 2 O 2 . After 3 hours of cyclic deposition of the aqueous solution, a Hastelloy G-35 alloy pipe with deposited Ni and Fe is obtained. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form Ni and Fe dopant thin layers with 130nm thickness on the contact surface of the reactor, and then naturally cooling to obtain the Ni-CeHastelloy G-35 metal catalytic reactor, wherein the doping amounts of Ni and Fe were 8.5wt.% and 7.8wt.%, respectively.
Example 22
Deposition by conversion
Selecting Monel 400 alloy pipe (inner diameter 12 outer diameter 16, id12od 16), steaming in 15% NaOH solution for 1 hr, deoiling, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And heating treatment is carried out for 2 hours in the atmosphere. Preparation of 20% Ba (NO) 3 ) 2 And 15% Fe (NO) 3 ) 3 33ml of 0.1mol/L citric acid and 40ml of 10% H are added 2 O 2 . And (3) circularly depositing the aqueous solution for 1.5 hours to obtain the Monel 400 alloy pipe deposited by Ba and Fe. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form a Ba and Fe dopant thin layer with the thickness of 120nm on the contact surface of the reactor, and then naturally cooling to obtain the Ba-Fe Monel 400 metal catalytic reactor, wherein the doping amounts of Ba and Fe are 2.2wt.% and 3wt.%, respectively.
Example 23
Deposition by conversion
Selecting GH1015 alloy pipe (inner diameter 10 outer diameter 14, id10od 14), steaming in 15% NaOH solution for 1 hr, deoiling, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300deg.C 2 And heating treatment is carried out for 2 hours in the atmosphere. Preparation of 15% Ni (NO) 3 ) 2 And 25% Mg (NO) 3 ) 2 45ml of 0.1mol/L citric acid and 45ml of 10% H were added 2 O 2 . And (3) after the aqueous solution is circularly deposited for 3 hours, obtaining the GH1015 alloy pipe deposited by Ni and Mg. Then treating for 2 hours in high-purity hydrogen atmosphere at 500 ℃ to form a Ni and Mg dopant thin layer with the thickness of 120nm on the contact surface of the reactor, and then naturally cooling to obtain the Ni-MgGH1015 metal catalytic reactors, wherein the doping amounts of Ni and Mg are 5.2wt.% and 4.6wt.%, respectively.
Example 24
Deposition by conversion
Selecting Inconel 783 alloy pipe (inner diameter 12 outer diameter 16, id12od 16), steaming in 15% NaOH solution for 1 hr to deoil, washing with distilled water, air drying at room temperature, and continuously flowing 200ml/min N at 300 deg.C 2 And heating treatment is carried out for 2 hours in the atmosphere. Preparation of 20% Ni (NO) 3 ) 2 、10％Mn(NO 3 ) 2 、15％Fe(NO 3 ) 3 And 10% Zn (NO 3) 2 in water 2L, 40ml of 0.1mol/L citric acid was added, and 50ml of 10% H was added 2 O 2 . After 3 hours of the cyclic deposition of the aqueous solution, the Inconel 783 alloy pipe deposited by Ni, mn, fe and Zn is obtained. Then treating for 2 hours in high-purity hydrogen atmosphere with the temperature of 500 ℃, forming a thin layer of Ni, mn, fe and Zn dopant with the thickness of 160nm on the contact surface of a reactor, and then naturally cooling to obtain the Ni-Mn-Fe-ZnInconel 783 metal catalytic reactor, wherein the doping amounts of Ni, mn, fe and Zn are 5wt.%, 2.5wt.%, 3wt.%, and 1.5wt.%, respectively.
Directly catalyzing methane and carbon dioxide dry gas to be reformed into synthesis gas under continuous flow condition
All of the catalytic reactors described above are used directly without loading with catalyst.
All reaction examples are in successionThe continuous flow micro-reaction device is provided with a gas mass flowmeter, a gas deoxidizing and dehydrating pipe and an online product analysis chromatograph (the tail gas of the reactor is directly connected with a quantitative valve of the chromatograph for periodic real-time sampling analysis). N in the reaction feed gas unless otherwise specified 2 As an internal standard gas. On-line product analysis was performed using an Agilent 7890B gas chromatograph equipped with both FID and TCD detectors, wherein the FID detector was equipped with an HP-1 capillary column to analyze lower olefins, lower alkanes, and aromatics; the TCD detector was equipped with a Hayesep D packed column to analyze lower olefins, lower alkanes, methane, hydrogen and internal standard nitrogen. Methane conversion, product selectivity and carbon deposit, according to the carbon balance before and after the reaction, the calculation formula is as follows:
The conversion rate of methane is high, and the methane is not converted,
CO 2 the conversion rate of the catalyst is higher than that of the catalyst,
wherein,methane and carbon dioxide peak areas of the tail gas outlet after reaction on the detector; />Nitrogen peak area of tail gas outlet after reaction on TCD detector; />Methane and carbon dioxide peak areas at room temperature on the TCD detector; />Methane peak area at room temperature on TCD detector.
The selectivity of the CO is such that,
wherein,total number of carbon atoms entering the reactor; />The total carbon number of methane entering the reactor;the total carbon number of methane entering the reactor; />The relative correction factors of methane and nitrogen on the TCD detector; />The relative correction factor of ethane and nitrogen on the TCD detector; sel. CO Selectivity for CO product;
each of the products in the examples below was a product detectable by gas chromatography.
Comparative example
Using 1.6 m blanks without doped metal active components1.5wt.% Ni-1.1wt.% Co/SiO for 5g of 20-40 mesh was added to an Inconel 601 metal reactor 2 After 0.5L/min Ar gas replaces air in the reactor for about 30 minutes, the powder catalyst keeps the Ar flow rate unchanged, and the temperature is programmed to rise to 900 ℃ from room temperature at the heating rate of 6 ℃/min, and 40% CH is regulated at the same time 4 /40％CO 2 /20％N 2 (volume content, same below), flow rate of reaction feed gas was 2L/min, on-line analysis was started after 30 minutes, stability test was then performed for 200 hours, and carbon deposition caused reactor clogging to stop reaction Analysis results show that the methane conversion rate is 80% after 30 minutes, and the carbon dioxide conversion rate is 82%; after 200 hours, the methane conversion rate is reduced to 50%, the carbon dioxide conversion rate is reduced to 62%, and the whole CO/H is reduced 2 ＝0.9～1。
Application example 1
Using 1.6 m blanks without doped metal active componentsInconel 601 metal catalytic reactor, after 0.5L/min Ar gas replaced the air in the reactor for about 30 minutes, keep Ar flow rate unchanged, program temperature rise from room temperature to 900 ℃ at a temperature rise rate of 6 ℃/min, and adjust 40% CH at the same time 4 /40％CO 2 /20％N 2 The flow rate of the reaction feed gas (volume content, same as below) was 2L/min, and the analysis result showed that the conversion of methane was 5%, the conversion of carbon dioxide was 8.5% and the selectivity of CO was 96%.
Application example 2
In the case of using 1.6 m RuGH3030 Metal catalytic reactor (catalytic reactor preparation example 2), after replacing the air in the reactor with 0.5L/min Ar for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 800℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 75%, the conversion rate of carbon dioxide is 78%, the selectivity of CO is 99%, and the selectivity of CO/H is shown as follows 2 ＝1。
Application example 3
In the case of using 1.6 m RuGH3030 Metal catalytic reactor (catalytic reactor preparation example 2), after replacing the air in the reactor with 0.5L/min Ar for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 850℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 84%, the conversion rate of carbon dioxide is 85%, the selectivity of CO is 99%, and the selectivity of CO/H is as follows 2 ＝1。
Application example 4
In the case of using 1.6 m RuGH3030 Metal catalytic reactor (catalytic reactor preparation example 2), after replacing the air in the reactor with 0.5L/min Ar for about 30 minutes, the Ar flow rate was kept unchanged, the temperature was programmed from room temperature to 900℃at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 95%, the conversion rate of carbon dioxide is 97%, the selectivity of CO is 99%, and the selectivity of CO/H is that 2 ＝1。
Application example 5
Use of 1.6 m Ru-FeGH3030 Metal catalytic reactor (catalytic reactor preparation example 3), after replacing the air in the reactor with 0.5L/min Ar for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 850℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 90%, the conversion rate of carbon dioxide is 92%, the selectivity of CO is 99% and the selectivity of CO/H is higher than that of CO/H 2 ＝1。
Application example 6
Using 1.6 m Co-FeInconel 601 metal catalytic reactor (catalytic reactor preparation example 4), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was maintained constant at 6℃per minute from room temperatureThe temperature rise rate is programmed to 900 ℃ while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 90%, the conversion rate of carbon dioxide is 92%, the selectivity of CO is 99% and the selectivity of CO/H is higher than that of CO/H 2 ＝1。
Application example 7
Using Ni-CoInconel 601 metal catalytic reactor (catalytic reactor preparation example 5), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 850℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 90%, the conversion rate of carbon dioxide is 93%, the selectivity of CO is 99%, and the selectivity of CO/H is higher than that of the reaction raw material gas 2 ＝1。
Application example 8
Using Ni-CoInconel 601 metal catalytic reactor (catalytic reactor preparation example 5), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 900℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 90%, the conversion rate of carbon dioxide is 91%, the selectivity of CO is 99%, and the selectivity of CO/H is higher than that of the reaction raw material gas 2 ＝1。
Application example (9-20)
Use of 1.6 m Ru-CuInconel 600 metal catalytic reactor (catalytic reactor preparation example 6), 0.5L/min Ar gas was used to replace the empty space in the reactorAfter about 30 minutes of air, the Ar flow rate was kept unchanged, and the temperature was programmed from room temperature to the following temperature at a heating rate of 6 ℃ per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas was as follows, and after 30 minutes, the on-line analysis was started, and the analysis results were shown in the following table. />
Application example 21
Using 1.6 m Ni-CoMonel 400 Metal catalytic reactor (catalytic reactor preparation example 8), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, the temperature was programmed to 900℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 92%, the conversion rate of carbon dioxide is 93%, the selectivity of CO is 99% and the selectivity of CO/H is higher than that of CO/H 2 ＝1。
Application example 22
1.6 m Ni-Zn is usedInconel X-750 metal catalytic reactor (catalytic reactor preparation example 9), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 900℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 92%, the conversion rate of carbon dioxide is 93%, the selectivity of CO is 99% and the selectivity of CO/H is higher than that of CO/H 2 ＝1。
Application example 23
1.6 m Ni-La was usedHastelloy G-30 metal catalytic reactor (catalytic reactor preparation example 10), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 900℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 93%, the conversion rate of carbon dioxide is 94%, the selectivity of CO is 99%, and the selectivity of CO/H is higher than that of the on-line analysis 2 ＝1。
Application examples 24 to 35
1.6 m Ni-La was usedInconel 600 metal catalytic reactor (catalytic reactor preparation example 11), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to the following temperature from room temperature at a temperature-increasing rate of 6 ℃ C./min while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas was as follows, and after 30 minutes, the on-line analysis was started, and the analysis results were shown in the following table. />
Application examples 36 to 45
1.6 m La-Ce-Fe was usedIncoloy800 Metal catalytic reactor (catalytic reactor preparation example 15), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed from room temperature to the following temperature at a heating rate of 6 ℃ C./min while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas was as follows, and after 30 minutes, the on-line analysis was started, and the analysis results were shown in the following table.
Application example 46
1.6 m Ni-Zn is usedInconel 718 metal catalytic reactor (catalytic reactor preparation example 17), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 900℃from room temperature at a temperature increase rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 92%, the conversion rate of carbon dioxide is 94%, the selectivity of CO is 99%, and the selectivity of CO/H is higher than that of the on-line analysis 2 ＝1。
Application example 47
1.6 m La-Ce-Fe was usedInconel 600 Metal catalytic reactor (catalytic reactor preparation example 18), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 900℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, the online analysis is started after the reaction raw material gas is kept for 30 minutes, and 550-hour stability test is carried out, wherein the analysis result shows that the conversion rate of methane is 93-96%, the conversion rate of carbon dioxide is 94-98%, the CO selectivity is 99%, and the CO/H is shown 2 ＝1。
Application example 48
20 m La-Ce-FeInconel 600 Metal catalytic reactor (catalytic reactor preparation example 18), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 900℃from room temperature at a heating rate of 6℃per minute while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 14L/min, the reaction raw material gas is kept for 30 minutes and then starts to be analyzed on line, and the analysis result shows that the conversion rate of methane is 92-95%, the conversion rate of carbon dioxide is 94-97%, the selectivity of CO is 99% and the selectivity of CO/H is tested by 110 hours stability test 2 ＝1。
Application examples 49 to 50
20 m Ni-CeGH600 Metal catalytic reactor (catalytic reactor preparation example 19), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to the following temperature from room temperature at a temperature-increasing rate of 6 ℃ C./min while adjusting 40% CH 4 /40％CO 2 /20％N 2 The flow rate of the reaction raw material gas was as follows, and after 30 minutes, the on-line analysis was started, and the analysis results were shown in the following table.
Application example 51
1.6 m La-Ce-Fe was usedInconel 600 Metal catalytic reactor (catalytic reactor preparation example 18), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 900℃from room temperature at a heating rate of 6℃per minute while 38% CH was adjusted 4 /42％CO 2 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 97%, the conversion rate of carbon dioxide is 95%, the selectivity of CO is 99%, and the selectivity of CO/H is high 2 ＝1。
Application example 52
1.6 m La-Ce-Fe was usedInconel 600 Metal catalytic reactor (catalytic reactor preparation example 18), after replacing the air in the reactor with 0.5L/min Ar gas for about 30 minutes, the Ar flow rate was kept unchanged, and the temperature was programmed to 900℃from room temperature at a heating rate of 6℃per minute while 38% CH was adjusted 4 /38％CO 2 /2％C 2 H 6 /2％C 3 H 8 /20％N 2 The flow rate of the reaction raw material gas is 1.5L/min, and after the reaction raw material gas is kept for 30 minutes, the on-line analysis is started, and the analysis result shows that the conversion rate of methane is 95%, the conversion rate of carbon dioxide is 97%, the selectivity of CO is 96%, and the selectivity of CO/H is that 2 ＝0.95。
In summary, the reaction temperature is 700-950 ℃ in the mode of using the catalytic reactor; the reaction pressure is normal pressure; mixture gas (40% CH) 4 /40％CO 2 /20％N 2 ) 1 to 50L/min. The conversion rates of methane and carbon dioxide are 73-98 percent respectively; CO selectivity is as follows>96％；CO/H 2 >0.95; zero carbon deposition.
From this it follows that: the catalyst of the catalytic reactor has the characteristics of long service life (> 500 h), high product selectivity, low carbon deposition, easy product separation, good process repeatability, safe and reliable operation and the like, and has wide industrial application prospect.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully realize the full scope of the independent claims and the dependent claims, and the implementation process and method are the same as those of the above embodiments; and not specifically described in part are well known in the art.
While the invention has been described with respect to certain preferred embodiments, it will be apparent to those skilled in the art that various changes and substitutions can be made herein without departing from the scope of the invention as defined by the appended claims.

Claims (6)

1. The application of a metal catalytic reactor in reforming reaction of natural gas and carbon dioxide dry gas is characterized in that: the metal catalytic reactor comprises a metal pipe and a catalyst active component, wherein the catalyst active component is coated and doped on the contact surface of the metal pipe and the reaction raw material, a catalytic dopant thin layer is formed on the contact surface of the metal pipe and the reaction raw material, the catalyst active component and the contact surface of the metal pipe form a catalyst, and the contact surface refers to the inner wall and/or the outer wall of the metal pipe;
the existence state of the metal element is one or more of oxide, carbide, nitride, silicide and alloy; the metal element is one or more than two of magnesium, aluminum, calcium, barium, titanium, manganese, vanadium, niobium, tungsten, molybdenum, chromium, iron, cobalt, nickel, copper, zinc, tin, gallium, zirconium, lanthanum, cerium, ruthenium, gold, palladium or platinum;
when reforming natural gas and carbon dioxide dry gas for continuous reaction, the catalytic reaction temperature is 600-950 ℃, the reaction pressure is 0.05-1 MPa, and the flow rate of reaction raw material gas is 1-100L/min;
the catalyst active component is coated and doped on the contact surface of the metal tube and the reaction raw material by one or more of electroplating, chemical plating, electrochemical deposition, conversion deposition precipitation, chemical Vapor Deposition (CVD) or Physical Vapor Deposition (PVD).
2. Use of a metal catalytic reactor according to claim 1 in a natural gas and carbon dioxide dry gas reforming reaction, characterized in that: the thickness of the catalytic dopant thin layer is 100 nanometers-1 millimeter.
3. Use of a metal catalytic reactor according to claim 1 in a natural gas and carbon dioxide dry gas reforming reaction, characterized in that: the doping is lattice doping; the active component of the catalyst is metal element or a mixture of metal element and nonmetal element, and the doping amount of the metal element is 0.1-20wt% based on the total weight of the adulterant thin layer of 100%.
4. Use of a metal catalytic reactor according to claim 1 in a natural gas and carbon dioxide dry gas reforming reaction, characterized in that: the electrochemical deposition method comprises the following steps:
(1) Steaming the base pipe in 10-20wt% NaOH or KOH solution for 1-2h, deoiling, washing, and air drying at normal temperature;
(2) The matrix pipe processed in the step (1) is heated to N 2 Heating in atmosphere at 300-500 deg.c for 1-2 hr to form anticorrosive conducting film layer;
(3) Preparing an aqueous solution or an organic solution of a precursor doped with metal elements at room temperature, preparing the pH value of the solution to 3.3-6.5, immersing a metal pipe to be doped in the precursor solution, connecting the metal pipe to be doped with the precursor solution with the pH value as a cathode and platinum as an anode, adjusting the distance between the cathode and the anode to be 2-5cm after the metal pipe is connected with a circuit, adjusting a direct-current stabilized power supply, keeping a constant-current mode, keeping the current to be 5 mA-0.5A, and washing and drying the metal pipe with deionized water after electrodeposition is completed for 0.5-2 hours to obtain the metal reactor;
The conversion deposition precipitation method comprises the following steps:
(1) Steaming the base pipe in 10-20wt% NaOH or KOH solution for 1-2h, deoiling, washing, and air drying at normal temperature;
(2) The matrix pipe processed in the step (1) is heated to N 2 Heating in atmosphere at 300-500 deg.c for 1-2 hr to form anticorrosive conducting film layer;
(3) Preparing an aqueous solution or an organic solution of a precursor of the doped metal element at room temperature, preparing the pH value of the solution to 3.8-7.2, immersing the metal pipe to be doped in the precursor solution to enable the solution to be in a flowing state in the metal pipe to be deposited, and then adding 10-20wt% of H 2 O 2 And (3) carrying out conversion deposition precipitation on the aqueous solution, wherein the deposition time is 0.5-5 hours, and obtaining the metal reactor after the deposition is completed.
5. The use of a metal catalytic reactor according to claim 4 in a natural gas and carbon dioxide dry gas reforming reaction, characterized in that: the doping metal element precursor used in the electrochemical deposition method is one or more than two of metal nitrate, soluble halide, soluble sulfate, soluble carbonate, soluble phosphate, soluble methoxide, soluble ethoxide, soluble formate and soluble acetate;
The doping metal element precursor used in the conversion deposition precipitation method is one or more of metal chloride, methoxide, ethoxide, formate and acetate.
6. Use of a metal catalytic reactor according to claim 1 in a natural gas and carbon dioxide dry gas reforming reaction, characterized in that: the composition of the reaction raw material gas comprises methane and carbon dioxide, or a mixed gas of the methane, the carbon dioxide and other gases, wherein the other gases comprise one or two of inert atmosphere gas and non-inert atmosphere gas;
the inert atmosphere gas is one or more than two of nitrogen, helium, neon, argon and krypton, and the volume content of the inert atmosphere gas in the reaction raw material gas is 0-95%;
the non-inert atmosphere gas is one or a mixture of more than two of carbon monoxide, hydrogen and alkane with the C number of 2-4, and the volume content ratio of the non-inert atmosphere gas to methane is 0-10%;
the total volume content of methane and carbon dioxide in the reaction raw material gas is 5-100%;
the volume content ratio of the carbon dioxide to the methane is 0.5-2.
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