CN111333479B

CN111333479B - Method for preparing olefin, aromatic hydrocarbon and hydrogen by catalytic conversion of methane under hydrogen condition

Info

Publication number: CN111333479B
Application number: CN201811566377.8A
Authority: CN
Inventors: 包信和; 郭晓光; 潘秀莲; 方光宗; 戴丹; 柳海涛; 谭大力; 于洪飞
Original assignee: Dalian Institute of Chemical Physics of CAS; China Huanqiu Contracting and Engineering Corp; SABIC Global Technologies BV
Current assignee: Dalian Institute of Chemical Physics of CAS; China Huanqiu Contracting and Engineering Corp; SABIC Global Technologies BV
Priority date: 2018-12-18
Filing date: 2018-12-18
Publication date: 2021-08-31
Anticipated expiration: 2038-12-18
Also published as: CN111333479A

Abstract

The invention relates to a preparation method of a quartz catalytic reactor for converting methane to olefin, aromatic hydrocarbon and hydrogen under the hydrogen condition, which realizes the high-efficiency conversion of methane, the high-efficiency dissociation of the methane promoted by the hydrogen, the heavy hydrocarbon generation inhibition of the hydrogen, the high catalyst stability and the zero carbon deposit generation. The conversion rate of methane is 20-70%; the olefin selectivity is 70-95%; the benzene selectivity is 5-30%, and carbon deposition is avoided. The invention has the characteristics of long service life of the catalyst, good oxidation reduction and hydrothermal stability of the catalyst at high temperature, high methane conversion rate and product selectivity, zero carbon deposition, no need of amplification of 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

Method for preparing olefin, aromatic hydrocarbon and hydrogen by catalytic conversion of methane under hydrogen condition

Technical Field

The invention relates to an application of a quartz catalytic reactor in the preparation of olefin, aromatic hydrocarbon and hydrogen by converting methane under the hydrogen condition, which realizes the high-efficiency conversion of methane, the high-efficiency dissociation of methane promoted by hydrogen, the inhibition of heavy hydrocarbon generation by hydrogen, high catalyst stability and zero carbon deposit generation.

Background

The development and effective utilization of natural gas (methane) resources represent the development direction of modern energy structures, and are also one of important ways for ensuring sustainable development and energy greening. In recent years, developed countries in the western world have also made breakthrough progress in the development of shale gas and combustible ice, and a shale gas revolution is developed. The shale gas in China has many types and relatively centralized distribution, the recoverable resource potential is 25 billion cubic meters (without a Qinghai-Tibet region), the shale gas is equivalent to the conventional natural gas in the continental region of China and is close to 24 billion cubic meters in the United states, the shale gas is deployed in the development field during the 'fifteen' period of China, and the shale gas is expected to make a technical breakthrough in several shale gas regions of different types and initially establish the production capacity with economic benefits.

However, how to efficiently utilize gaseous hydrocarbon resources (methane) becomes an important link restricting the development of energy industry in China, and the conversion of the rich resources into fuels and high value-added chemicals (especially low-carbon olefins) arouses worldwide interest again, and is also an important step for improving the energy structure in China. Low carbon olefins, such as ethylene, are very important raw materials or intermediates in chemical processes, traditionally low carbon olefins (C)₂-C₄) Mainly comes from petrochemical processes such as naphtha cracking, and the like, so that the production of ethylene becomes a mark for measuring the petrochemical production level of a country and a region. With the increasing exhaustion of petroleum resources, the exploration of methods for producing lower olefins by non-traditional routes has become the focus of current research. Some typical alternative routes follow, such as obtaining low-carbon olefin by further conversion from synthesis gas through methanol or dimethyl ether, but the route has complex process and low atom economy. In order to shorten the reaction path, starting from synthesis gas, the reaction is carried out through a Fischer-Tropsch reactionFischer-Tropsch) route to directly synthesize lower olefins has also been extensively studied. However, all of the above alternative routes must consume CO or H₂To remove O from CO, the atomic utilization of C is inevitably lower than 50%. High CO content despite high capacity input₂Emissions and utilization below 50% atomic, but indirect processes are still predominant in natural gas industrial applications.

In contrast, the direct conversion of natural gas has great economic potential and is more environmentally friendly. However, the direct conversion of natural gas is still a problem in chemical and chemical processes. The main component of natural gas is methane, the C-H bond energy of which is as high as 434kJ/mol, while the methane molecule itself has almost no electron affinity and has large ionization energy and small polarizability, so the C-H bond activation of methane is considered as 'holy grail' in the chemical and even chemical fields. Keller and Bhasin reported on O₂The activation of the C-H bond of methane is realized under participation, and the two-bit pioneering work has burned the worldwide research high temperature: (>1073K) Under the condition of enthusiasm of preparing ethylene by methane oxidation coupling, hundreds of catalytic materials are synthesized and tested during the preparation, and the research reaches the peak in the last 90 th century. Due to molecular oxygen (O) during oxidative coupling₂) Inevitably leads to over-oxidation of methane and its products, thereby producing a large number of products that are thermodynamically more stable than methane, such as CO₂And H₂O, ultimately results in relatively low efficiency of C atom utilization. The development of the oxidative coupling process of methane has not been stopped due to the bottleneck of the development of new materials and new catalysts, and new processes with economic feasibility are still rarely reported so far. A recent study proposed the use of a weakly oxidizing gas phase S instead of molecular oxygen O₂And carrying out methane oxidative coupling reaction. At a temperature of 1323K (reaction gas: 5% CH)₄/Ar), optimum PdS/ZrO₂The catalyst can achieve a methane conversion of 16%, however C₂H₄The selectivity of (A) is only about 20%, but a large amount of CS is by-produced₂And H₂And S. The above studies indicate that oxygen (or an oxidizing agent) assisted methane activation will inevitably result in peroxidation.

Therefore, oxygen-free (or oxidant-free) direct conversion of methane is considered to be the most desirable route for activated conversion of methane. Under the condition of no oxygen (or no oxidant), the excessive oxidation of methane or products can be effectively avoided, and the greenhouse gas CO is inhibited₂And further improves the utilization rate of the C atoms. The challenges in the direct catalytic conversion of methane to ethylene are: 1) controllably activating methane to break a first C-H bond; 2) inhibit deep dehydrogenation on the surface of the catalyst; 3) avoiding the generation of greenhouse gas CO₂And carbon deposition. Wherein 1, 2 are directed to the catalyst and 3 is directed to the reaction process. Peroxidation of aerobic process products is unavoidable, resulting in CO₂Is also inevitable. Can avoid CO only by anaerobic process₂But is prone to carbon deposition, and therefore, the focus of current attention on the avoidance of carbon deposition is on the oxygen-free process. The key point for solving the problem of carbon deposition is to know the source of the carbon deposition, taking an oxygen-free aromatization process as an example, the carbon deposition mainly comes from: deep dehydrocarbon deposition of methane on the surface of the Mo species of the catalyst ("graphitization-like carbon deposition"); and (3) carrying out cyclization coupling carbon deposition on B acid sites of pore channels or pore openings of the carrier molecular sieve during the product diffusion process (namely poly-aromatic carbon deposition). Therefore, three challenges in the direct conversion of methane to ethylene are the design and construction of the catalyst.

In 1993, researchers at the institute of Dalian ligation reported for the first time CH on Mo/HZSM-5 catalyst in continuous flow mode₄And (3) carrying out oxygen-free aromatization reaction. At 973K and atmospheric pressure, CH₄Conversion is about 6%, selectivity to aromatics is greater than 90% (not counting reaction carbon build-up), to CH₄An important milestone for the study of the oxygen-free aromatization process. In the past decade, research work of many scientists has mainly focused on preparation and development of catalysts, reaction and deactivation mechanisms, but rapid carbon deposition deactivation of catalysts restricts further industrial scale-up.

Recently, the Siluria company (US201241246, US2013165728, US2014121433, CA2837201 and US8921256B29) in the United states utilizes the composite catalyst prepared by the biological template method to realize the methane conversion rate of 26% and the ethylene selectivity of 52% in the oxidative coupling reaction at 650 ℃ of 600-. For the selective oxidation of methane to prepare methanol or formaldehyde, the target products of methanol and formaldehyde are oxidized at a much higher speed than the raw material of methane, so that the selectivity of the reaction is low and the scale application is difficult.

Two patents (application numbers: 201310174960.5, 201511003407.0 and the two patents mainly apply for a metal-doped silicon-based catalyst, and then the silicon-based catalyst is placed in a reactor to catalyze and convert methane to olefin by a fixed bed or a fluidized bed or a moving bed, and the two methods have the defects of large pressure drop of a catalyst bed layer, large temperature difference of a catalyst heat conduction difference bed layer, harsh and difficult amplification of catalyst preparation conditions and the like.

The invention aims to dope active metal or nonmetal component crystal lattices on the inner wall of quartz or dope active metal or nonmetal component crystal lattices on the inner wall of a reactor, so that a catalyst and the reactor are integrated, and further methane and ethane are co-catalytically converted to prepare olefin, aromatic hydrocarbon and hydrogen. In contrast to the previous patent above (201610286107.6), the process can co-convert methane and ethane simultaneously with high efficiency, and the addition of ethane can greatly facilitate the conversion of methane.

Disclosure of Invention

The quartz catalytic reactor in the invention means that the active components of the catalyst are directly doped on the contact surface of the quartz tube and the raw material in a lattice manner; a thin layer of lattice-doped catalytic dopant is formed and a quartz reactor with a contact surface directly lattice-doped or coated with a thin layer with a catalytic function 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 quartz tube. By anaerobic methane conversion is meant the direct conversion of methane in the absence of an oxidizing agent (e.g., oxygen, elemental sulfur, sulfur dioxide, etc.). The contact surface refers to the inner wall or the outer wall of the quartz tube.

The quartz catalytic reactor comprises: directly doping the crystal lattice of the active component of the catalyst on the contact surface of the quartz tube and the raw material, or coating the Si-based material doped with the crystal lattice of the active component of the catalyst on the contact surface of the quartz tube and the raw material, wherein the doping is crystal lattice doping; by lattice doping is meant that the doping metal or metalloid element forms a chemical bond with certain elements in the host material such that the doping metal or metalloid element is confined to the lattice of the doped host material to produce a particular catalytic performance.

Compared with the traditional packed catalyst, the quartz catalytic reactor has the following advantages: 1) the catalyst induces methane to catalytically generate methyl free radicals, and then the methyl free radicals are coupled in a gas phase to obtain corresponding products, wherein the existence of the free radicals is limited by the space of a reactor in the gas phase coupling process; 2) the traditional packed catalyst greatly reduces the reaction space, so that the methane conversion rate is low; 3) based on the knowledge, the active component is loaded on the contact surface of the reactor, so that the reaction space is greatly increased, and the methane conversion rate can be effectively improved.

The metal doping amount in the catalyst doped with the metal element crystal lattice is more than 0.05wt.% and less than or equal to 5wt.%, based on 100% of the total weight of the dopant thin layer; the doping amount of the metal in the catalyst doped with the non-metal element crystal lattice is 0-5 wt.%. The amount of metal doping in the catalyst doped with the metal element lattice is preferably 0.1 wt.% to 2 wt.%. When the metal doping amount is more than 5wt.%, lattice doping is difficult to achieve, resulting in severe loss of active components and a decrease in conversion rate of raw materials.

So-called melt amorphous materials, in which the metal and the silicon-based material are all molten during the preparation process, form amorphous materials with long-range disorder and short-range order after being cooled very quickly.

The doped metal elements comprise: one or more of lithium, magnesium, aluminum, calcium, strontium, barium, titanium, manganese, vanadium, chromium, iron, cobalt, nickel, zinc, germanium, tin, gallium, zirconium, gold, lanthanum, cerium, praseodymium, neodymium, europium, erbium, ytterbium, ruthenium, gold, or platinum.

The doped metal element is preferably one or more of aluminum, barium, titanium, manganese, vanadium, chromium, iron, cobalt, nickel, zinc, germanium, tin, gallium, zirconium, gold, lanthanum, cerium, praseodymium, neodymium, europium, erbium, ytterbium, ruthenium, gold and platinum.

The doped non-metal elements comprise: boron and phosphorus.

The doped metal element exists in the state of one or more of oxide, carbide and silicide; the doped nonmetal element is oxide in the existing state of doped nonmetal;

the catalyst is obtained by taking SiO2 as a main body and doping metal elements into crystal lattices to form molten state solidification;

the metal element-doped precursor (the presence state of the pre-doped metal element) includes: one or more of nitrate, chloride, formate, acetate, methoxide and ethoxide; the precursor doped with the non-metal element (existence state of the pre-doped metal element) comprises: one or more of chloride or oxychloride;

the silicon-based material doped with the metal element is the inner wall of the reactor and is mainly SiO₂；

The thickness of the dopant thin layer is 100nm to 1mm, preferably 1 μm to 0.5 mm, more preferably 10 μm to 0.05 mm, and further preferably 100mm to 500 μm.

The reaction section of the quartz catalytic reactor is prepared by adopting the following solid phase doping technology; the solid phase doping technology is an improved chemical vapor deposition (MCVD) method, and the adopted equipment is an MCVD device.

The purpose of the following reaction section preparation process is to improve the dispersion degree of metal elements in silicon-based materials and more effectively dope the metal element crystal lattices into SiO₂In the melt amorphous material.

The solid phase doping technique comprises Modified Chemical Vapor Deposition (MCVD)

The first method comprises the following steps: under 1-3 atmospheric pressure, silicon tetrachloride liquid or non-metallic chloride doped in gas phase at 50-500 ℃ enters an MCVD device to react at 1400-1650 ℃ under the drive of carrier gas, and SiO with the thickness of 0.01-100 microns is deposited in the gas phase on the inner wall of the quartz reactor₂A thin layer, and then immersing the reactor in a doped metal salt (nitrate, soluble halide, soluble sulfate, soluble carbonate, soluble phosphate, soluble methoxide, soluble sulfate, soluble nitrate, soluble phosphate, soluble sulfate, soluble phosphate, soluble methoxide, soluble phosphate, or soluble salt thereof, or a mixture thereof at a temperature of 20-80 deg.C,One or more than two of soluble ethoxide, soluble formate and soluble acetate) in water solution for 0.1-20 hours; melting the reactor at 1800-2200 ℃ to obtain a reactor doped with metal lattices on the corresponding inner wall, forming a dopant thin layer with the thickness of 100nm-1mm on the inner wall of the quartz reactor, immediately cooling, and solidifying to obtain the quartz catalytic reactor with the specific active component doping amount;

and the second method comprises the following steps: under 1-3 atmospheric pressure, introducing silicon tetrachloride liquid and gas phase doping volatile doping metal salt (one or more than two of metal chloride, methoxide, ethoxide, formate and acetate) gasified at 50-950 ℃ or non-metal chloride gas phase doped at 50-500 ℃ into an MCVD device to react with oxygen at 1400-1650 ℃ under the drive of carrier gas (oxygen or helium), depositing for 10 minutes-2 hours, vapor-depositing a dopant thin layer on the inner wall of the reactor, melting at 1800-2200 ℃ to obtain a corresponding inner wall metal lattice doped reactor, forming a dopant thin layer with the thickness of 100nm-1mm on the inner wall of the quartz reactor, immediately cooling, and solidifying to obtain the quartz catalytic reactor with the specific active component doping amount;

and the third is that: under 1-3 atmospheric pressure, silicon tetrachloride liquid and normal-temperature liquid metal chloride (tin tetrachloride, titanium tetrachloride and germanium tetrachloride) or normal-temperature liquid non-metal chloride or oxygen chloride (boron trichloride and phosphorus oxychloride) enter an MCVD device to react at 1650 ℃ of 1400 ℃ for 10 minutes to 2 hours, then a dopant thin layer is deposited in a gas phase on the inner wall of the quartz reactor, then the quartz reactor doped with the metal lattice on the corresponding inner wall is melted at 1800-2200 ℃, the dopant thin layer with the thickness of 100nm-1mm is formed on the inner wall of the reactor, and then the quartz catalytic reactor with the specific active component doping amount is obtained after immediate cooling and solidification.

The metal salt used in the solid phase doping technology, i.e., the first method, is one or more of nitrate, soluble halide, soluble sulfate, soluble carbonate, soluble phosphate, soluble methoxide, soluble ethoxide, soluble formate and soluble acetate.

The solid phase doping technology is one or more of metal chloride, methoxide, ethoxide, formate and acetate used in the second method.

The normal-temperature liquid metal chlorides used in the solid phase doping technology-the third method are tin tetrachloride, titanium tetrachloride and germanium tetrachloride; the liquid nonmetal chloride or oxychlorides at normal temperature are boron trichloride and phosphorus oxychloride.

The preparation process of the solid phase doping technology-the first method comprises an impregnation process, wherein the solubility of an impregnation solution is 50 ppm-5%; the dipping time is 0.1-24 hours, preferably 1-18 hours; the impregnation temperature is preferably from 20 to 80 ℃.

In the preparation process of the catalyst of the solid phase doping technology, the deposition time is 10 minutes to 2 hours.

In the preparation process of the catalyst of the solid phase doping technology, the flow speed of the carrier gas is 0.01-50L/min, and the preference is given.

In the preparation process of the catalyst, the melting atmosphere is inert gas, air or oxygen, and the inert gas comprises one or more of helium, argon or nitrogen; the melting time is 0.01-3 hours.

The doping amount of the specific active component is controlled by the flow rate of the carrier gas and the vaporization temperature of the saturated vapor pressure.

The solidification is an important cooling process of the melted materials in the preparation process of the catalyst, and the cooling is rapid cooling or natural cooling;

the cooling is gas cooling; the cooling rate is preferably 50 ℃/s-2000 ℃/s, preferably; 100-1800 ℃/s; the gas in the gas cooling is one or more than two of inert gas, nitrogen, oxygen or air.

The carrier gas is high purity oxygen or helium (high purity means 99.999%).

The SiO₂The film-coated catalyst thin layer on the inner wall of the quartz reactor only contains lattice-doped metal elements, and no metal or metal compound is loaded on the surface.

The non-metal element crystal lattice is doped in SiO₂Amorphous catalyst of the melt formed inThe agent may be represented by

Wherein B represents a doped non-metallic element;

said

The metal element is doped with a catalyst, namely metal element A enters SiO₂The lattice of (a) wherein, after partial substitution of the Si atom, the metal element is bonded to the adjacent O atom (a-O);

said

Doping catalyst to make non-metal element B enter SiO₂The metal element is bonded to the adjacent O atom (B-O) after partial substitution of the Si atom;

the invention relates to a method for preparing olefin, aromatic hydrocarbon and hydrogen by co-catalytically converting methane and ethane in a quartz catalytic reactor, which comprises the steps of doping direct crystal lattices on a contact surface or coating a crystal lattice doped catalyst; by coating the lattice-doped catalyst is meant lattice-doping the catalytically active component to SiO using MCVD techniques₂The powder catalyst formed by the crystal lattice is coated on the contact surface of the quartz reactor and the raw material.

The invention relates to a method for preparing olefin, aromatic hydrocarbon and hydrogen by hydrogen-promoted methane dissociation and oxygen-free direct dissociation, wherein the reaction raw material gas composition comprises one or two of inert atmosphere gas and non-inert atmosphere gas besides methane and hydrogen; the inert atmosphere gas is one or more 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, carbon dioxide, water, monohydric alcohol (the number of C is 2-4) or alkane (the number of C is 3-4), and the volume content ratio of the non-inert atmosphere gas to methane is 0-10%; the total content of methane and ethane in the reaction raw material gas is 5-100%, and the volume content ratio of hydrogen to methane is 0.05-10.

The invention relates to a method for preparing olefin, aromatic hydrocarbon and hydrogen by hydrogen-promoted methane dissociation and oxygen-free direct dissociation. Continuous flow reaction mode: the reaction temperature is 800-1150 ℃; the reaction pressure is preferably 0.1-0.5 Mpa; when the inner diameter of the quartz catalytic reactor is 5-15mm, the mass space velocity of the reaction feed gas is 0.5-20.0L/g/h; when the inner diameter of the quartz catalytic reactor is more than 15-25mm, the mass space velocity of the reaction feed gas is preferably 2-40.0L/g/h; when the pipe diameter of the quartz catalytic reactor is more than 25-35mm, the mass space velocity of the reaction feed gas is preferably 4-60.0L/g/h; when the pipe diameter of the quartz catalytic reactor is more than 35-45mm, the mass space velocity of the reaction feed gas is preferably 5.0-80.0L/g/h; when the pipe diameter of the quartz catalytic reactor is more than 45-55mm, the mass space velocity of the reaction feed gas is preferably 5.0-100.0L/g/h; when the pipe diameter of the quartz catalytic reactor is more than 55-65mm, the mass space velocity of the reaction raw material gas is preferably 5.0-150.0L/g/h; when the pipe diameter of the quartz catalytic reactor is more than 65-75mm, the mass space velocity of the reaction raw material gas is preferably 5.0-200.0L/g/h; when the pipe diameter of the quartz catalytic reactor is more than 75-85mm, the mass space velocity of the reaction raw material gas is preferably 5.0-300.0L/g/h.

The invention relates to a method for preparing olefin, aromatic hydrocarbon and hydrogen by hydrogen-promoted methane dissociation and oxygen-free direct dissociation, wherein the aromatic hydrocarbon product comprises one or more of benzene, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene and naphthalene; the olefin products include ethylene, propylene, butylene, isobutylene, 1, 3-butadiene.

The invention relates to a method for preparing olefin, aromatic hydrocarbon and hydrogen by hydrogen-promoted methane dissociation and oxygen-free direct dissociation, wherein the catalyst not only can catalyze and dissociate methane (formula (1)), but also can catalyze and dissociate hydrogen to generate hydrogen free radicals (formula (2)), and the hydrogen free radicals can further dissociate methane in a gas phase. The advantages of this process are: the dissociation of methane can be realized on the surface of the catalyst and in the gas phase process, the conversion rate of methane can be greatly improved, and meanwhile, the formation of polycyclic aromatic hydrocarbons (such as naphthalene, anthracene, quinone and the like) is inhibited by the presence of hydrogen.

The invention provides a method for directly preparing ethylene, aromatic hydrocarbon and hydrogen by catalyzing methane under the anaerobic condition by using a silicon-based catalyst doped with metal lattices based on long-term methane anaerobic aromatization research, and the method has the following characteristics compared with the prior methane anaerobic conversion process, particularly with the patent application numbers of 201310174960.5 and 201511003407.0:

therefore, the method has the characteristics of high catalyst stability, high methane conversion rate, high product selectivity, zero carbon deposit, good process repeatability, safe and reliable operation and the like, and has wide industrial application prospect.

Although the product type of the process is closer to the existing methane oxygen-free aromatization process, the research finds that the two have essential difference (catalyst and reaction mechanism). Firstly, a catalyst for oxygen-free aromatization of methane is a molecular sieve supported catalyst; secondly, the currently accepted reaction mechanism of oxygen-free aromatization of methane (shown as formula 1): active species of methane in catalysts (MoC)_xWC, Re) surface to generate CH_xSpecies, then CH_xSpecies are coupled on the surface of the catalyst to form C₂H_ySpecies that are further coupled at the acid sites of the molecular sieve channels, while aromatics are produced by zigzag selection of the molecular sieve channels (j.energy chem.2013,22, 1-20).

Formula 1MoC_xThe Zeolite catalyst catalyzes the reaction mechanism of the oxygen-free aromatization of methane.

However, the catalyst of the invention is formed by doping the metal element lattice in SiO₂The molten amorphous material formed in (a); the reaction mechanism is the passage of methane through the active species (formation in the lattice)In-state metal element) to generate a methyl radical (. CH)₃) Then the methyl free radical is further coupled and dehydrogenated to obtain olefin and coproduce aromatic hydrocarbon and hydrogen.

The oxygen-free aromatization process differs from the process of the present invention in the following ways: 1) molecular sieves having specific pore sizes and structures, number and type of acid sites are necessary for the aromatization process; 2) the catalyst is a molten amorphous pore-free and acid-free material; 3) the aromatization mechanism is a concerted catalytic mechanism of active species and molecular sieves (pore channels and acidity), while the present invention is a free radical induction mechanism.

The conversion rate of methane is 20-70%; the olefin selectivity is 70-95%; the benzene selectivity is 5-30%, and carbon deposition is avoided. The method has the characteristics of long service life of the catalyst, good oxidation reduction and hydrothermal stability of the catalyst at high temperature (1700 ℃), high methane conversion rate and ethylene selectivity, zero carbon deposition, easy separation of products, no need of amplification of the catalyst, small industrialization difficulty, good process repeatability, safe and reliable operation and the like, and has wide industrial application prospect.

Drawings

FIG. 1 is a representation of the HAADF-STEM high resolution electron microscope and EDX for a 20mm diameter Fe-catalyzed quartz reactor. The electron micrograph shows the morphology of the Fe element in the dopant thin layer.

Detailed Description

The invention is described in detail below with reference to the figures and the embodiments. The following examples are only illustrative of the present invention, and the scope of the present invention shall include the full contents of the claims, not limited to the examples.

1. Preparation of catalytic reactor (thickness of thin layer and active component content need to be noted)

The preparation method of the lattice doped catalyst comprises a chemical vapor deposition (MCVD) coating solid phase doping technology or a solid-liquid phase sol-gel combined high temperature melting coating technology. The membrane layer catalyst is marked as:

preparation of lattice doped catalysts (examples 1 to 20).

Example 1

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using high purity helium at 200mL/min₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃After 10 minutes of oxidative deposition, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor, wherein the doping amount of Fe is 0.05 wt.%.

Example 2

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using high purity helium at 650mL/min₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃After 10 minutes of oxidative deposition, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor with a doping amount of Fe of 0.1 wt.%.

Example 3

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using 1.0L/min of high purity helium₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃After 10 minutes of oxidative deposition, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor with a doping amount of Fe of 0.25 wt.%.

Example 4

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using 1.5L/min of high purity helium₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃After 10 minutes of oxidative deposition, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor with a doping amount of Fe of 0.35 wt.%.

Example 5

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using 3.8L/min of high purity helium₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃Performing oxidation deposition for 10 minAfter that, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor with a doping amount of Fe of 1 wt.%.

Example 6

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using 5L/min of high purity helium₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃After 10 minutes of oxidative deposition, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor, wherein the doping level of Fe is 2.5 wt.%.

Example 7

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using high purity helium at 6L/min₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃After 10 minutes of oxidative deposition, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor, wherein the doping amount of Fe is 4.0 wt.%.

Example 8

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using high purity helium at 8L/min₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃After 10 minutes of oxidative deposition, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor, wherein the doping level of Fe is 5 wt.%.

Example 9

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using high purity helium at 12L/min₃Gas is introduced into a high-temperature MCVD apparatus with SiCl at 1600 ℃ on the inner wall of a quartz tube (wall thickness 1.5mm) having an outer diameter of 20mm and a length of 100mm₄And FeCl₃After 10 minutes of oxidative deposition, Fe-doped SiO was obtained₂Melting the powder material at 1980 deg.C under 2bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 100mm

Catalytic quartz reactor, wherein the doping amount of Fe is 6.5 wt.%.

The lattice doped catalytic reactor is characterized by a high-resolution electron microscope (HR-TEM), and the result shows that about 4.0-4.2% of Fe species lattice is doped on the contact surface of the inner wall of the quartz reactor, and about 2.3-2.5% of the other Fe species lattice cannot enter the quartz lattice and is only surface load.

Example 10

Modified chemical vapor deposition Method (MCVD)

SiCl was purged with 30mL/min high purity helium₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using 2.5L/min of high purity helium₃Introducing the gas into a high-temperature MCVD device, and carrying out SiCl treatment at 1650 ℃ on the inner wall of a quartz tube with the outer diameter of 20mm (the wall thickness is 1.5mm) and the length of 150mm₄And FeCl₃Reacting with high-purity oxygen to carry out oxidation deposition for 30 minutes to obtain Fe-doped SiO₂Melting the powder material at 1980 deg.C under 2bar high purity argon atmosphere for 40 min to form a dopant thin layer with thickness of 150nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 150mm

Catalytic quartz reactor with a doping amount of Fe of 0.6 wt.%.

Example 11

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and ZnCl under saturated vapor pressure at 450 ℃ using 2.6L/min of high purity helium₂Gas introduction into a high-temperature MCVD apparatus with SiCl at 1600 ℃ in a quartz tube having an outer diameter of 20mm (wall thickness 1.5mm) and a length of 200mm₄And ZnCl₂After an oxidative deposition for 30 minutes, Zn-doped SiO was obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 150nm on the inner wall of the reaction section, and naturally cooling to obtain the product with diameter of 20mm and length of 200mm

Catalytic quartz reactor with a doping amount of Zn of 0.55 wt.%.

Example 12

Modified chemical vapor deposition Method (MCVD)

SiCl was purged with 30mL/min high purity helium₄Liquid and use2.5L/min of high purity helium FeCl was pressed with 350 ℃ saturated steam₃Gas and 2.6L/min of high purity helium ZnCl at a saturated vapor pressure of 450 DEG C₂The gas is introduced into a high-temperature MCVD apparatus at the same time, and SiCl is introduced into a quartz tube with an outer diameter of 20mm (wall thickness of 1.5mm) and a length of 280mm at 1600 DEG C₄、FeCl₃And ZnCl₂Reacting with high-purity oxygen to carry out oxidation deposition for 30 minutes to obtain Fe and Zn doped SiO₂Melting the powder material at 2000 deg.C under 1.5bar high purity argon atmosphere for 40 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain powder material with diameter of 20mm and length of 280mm

A catalytic quartz reactor in which the doping levels of Fe and Zn were 0.6 wt.% and 0.55 wt.%, respectively.

Example 13

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at 350 ℃ saturated vapor pressure using 3.0L/min of high purity helium₃Gas and ZnCl at 450 ℃ under saturated vapor pressure using 2.8L/min of high purity helium₂Introducing the gas into a high-temperature MCVD (modified chemical vapor deposition), and carrying out SiCl treatment at 1600 ℃ on the inner wall of a quartz tube with the outer diameter of 50mm (the wall thickness of 2mm) and the length of 350mm₄、FeCl₃And ZnCl₂After 60 minutes of oxide deposition, Fe and Zn doped SiO was obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity argon atmosphere for 60 min to form a dopant thin layer with thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 150mm and length of 350mm

A catalytic quartz reactor in which the doping levels of Fe and Zn were 0.8 wt.% and 0.65 wt.%, respectively.

Example 14

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and saturation of 350 deg.C with 3.3L/min of high purity heliumFeCl under vapor pressure₃Gas and ZnCl at 450 ℃ under saturated vapor pressure using 2.7L/min of high purity helium₂Gas and POCl with high purity helium at 0.5L/min₃The liquid is brought into a high-temperature MCVD at the same time, and SiCl is carried out at 1600 ℃ in a quartz tube with the outer diameter of 20mm (the wall thickness is 1.5mm) and the length of 300mm₄、FeCl₃、ZnCl₂And POCl₃After performing the oxidation deposition for 45 minutes, Fe, Zn and P doped SiO is obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity argon atmosphere for 40 min to form 400nm thick dopant thin layer on the inner wall of the reactor, and naturally cooling to obtain powder material with diameter of 20mm and length of 300mm

Catalytic quartz reactor, wherein the doping amounts of Fe, Zn and P are 0.7 wt.%, 0.6 wt.% and 0.8 wt.%, respectively.

Example 15

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and SnCl using high purity helium at 1.0L/min₄Liquid and ZnCl under saturated vapor pressure at 450 ℃ using high purity helium at 2.7L/min₂Gas and POCl with high purity helium at 0.7L/min₃The liquid is simultaneously introduced into a high-temperature MCVD apparatus, and SiCl is introduced into a quartz tube with an outer diameter of 20mm (wall thickness of 1.5mm) and a length of 250mm at 1600 DEG C₄、SnCl₄、ZnCl₂And POCl₃After performing the oxidation deposition for 45 minutes, Sn, Zn and P doped SiO is obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity argon atmosphere for 40 min to form a dopant thin layer with thickness of 1 μm on the inner wall of the reactor, and naturally cooling to obtain the final product with diameter of 20mm and length of 250mm

Catalytic quartz reactor, wherein the doping amounts of Sn, Zn and P are 0.4 wt.%, 0.6 wt.% and 0.8 wt.%, respectively.

Example 16

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and SnCl using high purity helium at 0.8L/min₄Liquid and ZnCl under saturated vapor pressure at 450 ℃ using high purity helium at 2.7L/min₂Gas and POCl with high purity helium at 0.5L/min₃The liquid is simultaneously introduced into a high-temperature MCVD apparatus, and SiCl is introduced into a quartz tube with an outer diameter of 20mm (wall thickness of 1.5mm) and a length of 150mm at 1600 DEG C₄、SnCl₄、ZnCl₂And POCl₃Reacting with high-purity oxygen for oxidation deposition for 45 minutes to obtain Sn, Zn and P doped SiO₂Melting the powder material at 2000 deg.C under 1.5bar high purity oxygen atmosphere for 40 min to form 0.1 micrometer dopant thin layer on the inner wall of the reactor, and naturally cooling to obtain powder with diameter of 20mm and length of 150mm

Example 17

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and TiCl Using 0.8L/min high purity helium₄Liquid and FeCl at 320 ℃ saturated vapor pressure using 1.8L/min of high purity helium₃Gas and use of 0.5L/min high purity helium to mix BCl₃The liquid is simultaneously brought into a high-temperature MCVD with SiCl at 1600 ℃ in a quartz tube with an outer diameter of 20mm (wall thickness of 1.5mm) and a length of 600mm₄、TiCl₄、FeCl₃And BCl₃After performing the oxidation deposition for 45 minutes, Ti, Fe and B doped SiO is obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 240nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 20mm and length of 600mm

A catalytic quartz reactor in which the doping levels of Ti, Fe and B were 0.5 wt.%, 0.4 wt.% and 0.6 wt.%, respectively.

Example 18

Modified chemical vapor deposition Method (MCVD)

SiCl was purged with 30mL/min high purity helium₄Liquid and use of 0.5L/min high purity helium to mix GaCl at 220 deg.C₃Liquid and use of high purity helium at 0.75L/min to mix AlCl at 200 deg.C₃The gas is simultaneously introduced into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 20mm (the wall thickness is 1.5mm) and the length of 250mm₄、GaCl₃And AlCl₃Reacting with high-purity oxygen to carry out oxidation deposition for 40 minutes to obtain Ga and Al doped SiO₂Melting the powder material at 2000 deg.C under 1.5bar high purity helium atmosphere for 40 min to form a dopant thin layer with a thickness of 360nm on the inner wall of the reactor, and naturally cooling to obtain the product with a diameter of 20mm and a length of 250mm

Catalytic quartz reactor, wherein the doping amounts of Ga and Al are 0.5 wt.% and 0.6 wt.%, respectively.

Example 19

Modified chemical vapor deposition Method (MCVD)

SiCl was purged with 30mL/min high purity helium₄Liquid and YbCl at 550 ℃ under saturated vapor pressure using 0.8L/min of high purity helium₃Gas and AlCl at 200 deg.C using 0.5L/min of high purity helium₃Gas and POCl with high purity helium at 0.5L/min₃The liquid is simultaneously taken into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 20mm (the wall thickness is 1.5mm) and the length of 100mm₄、YbCl₃POCl and AlCl₃Reacting with high-purity oxygen to carry out oxidation deposition for 40 minutes to obtain Yb and Al doped SiO₂Melting the powder material at 2000 deg.C under 1.5bar pure oxygen atmosphere for 40 min to form dopant thin layer with thickness of 580nm on the inner wall of the reactor, and naturally cooling to obtain powder material with diameter of 20mm and length of 100mm

Catalytic quartz reactor in which the doping levels of Yb, Al and P were 0.2 wt.%, 0.5 wt.% and 0.6 wt.%, respectively.

Example 20

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and LaCl under saturated vapor pressure at 550 deg.C using 2.5L/min of high purity helium₃Gas and high purity helium at 1.3L/min were used to mix AlCl at 200 deg.C₃Gas and use of 1.4L/min high purity helium to mix BCl₃The liquid is simultaneously brought into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 50mm (the wall thickness is 2mm) and the length of 1500mm₄、LaCl₃、BCl₃And AlCl₃After 80 minutes of oxidative deposition, La, Al and B doped SiO was obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity helium atmosphere for 60 min to form a dopant thin layer with thickness of 150nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 50mm and length of 1500mm

A catalytic quartz reactor in which the doping levels of La, Al and B were 0.2 wt.%, 0.4 wt.% and 0.6 wt.%, respectively.

Example 21

Modified chemical vapor deposition Method (MCVD)

SiCl was purged with 30mL/min high purity helium₄Liquid and LaCl under saturated vapor pressure at 550 deg.C using 2.2L/min of high purity helium₃Gas and high purity helium at 1.0L/min were used to mix AlCl at 200 deg.C₃Gas and use of 1.1L/min high purity helium to mix BCl₃The gas is simultaneously introduced into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 50mm (the wall thickness is 2mm) and the length of 1200mm₄、LaCl₃、BCl₃And AlCl₃After 80 minutes of oxidative deposition, La, Al and B doped SiO was obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity argon atmosphere for 60 min to form a dopant thin layer with thickness of 450nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 50mm and length of 1200mm

Example 22

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and use of 0.6L/min high purity helium to mix BCl₃Gas and POCl with high purity helium at 0.4L/min₃The gas is brought into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 25mm (the wall thickness is 1.5mm) and the length of 250mm₄、BCl₃And POCl₃After 30 minutes of oxidative deposition, B-and P-doped SiO was obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 550nm on the inner wall of the reactor, and naturally cooling to obtain the product with diameter of 25mm and length of 250mm

Catalytic quartz reactor, wherein the doping amounts of P and B are 0.6 wt.% and 0.5 wt.%, respectively.

Example 23

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and RuCl at 80 ℃ saturated vapor pressure using 1.5L/min of high purity helium₃And POCl was reacted with high purity helium at 1.1L/min₃The liquid is simultaneously brought into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 30mm (the wall thickness is 1.5mm) and the length of 200mm₄、RuCl₃And POCl₃After 40 minutes of oxide deposition, Ru and P doped SiO were obtained₂Melting the powder material at 2000 deg.C under 1.5bar high purity helium atmosphere for 40 min to form a dopant thin layer with thickness of 270nm on the inner wall of the reactor, and naturally cooling to obtain a powder material with diameter of 30mm and length of 200mm

Catalytic quartz reactor, in which the doping amounts of Ru and P are 1 wt.% and 0.7 wt.%, respectively.

Example 24

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and MgCl at 430 ℃ under saturated vapor pressure using 1.5L/min of high purity helium₂Gas and MnCl at 410 ℃ under saturated steam pressure using 0.8L/min of high purity helium₂Gas and POCl with high purity helium at 0.6L/min₃The liquid is simultaneously taken into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 30mm (the wall thickness is 1.5mm) and the length of 900mm₄、MgCl₂、MnCl₂And POCl₃After 40 minutes of oxidative deposition, Mg, Mn and P doped SiO was obtained₂Melting the powder material at 2000 deg.C under 1.5bar pure oxygen atmosphere for 40 min to form a dopant thin layer with thickness of 370nm on the inner wall of the reactor, and naturally cooling to obtain a powder material with diameter of 30mm and length of 900mm

Catalytic quartz reactor, in which the doping amounts of Mg, Mn and P were 0.4 wt.%, 0.3 wt.% and 0.4 wt.%, respectively.

Example 25

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at 320 ℃ saturated vapor pressure using 1.8L/min of high purity helium₃Gas and MnCl at 410 ℃ under saturated steam pressure using 0.8L/min of high purity helium₂Gas and POCl with high purity helium at 0.7L/min₃Liquid and use of 1.2L/min of high purity helium to dissolve AlCl at 200 deg.C₃Gas and SnCl with high purity helium at 0.6L/min₄The liquid is simultaneously brought into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 20mm (the wall thickness is 1.5mm) and the length of 800mm₄、FeCl₃、MnCl₂、AlCl₃、SnCl₄And POCl₃After carrying out the oxidation deposition for 60 minutes, Fe, Mn, Sn, Al and P doped SiO is obtained₂Melting the powder material at 2050 deg.C under 1.5bar pure oxygen atmosphere for 60 min to form a dopant thin layer with thickness of 600nm on the inner wall of the reactor, naturally cooling,i.e. to obtain a diameter of 20mm and a length of 800mm

Catalytic reactor, wherein the doping amounts of Fe, Mn, Sn, Al and P are 0.4 wt.%, 0.3 wt.%, 0.2 wt.%, 0.45 wt.% and 0.4 wt.%, respectively.

Example 26

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Introducing liquid into MCVD at high temperature, and introducing SiCl at 1650 deg.C into quartz tube with outer diameter of 20mm (wall thickness of 1.5mm) and length of 500mm₄After 40 minutes of oxidative deposition, SiO was obtained₂The powder material was further immersed in 1.6mol/L SrCl at 50 ℃ in a 20mm quartz tube₂And 2.8mol/L Ba (NO)₃)₂For about 2 hours; then melting at 2000 deg.C under 1.5bar pure argon atmosphere for 40 min to form a dopant thin layer with thickness of 300nm on the inner wall of the reactor, and naturally cooling to obtain a product with diameter of 20mm and length of 500mm

Catalytic quartz reactor, wherein the doping amounts of Sr and Ba are 0.4 wt.% and 0.4 wt.%, respectively.

Example 27

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and LaCl under saturated vapor pressure at 550 deg.C using 2.6L/min of high purity helium₃Gas and high purity helium at 1.1L/min were used to mix AlCl at 200 deg.C₃Gas and use of 1.1L/min high purity helium to mix BCl₃The gas is simultaneously introduced into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 50mm (the wall thickness is 2mm) and the length of 200mm₄、LaCl₃、BCl₃And AlCl₃After 80 minutes of oxidative deposition, La, Al and B doped SiO was obtained₂The powder material was further immersed in AuCl at 50 ℃ in a 50mm quartz reactor₃For about 1 hour in an aqueous solution of (a); then melting at 2000 deg.C under 1.5bar pure oxygen atmosphere for 60 min, and reactingForming a thin layer of dopant with a thickness of 100nm on the inner wall of the reactor, and naturally cooling to obtain a product with a diameter of 50mm and a length of 200mm

Catalytic quartz reactor, in which the doping amounts of La, Al, Au and B were 0.4 wt.%, 0.5 wt.%, 0.1 wt.% and 0.4 wt.%, respectively.

Example 28

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and saturated vapor pressure at 550 deg.C using 2.6L/min of high purity helium and AlCl at 200 deg.C using 1.1L/min of high purity helium₃The gas is used to mix BCl with high purity helium at 1.1L/min₃The gas is simultaneously introduced into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 50mm (the wall thickness is 2mm) and the length of 300mm₄、LaCl₃、BCl₃And AlCl₃After 80 minutes of oxidative deposition, La, Al and B doped SiO was obtained₂The powder material was further immersed in AuCl at 50 ℃ in a 50mm quartz reactor₃For about 1 hour in an aqueous solution of (a); then melting at 2000 deg.C under 1.5bar pure oxygen atmosphere for 60 min to form a dopant thin layer with a thickness of 880nm on the inner wall of the reactor, and naturally cooling to obtain a product with a diameter of 50mm and a length of 300mm

Catalytic quartz reactor, wherein the doping amounts of La, Al, Au and B are 0.3 wt.%, 0.5 wt.%, 0.2 wt.% and 0.5 wt.%, respectively.

Example 29

Modified chemical vapor deposition Method (MCVD)

SiCl was reacted with high purity oxygen at 30mL/min₄Liquid and FeCl at a saturated vapor pressure of 350 ℃ using 2.5L/min of high purity helium₃Gas and ZnCl at 450 ℃ under saturated vapor pressure using 2.2L/min of high purity helium₂Gas and POCl with high purity helium at 0.8L/min₃The liquid is simultaneously brought into a high-temperature MCVD device, and SiCl is carried out at 1650 ℃ in a quartz tube with the outer diameter of 40mm (the wall thickness is 2mm) and the length of 300mm₄、FeCl₃、ZnCl₂And POCl₃After carrying out the oxidation deposition for 60 minutes, Fe, Zn and P doped SiO is obtained₂Melting the powder material at 2000 deg.C under 1.5bar pure argon atmosphere for 40 min to form a dopant thin layer with a thickness of 480nm on the inner wall of the reactor, and naturally cooling to obtain the final product with a diameter of 40mm and a length of 300mm

A catalytic quartz reactor in which the doping levels of Fe, Zn and P were 0.6 wt.%, 0.5 wt.% and 0.35 wt.%, respectively.

2. Characterization of catalytic reactor contact surface

1) Inductively coupled plasma emission spectroscopy (ICP-AES) characterization

Acid pickling (40 wt.% nitric acid and 20 wt.% HF acid) method with inductively coupled plasma emission spectrometer (ICP-AES), so-called acid pickling ICP process: if the metal is supported on the support surface, we can dissolve the metal on the support surface using an acid washing process (the acid can only dissolve the metal component or the metal oxide component but cannot dissolve the support), and the degree of acid washing (i.e., surface loading/(surface loading + doping amount)) can be obtained by ICP measurement, whereas if the metal element cannot be dissolved by the acid, it indicates that the metal element has been incorporated into the silicon-based matrix lattice and is protected. First we use dilute nitric acid to pickle 20mm in diameter

In reaction section a of the catalytic quartz reactor, ICP analysis showed that no Fe ions were dissolved, further indicating that the Fe ions had all entered the lattice of the silicon-based substrate. And if HF acid is used for dissolving both the silicon-based matrix and the metal components, the result of ICP analysis shows that all Fe ions are dissolved and the amount is just converted into the doping amount. The above analysis results indicate that Fe ions have been fully doped into the lattice of the silicon-based matrix, and surface-doped Fe is hardly detected.

2) Of 20mm diameter

HAADF-STEM high resolution electron microscopy and EDX characterization of reaction section A of a catalytic Quartz reactor

A in FIG. 1 represents a diameter of 20mm

Monoatomic electron micrograph of a catalytic quartz reactor (catalytic reactor production example 1); as can be seen from the electron microscope characterization result in a in fig. 1, the white circles are monoatomic doped Fe metal atoms, and EDX (B in fig. 1) further confirms that these white spots are monoatomic Fe species. Other elements such as Cu come from Cu gates. And the catalyst in the whole electron microscope photo is in an amorphous state with long-range disorder and short-range disorder.

3. Direct co-conversion of methane and ethane to olefins, aromatics and hydrogen under oxygen-free continuous flow conditions

All of the catalytic reactors described above were used directly without catalyst loading.

All reaction examples were carried out in a continuous flow microreaction apparatus equipped with a gas mass flow meter, a gas deoxygenation and dehydration tube and an on-line product analysis chromatograph (the off-gas from the reactor was directly connected to the quantitative valve of the chromatograph, and periodic real-time sampling analysis was carried out). Unless otherwise specified, N in the reaction feed gas₂As an internal standard gas. On-line product analysis is carried out by using Agilent 7890B gas chromatography and an FID and TCD dual detector, wherein the FID detector is provided with an HP-1 capillary column to analyze low-carbon olefin, low-carbon alkane and aromatic hydrocarbon; the TCD detector is provided with a Hayesep D packed column to analyze the low-carbon olefin, the low-carbon alkane, the methane, the hydrogen and the internal standard nitrogen. The methane conversion rate, the hydrocarbon product selectivity and the carbon deposit are calculated according to the carbon balance before and after the reaction according to the following formula:

the conversion rate of the methane is increased,

the conversion rate of ethane is increased, and the conversion rate of ethane is increased,

wherein the content of the first and second substances,

the area of the methane peak at the tail gas outlet after the reaction on the TCD detector;

the nitrogen peak area of the tail gas outlet after the reaction on the TCD detector;

methane peak area at room temperature on the TCD detector;

methane peak area at room temperature on the TCD detector;

ethane peak area at room temperature on TCD detector.

The selectivity of the product and the carbon deposit,

wherein the content of the first and second substances,

total number of carbon atoms entering the reactor;

the total number of carbon atoms of methane entering the reactor;

the total number of carbon atoms of methane entering the reactor;

relative correction factors for methane and nitrogen on the TCD detector;

relative correction factor of ethane to nitrogen on TCD detector;

is C_xH_yThe selectivity of the product; c_xH_yX is the number of C, and y is the number of H;

FID Detector upper C_xH_yRelative correction factor of product to benzene;

the peak area of the outlet tail gas on a TCD detector after reaction;

the peak area of the outlet tail gas on the FID detector after the reaction;

in the following examples, each product was detected by gas chromatography.

Example 1

Using a blank quartz tube not doped with a metal or nonmetal active component, after air in the reactor was replaced with 30ml/min Ar gas for about 30 minutes, keeping the Ar flow rate constant, programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction feed gas was 8.0L/g/h (flow rate was 3L/min), and on-line analysis was started after 30 minutes, and the analysis results showed that the conversion of methane was 4%, the selectivity for ethylene was 20%, the selectivity for propylene was 2%, the selectivity for butene was 3%, the selectivity for 1, 3-butadiene was 1%, the selectivity for isobutylene was 2%, the selectivity for benzene was 4%, the selectivity for toluene was 2%, the selectivity for xylene was 1%, the selectivity for naphthalene was 2%, and the selectivity for carbon deposit was 73%. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 1%, and the conversion rate of methane is increased by 3% after hydrogen is added.

Example 2

In that

Catalytic Quartz reactor (catalytic reactor preparation example 1), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH, keeping the Ar flow rate constant₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow velocity is 3L/min), online analysis is started after 30 minutes, and the analysis result shows that the conversion rate of methane is 9%, the selectivity of ethylene is 45%, the selectivity of propylene is 3%, the selectivity of butylene is 3%, the selectivity of 1, 3-butadiene is 10%, the selectivity of isobutene is 1%, the selectivity of benzene is 15%, the selectivity of toluene is 5%, the selectivity of xylene is 5%, the selectivity of naphthalene is 13%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 5%, and the conversion rate of methane is increased by 4% after hydrogen is added.

Example 3

In that

Catalytic Quartz reactor (catalytic reactor preparation example 3), after air in the reactor was replaced with 30ml/min Ar gas for about 30 minutes, the temperature rising rate from room temperature at 6 ℃/min was varied while keeping the Ar flow rate constantThe temperature is sequentially increased to 950 ℃, and 85 percent CH is adjusted simultaneously₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 10L/g/h (the flow rate is 3.5L/min), online analysis is started after 30 minutes, and the analysis result shows that the conversion rate of methane is 16%, the selectivity of ethylene is 58%, the selectivity of propylene is 2%, the selectivity of butylene is 3%, the selectivity of 1, 3-butadiene is 8%, the selectivity of isobutylene is 2%, the selectivity of benzene is 12%, the selectivity of toluene is 2%, the selectivity of xylene is 3%, the selectivity of naphthalene is 10%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 10%, and the conversion rate of methane is increased by 6% after hydrogen is added.

Example 4

In that

Catalytic Quartz reactor (catalytic reactor preparation example 4), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH, keeping the Ar flow rate constant₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow velocity is 3L/min), online analysis is started after 30 minutes, and the analysis result shows that the conversion rate of methane is 18%, the selectivity of ethylene is 60%, the selectivity of propylene is 1%, the selectivity of butylene is 4%, the selectivity of 1, 3-butadiene is 5%, the selectivity of isobutene is 5%, the selectivity of benzene is 14%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 8%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 11%, and the conversion rate of methane is increased by 7% after hydrogen is added.

Example 5

In that

Catalytic Quartz reactor (catalytic reactor preparation example 5), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, the reaction was carried outWhile maintaining the Ar flow rate, the temperature is programmed from room temperature to 950 ℃ at the temperature rise rate of 6 ℃/min, and the 85 percent CH is adjusted₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow velocity is 3L/min), online analysis is started after 30 minutes, and the analysis result shows that the conversion rate of methane is 23%, the selectivity of ethylene is 65%, the selectivity of propylene is 2%, the selectivity of butylene is 3%, the selectivity of 1, 3-butadiene is 10%, the selectivity of isobutene is 5%, the selectivity of benzene is 10%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 2%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 11% after hydrogen is added.

Example 6

In that

Catalytic Quartz reactor (catalytic reactor preparation example 6), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH, while maintaining the Ar flow rate unchanged₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow velocity is 3L/min), online analysis is started after 30 minutes, and the analysis result shows that the conversion rate of methane is 25%, the selectivity of ethylene is 50%, the selectivity of propylene is 1%, the selectivity of butylene is 3%, the selectivity of 1, 3-butadiene is 5%, the selectivity of isobutene is 5%, the selectivity of benzene is 25%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 8%, and carbon deposition is zero. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 13%, and the conversion rate of methane is increased by 12% after hydrogen is added.

Example 7

In that

Catalytic Quartz reactor (catalytic reactor preparation example 7), using 30After the air in the reactor is replaced by the Ar gas in ml/min for about 30 minutes, keeping the flow rate of the Ar unchanged, and carrying out temperature programming from room temperature to 950 ℃ at the temperature rising rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow velocity is 3L/min), online analysis is started after 30 minutes, and the analysis result shows that the conversion rate of methane is 24%, the selectivity of ethylene is 50%, the selectivity of propylene is 1%, the selectivity of butylene is 3%, the selectivity of 1, 3-butadiene is 7%, the selectivity of isobutene is 10%, the selectivity of benzene is 20%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 6%, and carbon deposition is zero. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 14%, and the conversion rate of methane is increased by 10% after hydrogen is added.

Example 8

In that

Catalytic Quartz reactor (catalytic reactor preparation example 8), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH, keeping the Ar flow rate constant₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow rate is 3L/min), online analysis is started after 30 minutes, and the analysis result shows that the conversion rate of methane is 25%, the selectivity of ethylene is 40%, the selectivity of propylene is 1%, the selectivity of butylene is 3%, the selectivity of 1, 3-butadiene is 5%, the selectivity of isobutylene is 5%, the selectivity of benzene is 30%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 13%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 15%, and the conversion rate of methane is increased by 10% after hydrogen is added.

Example 9

In that

CatalysisQuartz reactor (catalytic reactor preparation example 9), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, the temperature was programmed from room temperature to 950 ℃ at a temperature rising rate of 6 ℃/min while adjusting 85% CH, while keeping the Ar flow rate constant₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow rate is 3L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 18%, the selectivity of ethylene is 32%, the selectivity of propylene is 10%, the selectivity of benzene is 10%, the selectivity of naphthalene is 10%, and carbon deposition is 38%. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 10%, and the conversion rate of methane is increased by 8% after hydrogen is added.

The catalyst is surface supported because about 2.3-2.5% of Fe species can not enter into crystal lattice. A large amount of 41% of carbon deposit is generated in the reaction process.

Examples 10 to 20

In that

Catalytic Quartz reactor (catalytic reactor preparation example 10), after air in the reactor was replaced with 30ml/min Ar gas for about 30 minutes, the flow rate of Ar was maintained constant, the temperature was programmed from room temperature at a ramp rate of 6 ℃/min to the following temperature and corresponding space velocity, and 85% CH was adjusted₄/10％H₂/5％N₂The space velocity of the reaction feed gas is as shown in the following table, and the methane conversion rate and the selectivity of each product are as shown in the following table; using 90% CH under the same conditions₄/10％N₂The conversion rate of methane is improved by 2-10% in the reaction of raw gas. Others include (isobutylene, 1, 3-butadiene, toluene, xylene).

Example 21

In that

Catalytic quartzReactor (catalytic reactor preparation example 11), after replacing the air in the reactor with 30ml/min of Ar gas for about 30 minutes, the temperature was programmed from room temperature to 950 ℃ at a temperature rising rate of 6 ℃/min while adjusting 85% CH, while keeping the Ar flow rate constant₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow velocity is 2L/min), online analysis is started after 30 minutes, and the analysis result shows that the conversion rate of methane is 24%, the selectivity of ethylene is 60%, the selectivity of propylene is 2%, the selectivity of butylene is 3%, the selectivity of 1, 3-butadiene is 15%, the selectivity of isobutene is 5%, the selectivity of benzene is 10%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 2%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 12% after adding hydrogen.

Example 22

In that

Catalytic Quartz reactor (catalytic reactor preparation example 12), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow rate is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 25%, the selectivity of ethylene is 52%, the selectivity of butene is 3%, the selectivity of 1, 3-butadiene is 15%, the selectivity of isobutene is 5%, the selectivity of benzene is 20%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 2%, and carbon deposition is zero. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 13% after adding hydrogen.

Example 23

In that

Catalytic Quartz reactor (catalytic reactor preparation example 14), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction raw material gas is 8.0L/g/h (the flow rate is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 25%, the selectivity of ethylene is 52%, the selectivity of 1, 3-butadiene is 15%, the selectivity of isobutene is 8%, the selectivity of benzene is 20%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 2%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 13% after adding hydrogen.

Examples 24 to 34

In that

Catalytic Quartz reactor (catalytic reactor preparation example 15), after replacing the air in the reactor with 45ml/min Ar gas for about 60 minutes, while keeping the flow rate of Ar constant, the temperature was programmed from room temperature at a ramp rate of 6 ℃/min to the following temperature and corresponding space velocity, and 75% CH was adjusted₄/20％H₂/5％N₂The space velocity of the reaction feed gas is as shown in the following table, and the methane conversion rate and the selectivity of each product are as shown in the following table; using 90% CH under the same conditions₄/10％N₂The conversion rate of the reaction raw material gas is improved by 5-10%. Others include (isobutylene, 1, 3-butadiene, toluene, xylene).

Examples 35 to 45

In that

Catalytic Quartz reactor (catalytic reactor preparation example 13) with 80ml/min AAfter about 60 minutes, the air in the reactor is replaced by r gas, the flow rate of Ar is kept constant, the temperature is programmed to the following temperature from the room temperature at the heating rate of 6 ℃/min and the corresponding space velocity, and 70 percent CH is adjusted₄/25％H₂/5％N₂The space velocity of the reaction feed gas is as shown in the following table, and the methane conversion rate and the selectivity of each product are as shown in the following table; using 90% CH under the same conditions₄/10％N₂The conversion rate of methane is improved by 7-12% in the reaction of raw gas. Others include (isobutylene, 1, 3-butadiene, toluene, xylene).

Example 46

In that

Catalytic Quartz reactor (catalytic reactor preparation example 16), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 75% CH₄/20％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow velocity is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 25%, the selectivity of ethylene is 50%, the selectivity of benzene is 22%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 25%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 13% after adding hydrogen.

Example 47

In that

Catalytic Quartz reactor (catalytic reactor preparation example 17), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 75% CH₄/20％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow rate is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 20%, the selectivity of ethylene is 65%, the selectivity of 1, 3-butadiene is 7%, the selectivity of isobutene is 8%, the selectivity of benzene is 17%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 8% after hydrogen is added.

Example 48

In that

Catalytic Quartz reactor (catalytic reactor preparation example 18), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow rate is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 15%, the selectivity of ethylene is 70%, the selectivity of 1, 3-butadiene is 7%, the selectivity of isobutene is 8%, the selectivity of benzene is 12%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 3% after adding hydrogen.

Example 49

In that

Catalytic Quartz reactor (catalytic reactor preparation example 19), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 1020 ℃ at a ramp rate of 6 ℃/min while adjusting 55% CH₄/40％H₂/5％N₂The space velocity of the reaction raw material gas is 20.5L/g/h, the on-line analysis is started after the reaction raw material gas is kept for 20 minutes, and the catalyst is usedLong-term stability studies were performed. The results of the analysis after every 100 hours are shown in the following table. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane is improved by 12-15% in the reaction of raw gas. And the catalyst life is about 500-700 hours higher. Others include (isobutylene, 1, 3-butadiene, toluene, xylene).

Example 50

In that

Catalytic Quartz reactor (catalytic reactor preparation example 20), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 60% CH₄/35％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow rate is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 24%, the selectivity of ethylene is 65%, the selectivity of 1, 3-butadiene is 5%, the selectivity of isobutene is 10%, the selectivity of benzene is 10%, the selectivity of toluene is 3%, the selectivity of xylene is 7% and zero carbon deposition. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 12% after adding hydrogen.

Example 51

In that

Catalytic Quartz reactor (catalytic reactor preparation example 21), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 65% CH₄/30％H₂/5％N₂The space velocity of the reaction raw material gas is 8.0L/g/h (the flow rate is 2L/min), and the reaction raw material gas starts to be on-line after being kept for 30 minutesAnalysis showed 28% conversion of methane, 60% selectivity to ethylene, 7% selectivity to 1, 3-butadiene, 8% selectivity to isobutylene, 15% selectivity to benzene, 2% selectivity to xylene, 8% selectivity to naphthalene, and zero carbon deposition. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 10%, and the conversion rate of methane is increased by 18% after hydrogen is added.

Example 52

In that

Catalytic Quartz reactor (catalytic reactor preparation example 22), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction feed gas was 8.0L/g/h (flow rate was 2L/min), and on-line analysis was started after 30 minutes, showing that the conversion of methane was 4%, the selectivity for ethylene was 30%, the selectivity for 1, 3-butadiene was 2%, the selectivity for isobutylene was 3%, the selectivity for benzene was 10%, the selectivity for naphthalene was 20%, and the selectivity for carbon deposition was 35%. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 2%, and the conversion rate of methane is increased by 2% after hydrogen is added.

Example 53

In that

Catalytic Quartz reactor (catalytic reactor preparation example 23), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction feed gas was 8.0L/g/h (flow rate 2L/min), and on-line analysis was started after 30 minutes, showing that the conversion of methane was 27%, the selectivity for ethylene was 75%, the selectivity for 1, 3-butadiene was 5%, the selectivity for isobutylene was 10%, and the selectivity for benzene was 10%5 percent, selectivity of dimethylbenzene is 5 percent, and carbon deposition is avoided. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 10%, and the conversion rate of methane is increased by 17% after hydrogen is added.

Example 54

In that

Catalytic Quartz reactor (catalytic reactor preparation example 24), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction raw material gas is 8.0L/g/h (the flow velocity is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 16%, the selectivity of ethylene is 50%, the selectivity of 1, 3-butadiene is 7%, the selectivity of isobutene is 8%, the selectivity of benzene is 22%, the selectivity of toluene is 1%, the selectivity of xylene is 7%, the selectivity of naphthalene is 5%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 4% after hydrogen is added.

Example 55

In that

Catalytic Quartz reactor (catalytic reactor preparation example 25), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow rate is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 22%, the selectivity of ethylene is 55%, the selectivity of 1, 3-butadiene is 7%, the selectivity of isobutene is 8%, the selectivity of benzene is 22%, the selectivity of toluene is 6%, the selectivity of xylene is 2%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 10%, and the conversion rate of methane is increased by 12% after adding hydrogen.

Example 56

In that

Catalytic Quartz reactor (catalytic reactor preparation example 26), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 85% CH₄/10％H₂/5％N₂The space velocity of the reaction raw material gas is 8.0L/g/h (the flow velocity is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 14%, the selectivity of ethylene is 50%, the selectivity of 1, 3-butadiene is 7%, the selectivity of isobutene is 8%, the selectivity of benzene is 15%, the selectivity of toluene is 5%, the selectivity of xylene is 5%, the selectivity of naphthalene is 10%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 9%, and the conversion rate of methane is increased by 5% after hydrogen is added.

Example 57

In that

Catalytic Quartz reactor (catalytic reactor preparation example 27), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, the temperature was programmed from room temperature to 950 ℃ at a temperature rising rate of 6 ℃/min while adjusting 15% CH, while keeping the Ar flow rate constant₄/80％C₂H₆/5％N₂The space velocity of the reaction raw material gas is 8.0L/g/h (the flow velocity is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 26%, the selectivity of ethylene is 50%, the selectivity of 1, 3-butadiene is 7%, the selectivity of isobutene is 8%, the selectivity of benzene is 22%, the selectivity of toluene is 1%, the selectivity of xylene is 2%, the selectivity of naphthalene is 10%, and zero carbon deposition is achieved. Using 90% CH under the same conditions₄/10％N₂Reacting raw material gas with methane conversion rate of 12%, adding hydrogenThe methane conversion increased by 13%.

Example 58

In that

Catalytic Quartz reactor (catalytic reactor preparation example 28), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, the temperature was programmed from room temperature to 950 ℃ at a temperature rising rate of 6 ℃/min while adjusting 65% CH, while keeping the Ar flow rate constant₄/30％H₂/5％N₂The space velocity of the reaction feed gas was 8.0L/g/h (flow rate was 2L/min), and after 30 minutes, on-line analysis was started, which revealed that the conversion of methane was 26%, the selectivity for ethylene was 65%, the selectivity for 1, 3-butadiene was 7%, the selectivity for isobutylene was 8%, the selectivity for benzene was 17%, the selectivity for toluene was 1%, and the selectivity for xylene was 2% with zero carbon deposition. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 14% after ethane is added.

Example 59

In that

Catalytic Quartz reactor (catalytic reactor preparation example 29), after replacing the air in the reactor with 30ml/min Ar gas for about 30 minutes, while maintaining the Ar flow rate constant, the temperature was programmed from room temperature to 950 ℃ at a temperature rise rate of 6 ℃/min while adjusting 77% CH₄/18％H₂/5％N₂The space velocity of the reaction feed gas is 8.0L/g/h (the flow rate is 2L/min), online analysis is started after 30 minutes, and the results show that the conversion rate of methane is 24%, the selectivity of ethylene is 60%, the selectivity of 1, 3-butadiene is 7%, the selectivity of isobutene is 8%, the selectivity of benzene is 22%, the selectivity of toluene is 1%, the selectivity of xylene is 2% and zero carbon deposition are obtained. Using 90% CH under the same conditions₄/10％N₂The conversion rate of methane in the reaction raw material gas is 12%, and the conversion rate of methane is increased by 12% after adding hydrogen.

In conclusion, the reaction temperature is 750-1150 ℃ in a catalytic reactor mode; the reaction pressure is normal pressure; the mass space velocity of the methane is 1.0-30.0L/g/h. The conversion rate of methane is 20-70%; the olefin selectivity is 70-95%; the benzene selectivity is 5-30%, and carbon deposition is avoided.

It follows from this that: the catalyst of the catalytic reactor has the characteristics of long service life (>500h), good oxidation reduction and hydrothermal stability of the catalyst at high temperature, high product selectivity, zero 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 implement the full scope of the present invention as defined by the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.

The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims

1. A method for preparing olefin, aromatic hydrocarbon and hydrogen by converting methane under the hydrogen condition is characterized in that: the method adopts a quartz catalytic reactor for reaction operation, and takes methane and hydrogen mixed gas as raw material gas to be directly converted into olefin, aromatic hydrocarbon and hydrogen through catalytic reaction;

directly doping a catalyst active component into a crystal lattice on a contact surface of a quartz tube and a raw material, or coating a Si-based material doped with the catalyst active component into the crystal lattice on the contact surface of the quartz tube and the raw material to form a crystal lattice doped catalytic dopant thin layer, wherein a quartz reactor with the contact surface directly doped with the crystal lattice or coated with the crystal lattice doped thin layer with a catalytic function is called a catalytic reactor, and the quartz catalytic reactor has double functions of a reactor and a catalyst; the contact surface refers to the inner wall or the outer wall of the quartz tube;

the active component is a metal element, a metal or a mixture of non-metal elements, and the doping amount of the metal element is more than 0.05wt.% and less than or equal to 5wt.%, based on 100% of the total weight of the dopant thin layer; non-metal element doping amount is 0-5 wt.%;

the metal elements include: one or more of lithium, magnesium, aluminum, calcium, strontium, barium, titanium, manganese, vanadium, chromium, iron, cobalt, nickel, zinc, germanium, tin, gallium, zirconium, gold, lanthanum, cerium, praseodymium, neodymium, europium, erbium, ytterbium, ruthenium, gold, or platinum;

the non-metallic elements include: one or two of boron and phosphorus;

the quartz catalytic reactor is prepared by adopting the following solid phase doping technology; the solid phase doping technology is an improved chemical vapor deposition (MCVD) method, and is one of the following three;

the first method comprises the following steps: under 1-3 atmospheric pressure, silicon tetrachloride liquid is driven by carrier gas, or the silicon tetrachloride liquid and gas-phase-doped non-metallic chloride at 50-500 ℃ are driven by the carrier gas to enter an MCVD device to react with oxygen at 1650 ℃ of 1400-100 ℃, a silicon-based material thin layer with the thickness of 0.01-100 microns is vapor-deposited on the inner wall of the quartz reactor, and then the quartz reactor is immersed in the aqueous solution doped with metal salt at the temperature of 20-80 ℃ for 0.1-20 hours; melting the immersed quartz tube at 1800-2200 ℃ to obtain a corresponding metal lattice doped reactor, forming a dopant thin layer with the thickness of 100nm-1mm on the inner wall of the reactor, then immediately cooling, and solidifying to obtain the quartz reactor with catalytic activity;

and the second method comprises the following steps: under 1-3 atmospheric pressure, silicon tetrachloride liquid and gas phase doping volatile doping metal salt gasified at 50-950 ℃ are driven by carrier gas, or the silicon tetrachloride liquid, the gas phase doping volatile doping metal salt gasified at 50-950 ℃ and non-metal chloride doped at 50-500 ℃ are driven by carrier gas, enter an MCVD device to react with oxygen at 1400-1650 ℃, are deposited for 10 minutes-2 hours in a gas phase on the inner wall of the quartz tube, are melted at 1800-2200 ℃ to obtain a corresponding metal lattice doping reactor, and a dopant thin layer with the thickness of 100nm-1mm is formed on the inner wall of the reactor, and then are immediately cooled and solidified to obtain the reactor with catalytic activity;

and the third is that: under 1-3 atmospheric pressure, silicon tetrachloride liquid and normal-temperature liquid metal chloride or normal-temperature liquid non-metal chloride or oxychlorides enter an MCVD device to react with oxygen at the temperature of 1400-1650 ℃ under the drive of a carrier, the silicon tetrachloride liquid and the normal-temperature liquid metal chloride or the normal-temperature liquid non-metal chloride or the oxychlorides are deposited on the inner wall of the quartz tube to carry out vapor deposition for 10 minutes to 2 hours, then the silicon tetrachloride liquid and the MCVD device are melted at the temperature of 1800-2200 ℃ to obtain a reactor doped with corresponding metal lattices, a dopant thin layer with the thickness of 100nm-1mm is formed on the inner wall of the reactor, and then the reactor is immediately cooled and solidified to obtain the reactor with catalytic activity; the volume content ratio of the hydrogen to the methane is 0.05-10.

2. The method of claim 1, wherein: the thickness of the dopant thin layer is 100 nanometers to 1 millimeter.

3. The method of claim 2, wherein: the thickness of the dopant thin layer is 200 nanometers to 0.5 millimeter.

4. The method of claim 2, wherein: the thickness of the dopant thin layer is 500 nanometers to 200 micrometers.

5. The method of claim 2, wherein: the thickness of the thin layer of the dopant is 1-50 microns.

6. The method of claim 1, wherein: the active component is a metal element, a metal or a non-metal element mixture, and the doping amount of the metal element is 0.05-3 wt% based on 100% of the total weight of the dopant thin layer; the doping amount of the non-metal elements is 0.05 wt% -3 wt%.

7. The method of claim 1, wherein: the metal elements include: one or more of barium, titanium, manganese, vanadium, chromium, iron, cobalt, nickel, zinc, germanium, tin, gallium, zirconium, gold, lanthanum, cerium, praseodymium, neodymium, europium, erbium, ytterbium, ruthenium, gold and platinum.

8. The method of claim 1, wherein: the metal salt in the first type is one or more than two of nitrate, soluble halide, soluble sulfate, soluble carbonate, soluble phosphate, soluble methoxide, soluble ethoxide, soluble formate and soluble acetate.

9. The method of claim 1, wherein: the metal salt in the second type is one or more than two of metal chloride, methoxide, ethoxide, formate and acetate.

10. The method of claim 1, wherein: the normal temperature liquid metal chloride in the third type is one or more than two of tin tetrachloride, titanium tetrachloride and germanium tetrachloride; the normal temperature liquid nonmetal chloride or oxychloride is one or two of boron trichloride and phosphorus oxychloride.

11. The method of claim 1, wherein: in the preparation process of the quartz catalytic reactor, the deposition time is 10 minutes to 1 hour.

12. The method of claim 1, wherein: the flow rate of the carrier gas is 0.01-50L/min.

13. The method of claim 1, wherein: the melting atmosphere is one or more of inert gas, air or oxygen, and the inert gas comprises one or more of helium, argon or nitrogen; the melting time is 0.01-3 hours.

14. The method of claim 1, wherein: the cooling is gas cooling; the cooling rate is 50 ℃/s-2000 ℃/s; the gas in the gas cooling is one or more than two of inert gas, nitrogen, oxygen or air.

15. The method of claim 14, wherein: the cooling is gas cooling; the cooling rate is 100-1800 ℃/s.

16. The method of claim 1, wherein: the carrier gas is high purity oxygen with 99.9999% volume concentration or high purity helium with 99.9999% volume concentration.

17. The method of claim 1, wherein: all catalytically active components in the catalyst thin layer of the catalytic reactor contact surface are lattice-doped to the contact surface thin layer, and no metal or metal compound is loaded on the surface.

18. The method of claim 1, wherein: the catalytic reactor is adopted to directly convert the mixture gas of methane and hydrogen into olefin, aromatic hydrocarbon and hydrogen through catalytic reaction.

19. The method of claim 18, wherein: the temperature of the catalytic reaction is 750-1200 ℃.

20. The method of claim 19, wherein: the temperature of the catalytic reaction is 900-1150 ℃.

21. The method of claim 18, wherein: the reaction takes the mixed gas of methane and hydrogen as raw materials, and the reaction raw material gas is methane and hydrogen gas or comprises one or two of other inert atmosphere gas and non-inert atmosphere gas besides methane and hydrogen;

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, carbon dioxide, water and alkane with the C number of 3-4, and the volume content ratio of the non-inert atmosphere gas to methane is 0-10%.

22. The method of claim 18, wherein: when the continuous reaction is carried out, the reaction pressure is 0.05-1 MPa; when the inner diameter of the quartz catalytic reactor is 5-15mm, the space velocity of the reaction raw material gas is 0.5-20.0L ∙ g^-1∙h^-1(ii) a When the inner diameter of the quartz catalytic reactor is 15-25mm, the space velocity of the reaction raw material gas is 2-40.0L ∙ g^-1∙h^-1(ii) a When the pipe diameter of the quartz catalytic reactor is 25-35mm, the space velocity of the reaction feed gas is 4-60.0L ∙ g^-1∙h^-1(ii) a When the pipe diameter of the quartz catalytic reactor is 35-45mm, the space velocity of the reaction raw material gas is 5.0-80.0L ∙ g^-1∙h^-1(ii) a When the pipe diameter of the quartz catalytic reactor is 45-55mm, the space velocity of the reaction raw material gas is 5.0-100.0L ∙ g^-1∙h^-1(ii) a When the pipe diameter of the quartz catalytic reactor is 55-65mm, the space velocity of the reaction raw material gas is 5.0-150.0L ∙ g^-1∙h^-1(ii) a When the pipe diameter of the quartz catalytic reactor is 65-75mm, the space velocity of the reaction raw material gas is 5.0-200.0L ∙ g^-1∙h^-1(ii) a When the pipe diameter of the quartz catalytic reactor is 75-85mm, the space velocity of the reaction raw material gas is 5.0-300.0L ∙ g^-1∙h^-1。

23. The method of claim 22, wherein: when the reaction is carried out continuously, the reaction pressure is 0.1 to 0.5 MPa.

24. The method of claim 18, wherein: the product of the aromatic hydrocarbon comprises one or more than two of benzene, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene and naphthalene; the olefin product comprises one or more than two of ethylene, propylene, butylene, isobutene and 1, 3-dibutene.