Patent Description:
Development and effective utilization of natural gas (methane) resource represent the development direction of the contemporary energy structure and is also one of important ways of ensuring sustainable development and energy greening. In recent years, western developed countries have made breakthrough in the development aspect of shale gas and "combustible ice", resulting in a "shale gas revolution". In China, shale gas resources have many types and are distributed centrally relatively. The recoverable resource potential is <NUM> trillion cubic meters (Qinghai-Tibet region excluded), which is equivalent to that of conventional natural gas for land in China and close to <NUM> trillion cubic meters of America. The "Twelfth Five-year plan" in China has deployed in the development field of the shale gas to obtain technical breakthrough in several different kinds of shale oil and gas regions and to preliminarily establish productivity with economic benefits.

However, how to efficiently use gaseous hydrocarbon resources (methane) has already become an important link that restricts the development of energy industry of China. It reignites the world-wide interest to convert such abundant resources into fuel and high-added-value chemicals (especially light olefins), and also an important step for improving the energy structure of China. Light olefins, such as ethylene, etc., are very important raw material or intermediates in the chemistry and chemical engineering process. Traditional light olefins (C2-C4) mainly come from the petrifaction process of naphtha cracking, etc., so that the production of the olefins has already become a symbol for measuring the petrochemical production level of one country and region. As petroleum resources are increasingly exhausted, it is a focus of current study to explore a method for making the light olefins in a non-traditional route. Accordingly, some typical substitute routes arise at the historic moment, such as the route of starting from synthetic gas and further converting methanol or dimethyl ether to obtain the light olefins, but this route has complicated process and lower atom economy. To shorten the reaction route, a large number of studies are carried out on direct synthesis of the light olefins through a Fischer-Tropsch route starting from the synthetic gas. However, the above substitute route must consume CO or H<NUM> to remove O in CO, which may inevitably cause C atom utilization rate lower than <NUM>%. In spite of expensive productivity input, heavy CO<NUM> emission and atom utilization rate lower than <NUM>%, the indirect process still occupies a dominant status in application of natural gas industry.

In contrast, direct conversion of natural gas has enormous economic potential and is more environmentally friendly. However, direct conversion of natural gas remains a difficult problem in the chemistry and chemical engineering process. The essential component of natural gas is methane. The bond energy of C-H bond is as high as <NUM> kJ/mol, while the methane molecule itself almost has no electron affinity. In addition, ionization energy is large and polarization rate is small. Therefore, activation of the C-H bond of methane is regarded as a "holy grail" of chemistry and even chemistry field. Keller and Bhasin has reported activation of the C-H bond of methane under the participation of O<NUM>. Their pioneering work ignites the world-wide enthusiasm on studying preparation of ethylene from oxidative coupling of methane under high temperature (><NUM>), in which hundreds of catalysis materials are synthesized and tested. The study has reached the peak in the <NUM>. In the oxidative coupling process, because of the introduction of molecular oxygen (O<NUM>), over oxidation of methane and its products are inevitably caused, thereby producing a great number of products with stabler thermodynamics than methane, such as CO<NUM> and H<NUM>O and finally causing relatively low C atom utilization efficiency. Due to the bottleneck of the development of new material and raw catalysts, the development of the oxidative coupling process of methane stagnates. So far, new technologies with economic feasibility are rarely reported. A recent study proposes that gas-phase S with weak oxidability substitutes for molecular oxygen O<NUM> to generate an oxidative coupling reaction of methane. At temperature of <NUM> (reaction gas: <NUM>%CH<NUM>/Ar), an optimal PdS/ZrO<NUM> catalyst can realize <NUM>% of methane conversion; however, C<NUM>H<NUM> selectivity is only about <NUM>%, but can produce a great number of CS<NUM> and H<NUM>S. The above study reveals that oxygen (or oxidizer) assisted methane activation inevitably causes over oxidation.

Therefore, direct conversion of methane without oxygen (or without oxidizer) is considered to be an ideal activation and conversion route of methane. Under the condition of no oxygen (or no oxidizer), over oxidation of methane or products can be effectively avoided, thereby inhibiting emission of greenhouse gas CO<NUM> and then increasing C atom utilization rate. The challenges of preparing ethylene by direct catalytic conversion of methane are that: <NUM>) the first C-H bond is broken through controllable methane activation; <NUM>) depth dehydrogenation on a catalyst surface is suppressed; <NUM>) generation of greenhouse gas CO<NUM> and carbon deposition is avoided, wherein <NUM> and <NUM> are for the catalyst, while <NUM> is for the reaction process. Over oxidation of products of the aerobic process is inevitable, resulting in inevitable generation of CO<NUM>. Only the oxygen-free process can avoid producing CO<NUM>, but is easy to produce carbon deposition. Therefore, a study on how to avoid carbon deposition becomes a current focus of the oxygen-free process. The key to solve the carbon deposition problem is to understand a source of carbon deposition. By taking an oxygen-free aromatization process as an example, the carbon deposition mainly comes from: methane is deeply dehydrogenated to generate carbon deposition ("graphite-like carbon deposition") on the surface of Mo species of the catalyst; in the diffusion process, the products are cyclized and coupled on B acid site of a duct or orifice of a support and zeolite to generate carbon deposition ("polyaromatic carbon deposition"). Therefore, three challenges of preparing ethylene by direct catalytic conversion of methane are design and construction of the catalyst.

In <NUM>, researchers from Dalian Institute of Chemical Physics (DICP) reported CH<NUM> dehydroaromatization in a continuous flow pattern on the Mo/HZSM-<NUM> catalyst for the first time. At <NUM> and normal pressure,CH4 conversion is about <NUM>% and aromatics selectivity is greater than <NUM>% (exclusive of carbon deposition in the reaction), forming an important milestone of study on CH<NUM> dehydroaromatization process. In the past decades, the study work of multinational scientists mainly focuses on preparation, development, reaction and deactivation mechanism of the catalyst. Nevertheless, industrial applications are restricted by the rapid carbon deposition and deactivation of the catalyst.

Recently, a composite catalyst prepared by American siluria company (<CIT>, <CIT>, <CIT>, <CIT> and <CIT>) using a biological template method generates <NUM>% of methane conversion and <NUM>% of ethylene selectivity in the oxidative coupling reaction at <NUM>-<NUM>. At present, the company is performing pilot production, and is expected to conduct industrialized demonstration in <NUM>-<NUM>. For preparation of methanol or formaldehyde from selective oxidation of methane, because the oxidation velocity of target products of methanol and formaldehyde is much higher than that of methane as raw material, the reaction selectivity is lower and the products have hardly scale application prospect.

<CIT> discloses a rare earth-added optical fiber and its production. <CIT> discloses a specific metal ion-doped TiO<NUM> plate-type micro photocatalytic reactor. <CIT> discloses a process for making styrene using microchannel process technology. <CIT> discloses a doping device for an optical fiber preform. <CIT> discloses specific solid membranes, electrochemical reactors and reactor components, and their use in oxidation reactions. <CIT> discloses a method for producing a photocatalyst carrier. <CIT> discloses a method for doping optical fibers. <CIT> and <CIT> disclose nanowires useful as heterogeneous catalysts. <CIT> discloses a titanium oxide for water or air treatment and its production. <CIT> discloses a photocatalyst carrier and method for treating fluid. <CIT> discloses a fluorine-resistant glass for UV radiation and a lamp using it.

Two patents (application numbers: <CIT> and <CIT>) have been applied earlier. These two patents mainly apply for a metal doped silicon-based catalyst so as to realize the process of producing alkene through catalytic conversion of methane by a fixed bed or fluidized bed or mobile bed by placing the catalyst into a reactor. The two methods have the disadvantages of large pressure drop of catalyst bed layer, poor heat conduction of catalyst, large temperature difference of bed layer, harsh preparation condition of catalyst, difficult scaleup, etc. See also <CIT>.

Therefore, the purpose of the present invention is to lattice-dope active metal or non-metal component into the inner wall of a quartz or silica carbide reactor with a unique shape, or lattice-dope active metal or non-metal component into quartz or silica carbide and coat on the inner wall of the reactor, so that the catalyst and the reactor become a whole. Compared with the above two patents, the method has the following advantages:.

The process is easier for industrial amplification. At present, the industrialized methane reforming and ethane pyrolysis adopts the shell and tube reactors (no catalyst bed). Namely, the adopted shell and tube reactors are directly replaced with the catalytic reactor of the present invention to realize production of ethylene through methane.

The present invention to solve the technical problem is: to overcome defects of the prior art and to provide a catalytic reactor configuration, preparation and a method of direct synthesis of ethylene through oxygen-free catalysis of methane. The present invention has the characteristics of long life of catalysts, high stability of redox and hydrothermal conditions at high temperature, high conversion rate of methane, high selectivity of products, zero coke deposition, no scaleup of catalyst, small industrialization difficulty, easy separation of products, good process reproducibility, safe and reliable operation.

The so-called catalytic reactor in the present invention refers to directly lattice-doping active components to the inner wall of a quartz or silica carbide tube; or coating Si-based material lattice-doped by the active components to the inner wall of the quartz tube or the silica carbide tube to form a dopant thin layer, and finally melting at high temperature to form a catalytic reactor. The so-called oxygen-free conversion of methane refers to a manner that methane is converted directly in absence of oxidizer (such as oxygen, elemental sulfur, sulphur dioxide, etc.).

The catalytic reactor refers to lattice-doping metal atoms or nonmetallic atoms to the inner wall of a quartz or silica carbide reaction tube. The doping refers to lattice doping. The so-called lattice doping is that the dopant metallic elements form a chemical bonding with some elements in the metallic elements or nonmetallic elements, which will lead to the dopant metallic elements being confined in the lattice of the doped base material, resulting in specific catalytic performance.

The metal doping amount of the metal lattice-doped catalysts are more than 10ppm, but less than or equal to <NUM>. % of total weight (<NUM>%) of the catalyst; the metal doping amount of the nonmetal lattice-doped catalysts shall be more than 10ppm, but less than or equal to 1wt. The metal doping amount of the metal lattice-doped catalysts is preferably 100ppm-<NUM>. The doping amount of the metal or metal compounds in the Si material is <NUM>-<NUM>. If the doping amount is higher than 1wt. %, it will be difficult to form lattice doping.

The so-called amorphous-molten-state materials are that the metal and silicon-based materials are all in a molten state in the preparation process, and then amorphous materials with long-range disorder and short-range order are formed after being rapidly cooled.

The dopant metallic elements comprise: 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 and ytterbium.

The dopant nonmetallic elements comprise: boron and phosphorus.

For the dopant metallic elements, the states of the dopant metal are one or more of metal oxides, metal carbides and metal silicates. For the dopant nonmetallic elements, the states of the dopant non-metal are metal oxides.

The catalysts are silicon-based materials that comprise Si bonded with one or more than two of C and O as the main body, which is obtained by doping in its lattice metal dopants, forming a molten state, and solidifying the molten material.

The precursors (states for pre-dopant metallic elements) of dopant metallic elements include one or more than two of nitrates, chloride, organic acid salts of C atom number from <NUM> to <NUM> and organic alcohol salt of C atom number from <NUM> to <NUM>. The precursors (states for pre-dopant metallic elements) of dopant non-metallic elements include one or more than two of chloride or oxygen chloride.

The silicon-based material of the dopant metallic elements is the inner wall of the reactor, and mainly includes SiO<NUM> or SiC.

As shown in <FIG>, a catalytic reactor configuration at least comprises a preheating section and a reaction section, wherein the reaction section refers to directly lattice doping active components to the inner wall of a quartz tube or a silica carbide tube, or coating Si-based material lattice-doped by the active components to the inner wall of the quartz tube or the silica carbide tube to form a dopant thin layer, and the quartz tube or the silica carbide tube with the inner wall which is directly doped or doped by coating is called as the reaction section; reaction conditions of the catalytic reactor configuration also include an inlet section located at the front of the preheating section or a transition section located between the preheating section and the reaction section or an outlet section located at the rear of the reaction section, or simultaneously include the above inlet section, the transition section and the outlet section; and one or more sections of the inlet section, the preheating section, the transition section, the reaction section and the outlet section are respectively manufactured and connected.

The length II of the preheating section and the length IV of the reaction section are respectively <NUM>-<NUM>. The inner diameter A of the inlet section, the inner diameter B of the preheating section, the inner diameter C of the transition section, the inner diameter D of the reaction section and the inner diameter E of the outlet section are respectively <NUM>-<NUM>, and preferably <NUM>-<NUM>. The length I of the inlet section, the length III of the transition section and the length V of the outlet section are not larger than <NUM>, and <NUM>< I+III+V <<NUM>. The length I of the inlet section, the length II of the preheating section, the length III of the transition section, the length IV of the reaction section and the length V of the outlet section satisfy: <NUM>< I + II + III + IV + V <<NUM>.

Moreover, the inner diameter of each section needs to satisfy: D>A =B=C=E, or D=B>A =C=E, or B>D>A=C=E, or D>B>A=C=E, or A=B>D>C=E, or A=B>D>C>E, or A=B=C=D=E, or A=E>B=C=D, or A=C=E>B=D.

The thickness of the dopant thin layer is <NUM>-<NUM>, preferably <NUM>-<NUM>, more preferably <NUM>-<NUM> and further preferably <NUM>-<NUM>.

The reaction section in the catalytic reactor is prepared through the following solid phase doping technology. The solid phase doping technology is a modified chemical vapor deposition (MCVD) method which uses an MCVD apparatus.

The purpose of the following preparation process of the reaction section is to improve the dispersion of the metallic elements in the silicon-based materials, and to dope the metallic elements more effectively in the lattice of amorphous-molten-state materials made from Si bonded with one or more than two of C and O element.

The solid phase doping technology comprises the modified chemical vapor deposition (MCVD) method.

The first method: at <NUM>-<NUM> atmospheric pressure, bringing silicon tetrachloride liquid and nonmetallic chloride which is gas-phase doped at <NUM>-<NUM> under the drive of support gas to enter the MCVD apparatus to react at <NUM>-<NUM>; conducting vapor deposition of SiO<NUM> thin layer with a thickness of <NUM>-<NUM> micrometers on the inner wall of the reaction section IV; subsequently immersing the reaction section IV at <NUM>-<NUM> into metal salt (one or more than two of nitrate, soluble halogenide, soluble sulphate, soluble carbonate, soluble calcium phosphate, soluble organic alkoxide with C number of <NUM>-<NUM>, or organic acid salt with C number of <NUM>-<NUM>) doped aqueous solution for <NUM>-<NUM> hours; then melting the reaction section IV at <NUM>-<NUM> to obtain the corresponding metal lattice doped reaction section of the inner wall; forming a dopant thin layer with a thickness of <NUM>-<NUM> on the inner wall of the reaction section; then immediately cooling; and curing to obtain the reaction section of the catalytic reactor.

The second method: at <NUM>-<NUM> atmospheric pressure, bringing silicon tetrachloride liquid and gas-phase-doped volatile metal salt (one or more than two of metal chloride, organic alkoxide with C number of <NUM>-<NUM>, and organic acid salt with C number of <NUM>-<NUM>) which is gasified at <NUM>-<NUM> or nonmetallic chloride which is gas-phase doped at <NUM>-<NUM> under the drive of the support gas (oxygen or helium) to enter an MCVD apparatus to react with oxygen at <NUM>-<NUM>; depositing for <NUM>-<NUM> and then conducting vapor deposition for the dopant thin layer on the inner wall of the reaction section; subsequently melting at <NUM>-<NUM> to obtain the corresponding metal lattice doped reaction section of the inner wall; forming a dopant thin layer with a thickness of <NUM>-<NUM> on the inner wall of the reaction section; then immediately cooling; and curing to obtain the reaction section of the catalytic reactor.

The third method: at <NUM>-<NUM> atmospheric pressure, bringing silicon tetrachloride liquid and normal-temperature liquid metal chloride (tin tetrachloride, titanium tetrachloride and germanium tetrachloride) or normal-temperature liquid nonmetallic chloride or oxygen chloride (boron trichloride and phosphorous oxychloride) under the drive of support gas to enter an MCVD apparatus to react at <NUM>-<NUM>; depositing for <NUM>-<NUM> and then conducting vapor deposition for the dopant thin layer on the inner wall of the reaction section; subsequently melting at <NUM>-<NUM> to obtain the corresponding metal lattice doped reaction section of the inner wall; forming a dopant thin layer with a thickness of <NUM>-<NUM> on the inner wall of the reaction section; then immediately cooling; and curing to obtain the reaction section of the catalytic reactor.

The reaction section of the catalytic reactor can also be prepared by a solid-liquid phase doping technology. A sol-gel method is combined with a high temperature melting technology. The purpose of the following preparation process is to improve the dispersion of the metallic elements in the silicon-based materials, and to dope the metal elements more effectively in the lattice of amorphous-molten-state materials made from Si bonded with one or more of C and O element.

At room temperature, the inner wall of the reaction section IV is etched using HF or NaOH solution for <NUM>-<NUM>, or the inner wall of the reaction section IV is ground for <NUM>-<NUM> using SiC particles of <NUM>-<NUM> meshes; meanwhile, a mixed solution of metal salt/silicate/water is prepared; the mixed solution is uniformly covered on the inner wall of the etched reaction section; sol-gel reaction is conducted at <NUM>-<NUM>; after sol and gel treatment of the inner wall of the reaction section IV for <NUM>-<NUM>, melting is conducted at <NUM>-<NUM> to obtain the corresponding metal lattice doped reactor of the inner wall; the thickness of the active component film is formed on the inner wall of the reactor, i.e., the thickness is <NUM>-<NUM>; then immediate cooling is conducted; and curing is made to obtain the reaction section of the catalytic reactor.

The metal salt used in the solid phase doping technology (the first method) is one or more than two of nitrate, soluble halogenide, soluble sulphate, soluble carbonate, soluble calcium phosphate, soluble organic alkoxide with C number of <NUM>-<NUM>, or organic acid salt with C number of <NUM>-<NUM>.

The metal salt used in the solid phase doping technology (the second method) is one or more than two of metal chloride, organic alkoxide of C number of <NUM>-<NUM>, and organic acid salt of C number of <NUM>-<NUM>.

The normal-temperature liquid metal chloride used in the solid phase doping technology (the third method) includes tin tetrachloride, titanium tetrachloride and germanium tetrachloride; and the normal-temperature liquid nonmetallic chloride or oxygen chloride includes boron trichloride and phosphorous oxychloride.

The preparation process of the solid phase doping technology (the first method) comprises an immersing process, and the solubility of immersion liquid is 50ppm-<NUM>%; immersion time is <NUM>-<NUM>, and preferably <NUM>-<NUM>; and immersion temperature is preferably <NUM>-<NUM>.

In the preparation process of the catalyst of the solid phase doping technology, deposition time is <NUM>-<NUM>.

In the preparation process of the catalyst of the solid phase doping technology, the flow velocity of the support gas is <NUM>-<NUM>/min.

The preparation process of the solid-liquid phase doping technology (sol-gel bonded with high temperature melting) comprises a sol-gel process, and the concentration of the metallic elements is 50ppm-<NUM>%; the treatment time of sol is <NUM>-<NUM>, and preferably <NUM>-<NUM>; gel temperature is <NUM>-<NUM>, and preferably <NUM>-<NUM>; and the treatment time of gel is <NUM>-<NUM>, and preferably <NUM>-<NUM>.

In the preparation process of the solid-liquid phase doping technology (sol-gel bonded with high temperature melting), the silicate comprises one or more than two of tetramethyl orthosilicate, tetraethoxysilane, tetrapropyl orthosilicate, isopropyl silicate, tetrabutyl orthosilicate or trimethylsiloxysilicate.

In the preparation process of the solid-liquid phase doping technology (sol-gel bonded with high temperature melting), the content ratio of the metal salt to the silicate is <NUM>:<NUM> to <NUM>:<NUM>, and the content ratio of the silicate to water is <NUM>:<NUM> to <NUM>:<NUM>.

In the preparation process of the catalyst, a melting atmosphere is inert gas, air or oxygen; the inert gas comprises one or more of helium, argon or nitrogen; and melting time is <NUM>-<NUM>.

In the preparation process of the catalyst, the thickness of the active component film is preferably <NUM>-<NUM>, more preferably <NUM>-<NUM> and further preferably <NUM>-<NUM>.

The solidification is that the catalyst preparation process involves an important cooling process after the melting process; and the said cooling process includes rapid cooling or natural cooling.

The cooling is gas cooling. A cooling rate is preferably <NUM> /s-<NUM> /s, and preferably <NUM>-<NUM>/s; and the gas in the gas cooling is one or more than two of inert gases, nitrogen, oxygen or air.

The support gas is high purity oxygen or high purity helium (high purity refers to <NUM>%).

The coated catalyst layer on the inner wall of the quartz or silica carbide reactor only comprises lattice doped metallic elements, and supports no metal or metal compound on the surface.

The catalysts that have dopant metal in amorphous-molten-state materials made from one or more than two of Si, C and O element can be expressed as A©SiO<NUM>, A©SiC and A©SiCxOy (4x+2y=<NUM>, and x and y are not zero at the same time), and the ranges of x and y are <NUM>-<NUM> and <NUM>-<NUM>, and A denotes the dopant metallic elements.

The catalysts that have dopant non-metal in amorphous-molten-state materials made from one or more than two of Si, C and O element can be expressed as B©SiO<NUM> and B©SiCxOy (4x+2y=<NUM>, and x and y are not zero at the same time), and the ranges of x and y are <NUM>-<NUM> and <NUM>-<NUM>, and A denotes the dopant nonmetallic elements.

In A©SiO<NUM> metal doped catalysts, the metal element A is inserted in the lattice of SiO<NUM>, and by partially replacing Si atoms, bonds with the adjacent O atoms (A-O). In A©SiC doped catalysts, the metal element A is inserted in the lattice of SiC, and by partially replacing Si or C atoms, bonds with the adjacent C or Si atoms (A-C or Si-A). In A©SiCxOy doped catalysts, the metal element A is inserted the lattice of SiCxOy, and by partially replacing Si or C atoms, bonds with the adjacent C, O or Si atoms (A-C, A-O or A-Si).

In the B©SiO<NUM> doped catalysts, the nonmetallic element B is inserted in the lattice of SiO<NUM>, and by partially replacing Si atoms, bonds with the adjacent O atoms (B-O). In the B©SiCxOy doped catalysts, the metal element B is inserted the lattice of SiCxOy, and by partially replacing Si or C atoms, bonds with the adjacent C, O or Si atoms (B-C, B-O or B-Si).

The present invention relates to a synthesis method of ethylene from oxygen-free direct conversion of methane. Besides methane, the reaction feed gas includes possibly one or two of inert gases and non-inert gases. The inert gases include one or more than two of nitrogen, helium and argon, and the volume content of the inert gases in the reaction feed gas is <NUM>-<NUM>%. The non-inert gases include one or a mixture of more than two of carbon monoxide, hydrogen, carbon dioxide, water, monohydric alcohol (with <NUM> to <NUM> carbon atoms) or alkanes with <NUM> to <NUM> carbon atoms, and the volume ratio of non-inert gases to the methane is <NUM>-<NUM>%. The volume content of the methane in the reaction feed gas is <NUM>-<NUM>%.

The present invention relates to a synthesis method of ethylene from oxygen-free direct conversion of methane. The reaction process includes a pretreatment process of a catalytic reactor, and the atmosphere of the pretreatment is reaction feed gas or hydrogen; pretreatment temperature is <NUM>-<NUM>; pretreatment pressure is <NUM>-1Mpa; and weight hourly space velocity of the reaction feed gas is <NUM>-<NUM>/g/h, preferably <NUM>-<NUM>/g/h.

The present invention relates to a synthesis method of ethylene from oxygen-free direct conversion of methane. The reaction process is in a continuous flow reaction mode. Under the continuous flow reaction mode, the reaction temperature is <NUM>-<NUM>; the reaction pressure is preferably <NUM>-<NUM> MPa; and the weight hourly space velocity of the reaction feed gas is <NUM>-<NUM>/g/h, preferably <NUM>-<NUM>/g/h.

The present invention relates to a synthesis method of ethylene from oxygen-free direct conversion of methane, which also co-produces propylene, butylene, aromatics and hydrogen, and the aromatic hydrocarbon products include one or more of benzene, toluene, xylene, o-xylene, m-xylene, ethylbenzene, and naphthalene.

Based on the research of the methane dehydroaromatization process, the present invention proposes a metal lattice doped silicon-based catalyst for ethylene, aromatic hydrocarbon and hydrogen production by direct catalytic conversion of methane under oxygen-free reaction mode. Compared with the previous oxygen-free methane conversion process, especially with the patents with application numbers of <CIT>and <CIT>, this method has the following characteristics:.

Therefore, the method has the characteristics of high stability of catalyst, large conversion rate of methane, high selectivity of products, zero coke deposition, good process reproducibility, safe and reliable operation, etc., and has wide industrial application prospect.

Although it seems that there are some similarities in the product types between the process of the present invention and the existing methane dehydroaromatization, the study finds that there are fundamental differences (in catalysts and reaction mechanism). Firstly, the methane dehydroaromatization catalyst is a zeolite supported catalyst. Secondly, the current accepted reaction mechanism for methane dehydroaromatization (shown in Formula <NUM>) is: methane is dissociated on the surface of the resulting active sites (such as MoCx, WC, Re) of the catalyst to produce CHx species; subsequently, CHx species are coupled on the surface of catalyst to form the C<NUM>Hy species; then C<NUM>Hy species are coupled on the acidic sites of the zeolite channel, in which aromatic hydrocarbon is formed by the shape selectivity of zeolite channel. <CHM>
Formula <NUM>: Reaction mechanism of the methane dehydroaromatization over MoCx/Zeolite catalyst.

However, the catalysts of the present invention are amorphous molten materials formed by lattice-doping the metal elements in one or more than two of Si, C and O. The reaction mechanism is that methane is induced by the active species (combined metallic elements in the lattice) to produce ·CH<NUM> radicals, which are further coupled and dehydrogened to obtain the olefins, aromatic hydrocarbon and hydrogen (as shown in Formula <NUM>).

Formula <NUM> Radical mechanism of oxygen-free production of alkene from catalysis of methane by A©SiOxCyNz catalyst.

The differences between the methane dehydroaromatization and the present invention are as follows: <NUM>) it is necessary for the methane dehydroaromatization to possess zeolite with specific channel size and structure, as well as acidic sites with certain amount and types; <NUM>) the catalysts in the present invention are amorphous molten state materials without channel and acid; <NUM>) the mechanism of methane dehydroaromatization is a synergistic catalysis mechanism between active species and zeolite (channel and acidic), while the present invention is a radical induction mechanism.

In the present invention, the methane conversion is <NUM>-<NUM>%; ethylene selectivity is <NUM>-<NUM>%; propylene and butylene selectivities are <NUM>-<NUM>%; aromatic hydrocarbon selectivity is <NUM>-<NUM>%; and zero coke deposition. The method has the characteristics of long life of catalysts (><NUM>), high stability of redox and hydrothermal conditions at high temperature (<<NUM>), high conversion rate of methane, high selectivity of ethylene, zero coke deposition, easy separation of products, no scaleup of catalyst, small industrialization difficulty, good process reproducibility, safe and reliable operation and the like, and has wide industrial application prospect.

The present invention is described below in details in combination with the drawings and the specific embodiments. However, the following embodiments are limited to explaining the present invention. The protection scope of the present invention should include all contents of claims, not limited to the embodiments.

As shown in <FIG>, the preparation method of the present invention is specifically realized as follows:.

The preparation methods of the lattice doped catalyst include a modified chemical vapor deposition (MCVD) coated solid phase doping technology or a solid-liquid phase sol-gel combined high temperature melting and coating technology. The catalyst of the film is marked as A©SiOxCy.

The preparation of A©SiO<NUM> lattice doped catalysts (embodiments <NUM>-<NUM>); the preparation of A©SiC lattice doped catalysts (embodiments <NUM>-<NUM>); the preparation of A©SiOC<NUM> all lattice doped catalysts (embodiments <NUM>-<NUM>); the preparation of A/SiO<NUM> support type catalysts (embodiment <NUM>) (Active components are dispersed on the support surface); the preparation of A@SiO<NUM> partial lattice doped catalysts (embodiments <NUM>-<NUM>) (Active components are partially dispersed on the support surface, and a part of lattice is doped in the support, such as patent <CIT>).

SiCl<NUM> liquid and FeCl<NUM> gas of <NUM> are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM> and FeCl<NUM> conduct oxidation deposition on the inner wall of a quartz tube (with a wall thickness of <NUM>) with an outer diameter of <NUM> and a length of <NUM> for <NUM> minutes to obtain Fe doped SiO<NUM> powder material; subsequently, under a temperature of <NUM> and <NUM> bars of highly pure helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section A of a Fe© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Fe is <NUM>.

SiCl<NUM> liquid and FeCl<NUM> gas of <NUM> are brought into high temperature MCVD by using <NUM>/min of high purity helium; at <NUM>, SiCl<NUM> and FeCl<NUM> conduct high purity oxygen reaction on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for oxidization deposition for <NUM> minutes to obtain Fe doped SiO<NUM> powder material; subsequently, under a temperature of <NUM> and <NUM> bars of highly pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section B of a Fe© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Fe is <NUM>.

SiCl<NUM> liquid and ZnCl<NUM> gas of <NUM> are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM> and ZnCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain Zn doped SiO<NUM> powder material; subsequently, under a temperature of <NUM> and <NUM> bars of highly pure helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section C of a Zn© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Zn is <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, and ZnCl<NUM> gas of <NUM> are brought into high temperature MCVD by using <NUM>/min of high purity helium; at <NUM>, SiCl<NUM>, FeCl<NUM>, and ZnCl<NUM> react with highly pure oxygen to conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe and Zn; subsequently, under a temperature of <NUM> and <NUM> bars of highly pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section D of a Fe-Zn-P© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe and Zn are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, and ZnCl<NUM> gas of <NUM> are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, and ZnCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe and Zn; subsequently, under a temperature of <NUM> and <NUM> bars of highly pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section E of a Fe-Zn© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe and Zn are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, ZnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe, Zn and P; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section F of a Fe-Zn-P© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe, Zn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, SnCl<NUM> liquid, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, SnCl<NUM>, ZnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Sn, Zn and P; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section G of a Fe-Zn-P© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Sn, Zn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, SnCl<NUM> liquid, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity helium; at <NUM>, SiCl<NUM>, SnCl<NUM>, ZnCl<NUM> and POCl<NUM> react with the high purity oxygen to conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Sn, Zn and P; subsequently, under a temperature of <NUM> and <NUM> bars of high purity oxygen atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section H of a Sn-Zn-P© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Sn, Zn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, TiCl<NUM> liquid, FeCl<NUM> gas of <NUM> and BCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, TiCl<NUM>, FeCl<NUM> and BCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Ti, Fe and B; subsequently, under a temperature of <NUM> and <NUM> bars of pure helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section I of a Ti-Fe-B© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Ti, Fe and B are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, GaCl<NUM> liquid of <NUM>, and AlCl<NUM> gas of <NUM> are brought into high temperature MCVD by using <NUM>/min of high purity helium; at <NUM>, SiCl<NUM>, GaCl<NUM>, and AlCl<NUM> react with highly pure oxygen to conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Ga and Al; subsequently, under a temperature of <NUM> and <NUM> bars of highly pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section J of a Ga-Al© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Ga and Al are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, YbCl<NUM> liquid of <NUM>, AlCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity helium; at <NUM>, SiCl<NUM>, YbCl<NUM>, POCl<NUM> and AlCl<NUM> react with highly pure oxygen to conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Yb and Al; subsequently, under a temperature of <NUM> and <NUM> bars of high purity oxygen atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section K of a Yb-Al-P© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Yb, Al and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, LaCl<NUM> liquid of <NUM>, AlCl<NUM> gas of <NUM> and BCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, LaCl<NUM>, BCl<NUM> and AlCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with La, Al and B; subsequently, under a temperature of <NUM> and <NUM> bars of high purity helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section L of a La-Al-B© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of La, Al and B are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, LaCl<NUM> liquid of <NUM>, AlCl<NUM> gas of <NUM> and BCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity helium; at <NUM>, SiCl<NUM>, LaCl<NUM>, BCl<NUM> and AlCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with La, Al and B; subsequently, under a temperature of <NUM> and <NUM> bars of high purity argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section M of a La-Al-B© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of La, Al and B are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, BCl<NUM> liquid, and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, BCl<NUM>, and POCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with B and P; subsequently, under a temperature of <NUM> and <NUM> bars of highly pure helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section N of a P-B© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of P and B are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, MgCl<NUM> liquid of <NUM>, MnCl<NUM> liquid of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, MgCl<NUM>, MnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Mg, Mn and P; subsequently, under a temperature of <NUM> and <NUM> bars of highly pure helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section O of a Mg-Mn-P© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Mg, Mn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, MgCl<NUM> liquid of <NUM>, MnCl<NUM> liquid of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, MgCl<NUM>, MnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO2 powder material doped with Mg, Mn and P; subsequently, under a temperature of <NUM> and <NUM> bars of pure oxygen atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section P of a Mg-Mn-P© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Mg, Mn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, MnCl<NUM> liquid of <NUM>, POCl<NUM> liquid, AlCl<NUM> gas of <NUM> and SnCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, MnCl<NUM>, AlCl<NUM>, SnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe, Mn, Sn, Al and P; subsequently, under a temperature of <NUM> and <NUM> bars of pure oxygen atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section Q of a Fe-Mn-Sn-Al-P© catalytic reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe, Mn, Sn, Al and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid is brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM> conducts oxidation deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material; subsequently, under a temperature of <NUM>, the quartz tube of <NUM> is immersed in an aqueous solution of SrCl<NUM> and Ba(NO<NUM>)<NUM> to for about <NUM>; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section R of a Sr-Ba© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Sr and Ba are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, LaCl<NUM> liquid of <NUM>, AlCl<NUM> gas of <NUM> and BCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, LaCl<NUM>, BCl<NUM> and AlCl<NUM> conduct oxidation deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with La, Al and B; subsequently, under a temperature of <NUM>, the quartz reactor of <NUM> is immersed in an aqueous solution of AuCl<NUM> to for about <NUM>; subsequently, under a temperature of <NUM> and <NUM> bars of pure oxygen atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section S of a La-Al-Au-B© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of La, Al, Au and B are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, LaCl<NUM> liquid of <NUM>, AlCl<NUM> gas of <NUM> and BCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, LaCl<NUM>, BCl<NUM> and AlCl<NUM> conduct oxidation deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with La, Al and B; subsequently, under a temperature of <NUM>, the quartz reactor of <NUM> is immersed in an aqueous solution of AuCl<NUM> to for about <NUM>; subsequently, under a temperature of <NUM> and <NUM> bars of pure oxygen atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section T of a La-Al-Au-B© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of La, Al, Au and B are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, ZnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a quartz tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe, Zn and P; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section U of a Fe-Zn-P© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe, Zn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, ZnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe, Zn and P; subsequently, under a temperature of <NUM>, CH<NUM> is led to conduct carbonizing treatment for <NUM> minutes; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section V of a Fe-Zn-P© catalytic silica carbide reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe, Zn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, ZnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe, Zn and P; subsequently, under a temperature of <NUM>, CH<NUM> is led at <NUM>/min to conduct carbonizing treatment for <NUM> minutes; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section W of a Fe-Zn-P© catalytic silica carbide reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe, Zn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, ZnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe, Zn and P; subsequently, under a temperature of <NUM>, CH<NUM> is led at <NUM>/min to conduct carbonizing treatment for <NUM> minutes; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section X of a Fe-Zn-P© catalytic silica carbide reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe, Zn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, ZnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe, Zn and P; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the SiO<NUM> coated reaction section Y of a Fe-Zn-P© catalytic silica carbide reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe, Zn and P are respectively <NUM>. % and <NUM>.

SiCl<NUM> liquid, FeCl<NUM> gas of <NUM>, ZnCl<NUM> gas of <NUM> and POCl<NUM> liquid are brought into high temperature MCVD by using <NUM>/min of high purity oxygen; at <NUM>, SiCl<NUM>, FeCl<NUM>, ZnCl<NUM> and POCl<NUM> conduct oxidization deposition on the inner wall of a silica carbide tube with an outer diameter of <NUM> (with a wall thickness of <NUM>) and a length of <NUM> for <NUM> minutes to obtain SiO<NUM> powder material doped with Fe, Zn and P; subsequently, under a temperature of <NUM> and <NUM> bars of pure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the SiO<NUM> coated reaction section Z of a Fe-Zn-P© catalytic silica carbide reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe, Zn and P are respectively <NUM>. % and <NUM>.

A sol-gel method is combined with a high temperature melting technology.

The inner wall of the quartz tube with an outer diameter of <NUM> is treated for <NUM> by using <NUM>% of HF solution; meanwhile, a mixed solution of <NUM> of Fe(NO<NUM>)<NUM>·<NUM><NUM>, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and normal pressure air atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AA of a Fe© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Fe is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM>% of HF solution; meanwhile, a mixed solution of <NUM> of Mg(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and normal pressure air atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AB of a Mg© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Mg is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM>% of HF solution; meanwhile, a mixed solution of <NUM> of Zn(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and normal pressure air atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AC of a Zn© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Zn is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM>% of HF solution; meanwhile, a mixed solution of <NUM> of La(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and normal pressure air atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AD of a La© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of La is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM>% of HF solution; meanwhile, a mixed solution of <NUM> of Ce(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of pure oxygen atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AE of a Ce© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Ce is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM>% of HF solution; meanwhile, a mixed solution of <NUM> of Ga(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of pure oxygen atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AF of a Ga© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Ga is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM>% of HF solution; meanwhile, a mixed solution of <NUM> of Mg(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of Fe(NO<NUM>)<NUM>·<NUM><NUM>, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of air atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AG of a Fe-Mg© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe and Mg are <NUM>. % and <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> is treated for <NUM> by using <NUM>% of HF solution; meanwhile, a mixed solution of <NUM> and <NUM> of Fe(NO<NUM>)<NUM>·<NUM><NUM>, <NUM> of La(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and normal pressure air atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AH of a Mg© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Mg is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM> of NaOH solution; meanwhile, a mixed solution of <NUM> of Fe(NO<NUM>)<NUM>·<NUM><NUM>, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and normal pressure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AI of a Fe© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Fe is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM> of NaOH solution; meanwhile, a mixed solution of <NUM> of Mg(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and normal pressure argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> micrometer is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AJ of a Mg© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Mg is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM> of NaOH solution; meanwhile, a mixed solution of <NUM> of Zn(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AK of a Zn© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Zn is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM> of NaOH solution; meanwhile, a mixed solution of <NUM> of La(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AL of a La© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of La is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM> of NaOH solution; meanwhile, a mixed solution of <NUM> of Ce(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of argon atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AM of a Ce© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Ce is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM> of NaOH solution; meanwhile, a mixed solution of <NUM> of Ga(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AN of a Ga© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amount of Ga is <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using <NUM> of NaOH solution; meanwhile, a mixed solution of <NUM> of Mg(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of Fe(NO<NUM>)<NUM>·<NUM><NUM>, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AO of a Fe-Mg© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe and Mg are <NUM>. % and <NUM>.

The inner wall of the quartz tube with an outer diameter of <NUM> and a length of <NUM> is treated for <NUM> by using superfine SiC particles with <NUM>-<NUM> meshes to coarsen the inner surface of the quartz tube; meanwhile, a mixed solution of <NUM> and <NUM> of Fe(NO<NUM>)<NUM>·<NUM><NUM>, <NUM> of La(NO<NUM>)<NUM>·<NUM><NUM>O, <NUM> of tetraethoxysilane TEOS and <NUM> of deionized water is prepared; after uniformly stirred, <NUM> is taken and coated on the HF etched inner wall of the quartz tube; subsequently, treatment is made in an oven under a temperature of <NUM> for <NUM>; finally, under a temperature of <NUM> and <NUM> bars of helium atmosphere, the material is melted for <NUM> minutes; then, a dopant thin layer with a thickness of <NUM> is formed on the inner wall of the reaction section; and the material is cooled naturally to obtain the reaction section AP of a Fe-La© catalytic quartz reactor with a diameter of <NUM> and a length of <NUM>, wherein the doping amounts of Fe and La are <NUM>. % and <NUM>.

The ICP-AES acid leaching (nitric acid and HF acid) method is used. The so-called ICP-AES acid leaching process is that the metal on the surface of the support can be dissolved by an acid leaching process if the metal is loaded on the surface of the support (the acid can only dissolve the metal component, but the metal oxide component cannot dissolve the support); degree of acid leaching (i.e., a ratio of surface loadings to surface loading and doping amount) can be obtained through ICP measurement; however, if the metallic elements cannot be dissolved by acid, it indicates that the metallic elements are doped in the Si-based support lattice and protected. Firstly, the reaction section A of the Fe©catalytic quartz reactor with a diameter of <NUM> is leached by dilute nitric acid, and the ICP analysis results show that no Fe ion is dissolved, and further indicate that all of Fe ions enter the lattice of Si-based substrate. However, if HF acid is adopted, not only the Si-based substrate can be dissolved, but also the metal components can be dissolved. The ICP analysis results show that all of Fe ions are dissolved, and the amount is just converted into the doping amount. The above analysis results show that all of Fe ions have been doped inside the lattice of Si-based substrate, and almost no Fe can be detected on the surface of Si-based substrate.

A in <FIG> represents a single atom electron microscopic photo of the reaction section A (in embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe© catalytic quartz reactor with a diameter of <NUM>. It can be seen from the electron microscopic characterization result by A in <FIG> that white circles are the single atom doped Fe metal atoms. EDX (B in <FIG>) further confirms that these white points are single atom Fe species. Other elements, such as Cu, are from Cu grilles. Moreover, in the total electron microscopic photo, catalysts present an amorphous form with long-range disorder and short-range disorder.

All of the above catalytic reactors are directly used without loading the catalysts.

All of the reaction examples are achieved in a continuous flow micro-reaction apparatus, which is equipped with gas mass flow meters, gas deoxy and dehydration tubes, and online product analysis chromatography (The tail gas of the reactor is directly connected with the metering valve of chromatography, and periodic and real-time sampling and analysis will be achieved. The reaction feed gas is composed of <NUM> vol. % N<NUM> and <NUM> vol. % CH<NUM> without specification, in which the nitrogen (N<NUM>) is used as internal standard gas. To achieve the online product analysis, the Agilent 7890A chromatography with dual detectors of FID and TCD is used, wherein the FID detector with HP-<NUM> capillary column is used to analyze the light olefin, light alkane and aromatic hydrocarbon; and the TCD detector with Hayesep D packed column is used to analyze the light olefin, light alkane, methane, hydrogen and internal standard N<NUM>. According to the carbon balance before and after reaction, methane conversion, carbonic product selectivity and coke deposition are calculated by the method from the patents (<CIT> and <CIT>).

The reaction section A (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe© catalytic quartz reactor, the quartz preheating section (with a diameter of <NUM> and a length of <NUM>) and the quartz transition section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM>/min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene selectivity, <NUM>% of benzene selectivity and <NUM>% of naphthalene selectivity, no coke deposition. For the <NUM>. %Fe©SiO<NUM> catalyst prepared by the method from patents <CIT> and <CIT>, under the same condition, the analysis results show that: the methane conversion is higher than those of the first two methods by about <NUM>-<NUM>%.

The reaction section J (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Ga-Al© catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to the following temperature and corresponding WHSV at a heating rate of <NUM>/min. The WHSV of the reaction feed gas is adjusted to the following WHSV. The results of methane conversion and product selectivity are shown in the following table. For the <NUM>. % Ga-<NUM>. %Al©SiO<NUM> catalyst prepared by the method from patents <CIT> and <CIT>, under the same condition, the analysis results show that: the conversion is higher than those of the patents <CIT>and<CIT> by <NUM>-<NUM>%.

The reaction section O (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Mg-Mn-P© catalytic quartz reactor, the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to the following temperature and corresponding WHSV at a heating rate of <NUM>/min. The WHSV of the reaction feed gas is adjusted to the following WHSV. The results of methane conversion and product selectivity are shown in the following table. For the <NUM>. %P©SiO<NUM> catalyst prepared by the method from patents <NUM> and <NUM>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the patents <NUM> and <NUM> by <NUM>-<NUM>%.

The reaction section L (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the La-Al-B © catalytic quartz reactor, the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to the following temperature and corresponding WHSV at a heating rate of <NUM>/min. The WHSV of the reaction feed gas is adjusted to the following WHSV. The results of methane conversion and product selectivity are shown in the following table. For the <NUM>. %B©SiO<NUM> catalyst prepared by the method from patents <NUM> and <NUM>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the patents <NUM> and <NUM> by <NUM>-<NUM>%.

The reaction section P (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe-Mn-Sn-Al-P © catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM>/min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started, and the stability of the catalyst is studied for a long time. The analysis results are shown every <NUM> hours below, as shown in the following table. The methane conversion rate listed in the table is higher than those of the first two methods (compared with <NUM>. %P ©SiO<NUM> in <NUM> and <NUM> patents) by <NUM>-<NUM>%, and the catalyst life is higher by about <NUM>-<NUM> hours.

The reaction section V (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe-Zn-P © catalytic silica carbide reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic silica carbide reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM>/min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene and butylene selectivity, <NUM>% of benzene selectivity and <NUM>% of naphthalene selectivity. For the <NUM>. %P ©SiO<NUM> catalyst prepared by the method from patents <CIT>and <CIT>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section W (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe-Zn-P © catalytic silica carbide reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic silica carbide reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM>/min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of benzene selectivity and <NUM>% of naphthalene selectivity. For the <NUM>. %Zn -<NUM>. %P ©SiO<NUM> catalyst prepared by the method from patents <NUM> and <NUM>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section X (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe-Zn-P © catalytic silica carbide reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic SiO<NUM> coated silica carbide reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM>/min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene and butylene selectivity and <NUM>% of benzene selectivity. For the <NUM>. %Fe -<NUM>. %P ©SiO<NUM> catalyst prepared by the method from patents <CIT>and <CIT>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section AA (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe © catalytic quartz reactor, the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM> /min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene and butylene selectivity and <NUM>% of benzene selectivity. For the <NUM>. %Fe©SiO<NUM> catalyst prepared by the method from patents <CIT> and<CIT>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section AC (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Zn © catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with the figure to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM>/min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene and butylene selectivity and <NUM>% of benzene selectivity. For the <NUM>. %Zn©SiO<NUM> catalyst prepared by the method from patents <CIT> and <CIT>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section AD (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the La © catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM>/min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene and butylene selectivity and <NUM>% of benzene selectivity. For the <NUM>. %La©SiO<NUM> catalyst prepared by the method from patents <CIT> and <CIT>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section AL (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the La © catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The La©SiO<NUM>-coated quartz reactor AL with a diameter of <NUM> is used. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM>/min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene and butylene selectivity and <NUM>% of benzene selectivity. For the <NUM>. %La©SiO<NUM> catalyst prepared by the method from patents <CIT>and <CIT>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section AL (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe-Mg © catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM> /min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene and butylene selectivity and <NUM>% of benzene selectivity. For the <NUM>. %Fe- <NUM>. %Mg©SiO<NUM> catalyst prepared by the method from patents <NUM> and <NUM>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section J (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe-Zn-P© catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM> /min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas (5vol. %CO<NUM>, 85vol. %CH<NUM>, 10vol. %N<NUM>) is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene selectivity, <NUM>% of benzene selectivity and <NUM>% of naphthalene selectivity. For the <NUM>. %P©SiO<NUM> catalyst prepared by the method from patents <NUM> and <NUM>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section J (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe-Zn-P© catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM> /min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas (5vol. %H<NUM>O, 85vol. %CH<NUM>, 10vol. %N<NUM>) is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of propylene selectivity, and <NUM>% of benzene selectivity. For the <NUM>. %P©SiO<NUM> catalyst prepared by the method from patents <CIT>and<CIT>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

The reaction section J (with a diameter of <NUM> and a length of <NUM>) (embodiment <NUM> for preparation of the reaction section of the catalytic reactor) of the Fe-Zn-P© catalytic quartz reactor, the quartz inlet section (with a diameter of <NUM> and a length of <NUM>), the quartz preheating section (with a diameter of <NUM> and a length of <NUM>), the transition section (with a diameter of <NUM> and a length of <NUM>) and the outlet section (with a diameter of <NUM> and a length of <NUM>) are connected in accordance with <FIG> to form the catalytic quartz reactor. The air in the reactor is replaced with Ar gas of <NUM>/min for about <NUM> mins. A constant flow rate of Ar is maintained, and the reactor is programmed from room temperature up to <NUM> at a heating rate of <NUM> /min. Meanwhile, the weight hourly space velocity (WHSV) of reaction feed gas (2vol. %C<NUM>H<NUM>, 85vol. %CH<NUM>, 10vol. %N<NUM>) is adjusted to <NUM>/g/h. After the WHSV being kept for <NUM> mins, online analysis is started. The analysis results are as follows: <NUM>% of methane conversion, <NUM>% of ethylene selectivity, <NUM>% of benzene selectivity and <NUM>% of naphthalene selectivity. For the <NUM>. %P©SiO<NUM> catalyst prepared by the method from patents <CIT> and <CIT>, under the same condition, the analysis results show that: the conversion of the present invention is higher than those of the two patents by <NUM>%.

In summary, under the pattern in the catalytic reactor of the present invention, reaction temperature is <NUM>-<NUM>; reaction pressure is normal pressure; the weight hourly space velocity of methane is <NUM>-<NUM>/g/h; methane conversion is <NUM>-<NUM>%; ethylene selectivity is <NUM>-<NUM>%; propylene and butylene selectivities are <NUM>-<NUM>%; and aromatic hydrocarbon selectivity is <NUM>-<NUM>%.

It is concluded that the present invention has the characteristics of long catalyst life (><NUM> hrs) of the catalytic reactor, high stability of redox and hydrothermal properties under high temperature (<<NUM>), high product selectivity, zero coke deposition, easy separation of products, good process reproducibility, safe and reliable operation, etc., and has wide industrial application prospect.

It should be noted that in accordance with the above embodiments of the present invention, those skilled in the art can completely realize the full scope of independent claims and dependent claims of the present invention; the realization processes and methods are the same as those of the above embodiments; and a part not described in detail in the present invention belongs to a widely-known technology in the field.

Claim 1:
A catalytic reactor configuration suitable for direct synthesis of ethylene through oxygen-free catalysis of methane, the catalytic reactor configuration at least comprising a preheating section and a reaction section,
wherein the reaction section refers to a quartz tube or a silica carbide tube whose inner wall is:
(i) directly lattice doped with active components, or
(ii) coated with a Si-based material, which Si-based material is lattice-doped by active components to form a dopant thin layer,
wherein the active components are metallic elements and/or nonmetallic elements and the quartz tube or the silica carbide tube with the inner wall which is directly doped or doped by coating is called the reaction section;
wherein the catalytic reactor configuration includes an inlet section located at the front of the preheating section, a transition section located between the preheating section and the reaction section, and an outlet section located at the rear of the reaction section;
and wherein the inlet section, the preheating section, the transition section, the reaction section and the outlet section are respectively manufactured and connected to form the catalytic reactor configuration.