CN1408637A

CN1408637A - Method for producing synthetic gas from low carbon hydrocarbon and inorganic compact oxygen permeatable membrane reactor

Info

Publication number: CN1408637A
Application number: CN 01127228
Authority: CN
Inventors: 陈初升; 冯绍杰; 冉申; 朱德春; 江国顺; 刘卫
Original assignee: University of Science and Technology of China USTC
Current assignee: University of Science and Technology of China USTC
Priority date: 2001-09-18
Filing date: 2001-09-18
Publication date: 2003-04-09
Anticipated expiration: 2021-09-18
Also published as: CN1227154C

Abstract

The present invention features that the catalyst bed layer is separated from the oxygen permeable assembly; that hot air and oxygen-rich gas are led to the oxygen permeable side of the membrane and natural gas and low carbon hydrocarbon or reducing mixed gas of low carbon hydrocarbon and CO and/or H2 are led to the reaction side to produce deep oxidation at 800-1000 deg.c and 0.1-1 MPa obtaining the mixture of low carbon hydrocarbon CO2 and/or steam; and that the mixture is led to one other area with reforming catalyst to produce combined catalytic reforming reaction of hydrocarbon, CO2 and H2O producing synthetic gas at 800-1000 deg.c and 0.1-1 MPa. The present invention has long service life of oxygen permeable membrane, expanded range of applicable membrane, reaction capacity at the conditions of high space velocity and great concentration, reasonable energy utilization.

Description

Method for preparing synthesis gas from low-carbon hydrocarbon and inorganic compact oxygen-permeable membrane reactor

The technical field is as follows:

the invention relates to a method for preparing hydrogen and carbon monoxide synthesis gas from natural gas or low-carbon hydrocarbon and an inorganic compact oxygen-permeable membrane reactor with a catalyst bed layer and an oxygen-permeable membrane component separated.

Background art:

a mixture of hydrogen and carbon monoxide, called synthesis gas, is used to produce liquid fuels, olefins (C)₂～C₄) Methanol, dimethyl ether and the like. Synthesis gas from low carbon hydrocarbons, especially natural gas, followed by synthesis of liquid fuels, olefins (C)₂～C₄) Chemical products such as methanol and the like are comprehensive utilization ways with industrial prospects. Natural gas is the largest reserve of lower hydrocarbons, the major constituent of which is methane. Natural gas will be an important carbon source for chemical products following petroleum and coal. In the United states of America, chemical News (Haggin, Chicago C.E., chem.Eng.News, 70 (17): 33(1992)), it is pointed out that in the current process for preparing synthetic gas andthen synthesizing liquid fuel and chemicals by using natural gas, the production cost of the synthetic gas accounts for about 50-60% of the total cost, and the cost is too high to be the biggest obstacle for developing and utilizing natural gas. Therefore, the production cost of the synthesis gas is reduced, and the method has important significance for the development and utilization of natural gas.

The currently widely used industrial process for producing synthesis gas from low carbon hydrocarbons such as natural gas is mainly a steam reforming process such as Steam Methane Reforming (SMR). Journal of physical chemistry (choudhury, v.r., Rajput, a.m., Rane, v.h., j.phys.chem., 96, 8686(1992)), Journal of Catalysis (Bharadwaj, s.s., and Schmidt, l.d., Journal of Catalysis 146, 11-21(1994)), states that since the reaction is a strong endothermic reaction, the equipment investment and energy consumption are high; and CO/H₂The product is comparatively high and can be used in the subsequent process by adjustment of the ratio. In recent years, non-catalytic Partial Oxidation (POX) and combined reforming process (SMR/O) have been newly developed₂R), autothermal reforming (ATR), and the like. Catalysis Today (Balachandran, U.S., Dusek, J.T., Maiya, P.S., et al, Catalysis Today36(1997) 265)Notification (Dong Hui, Xiong Guxing, Shao Zongping, et al, Chinese Science Bulletin 45(3) 224-. To avoid N₂The pure oxygen is required to be used as a reactant, so the equipment investment is large, and the operation cost is high. As shown in the US patent 6048472, the ATR process requires 95-99.9% oxygen concentration, and the equipment investment and operation cost of oxygen production account for a large proportion of the cost. Therefore, reducing the cost of oxygen production becomes a leading factor in reducing the cost of syngas.

The inorganic compact oxygen permeable membrane is a kind of ion conductor membrane, and the principles of the materials are discussed in detail in the fast ion conductor-base, materials and applications of the offers of forestry and ancestors (Shanghai science publishers, 1983), and in the solid ionization science of flute and stamina (the board of Prime, et al, Beijing science publishers, 1984). There are two broad classes of ion conductors currently available for oxygen separation: one is an ion conductor without (or with very low) electronic conductivity, and under the action of an external electric field or an external electrode, under the action of oxygen concentration gradient, oxygen ion conduction is carried out by utilizing lattice defects or gaps in the material, so that the selective permeation of oxygen is realized, and the purpose of oxygen separation is achieved; another widely studied class of materials is mixed ion conductors, i.e., materials themselves have both ion conductivity and electron conductivity, and under the action of an oxygen concentration gradient, oxygen ions migrate from the side with a high oxygen chemical potential (high oxygen concentration) to the side with a low oxygen chemical potential (low oxygen concentration) through oxygen vacancies or gaps, and electrons (electron holes) move in the opposite direction, so that membrane separation of oxygen can be achieved without an external circuit. The inorganic compact oxygen permeable membrane has oxygen permeating selectivity of 100% in theory, is suitable for oxygen separator and membrane reactor, and may be used in oxygen supplying in site especially in high temperature oxygen supplying process. Under certain oxygen permeation temperature and reaction conditions, the improvement of the oxygen permeation capability, the mechanical stability and the chemical stability of the material is still the current research focus.

The production of synthetic gas is carried out by adopting an inorganic compact oxygen-permeable membrane reactor, and the in-situ utilization of an oxygensource in the air is an effective method for economic oxygen supply. Such as the process set forth in U.S. patent 6048472. This process is still essentially a combined reforming process, with the inorganic oxygen permeable membrane serving as an oxygen supply in the secondary reforming. The whole process still needs two reactors, and the problems of high energy consumption and high investment are still not solved. U.S. patent 6077323 teaches a process wherein a catalyst is coated onto the surface of the membrane and a mixture of methane and water vapor is passed to the reactive side of the membrane to react with the permeated oxygen to produce synthesis gas. The process has high requirements on the membrane material, not only needs to consider the problem of thermal property matching between the membrane material and the catalyst, but also needs the catalyst to have no influence on the chemical structure of the membrane at high temperature, and once the carbon on the surface of the catalyst is inactivated, the membrane material needs to be replaced; on the other hand, the reaction process is complicated and difficult to control. We have proposed an oxygen permeable membrane separator (chinese patent application No. 99124427.3) in which it is mentioned that the device can be used as an oxygen-related chemical membrane reactor, but the technical requirements of catalyst coating on the surface of the membrane and matching with the membrane material limit the scope of its application.

The preparation of synthesis gas in inorganic membrane reactors using expensive Rh-based catalysts is reported in the catalysts of Today (Balachandran, U.S., Dusek, J.T., Maiya, P.S., et al, Catalysis Today36(1997) 265-an 272). The disadvantage of the relatively inexpensive Ni-based catalysts used in the partial oxidation of methane is their tendency to deactivate, which was indicated by Applied Catalysis (A. Slagn, Unni Olsbye, Applied catalysts A: General110(1994) pages 99-108) that Ni-based catalystsdeactivate in the partial oxidation of methane only 17 hours; the same conclusion was also obtained in Journal of Catalysis (V.A. Tsipouriari, Z.Zhang, and X.E. Verykios, Journal of Catalysis179(1998), 283-.

The technical content is as follows:

the invention provides a method for preparing hydrogen and carbon monoxide synthesis gas from natural gas or low-carbon hydrocarbon based on an inorganic compact oxygen-permeable membrane reactor and the inorganic compact oxygen-permeable membrane reactor with a catalyst bed layer and an oxygen-permeable membrane component separated, which aims to overcome the problems in the prior art.

The invention relates to a method for preparing hydrogen and carbon monoxide synthesis gas from natural gas or low-carbon hydrocarbon, which is characterized by comprising the following steps: hot air or oxygen-enriched combustion gas is introduced into the oxygen-permeable side of the inorganic compact oxygen-permeable membrane, natural gas or low-carbon hydrocarbon is introduced into the reaction side of the membrane, or low-carbon hydrocarbon and CO or/and H are introduced₂The reducing mixed gas is adjusted to 1.0 × 10^-3～80ml·cm^-2·min^-1Performing deep oxidation reaction at the temperature of 800-1000 ℃ and the pressure of 0.1-1 MPa (calculated by the surface area of each square centimeter of membrane material) to obtain a mixture of low-carbon hydrocarbon, carbon dioxide and/or water vapor with the required specified metering ratio; then introducing the mixture of low carbon hydrocarbon, carbon dioxide and/or steam into another area of reforming catalyst, under the conditions of 800-1000 deg.C and 0.1-1 MPa pressure, hydrocarbon and CO₂、H₂And performing combined catalytic reforming reaction on the O to prepare the synthesis gas.

The deep oxidation reaction is carried out by adjusting the input of the reducing mixed gas to obtain the mixture of the low-carbon hydrocarbon, the carbon dioxide and/or the water vapor with the required specified metering ratio, which is measured by the surface area of the membrane material per square centimeter according to the specifically selected inorganic compact oxygen permeable membrane material, the geometric dimension of the membrane component and the temperature of the oxygen permeable oxidation zone and is 1.0 multiplied by 10^-3～80ml·cm^-2·min^-1The extent of the reaction is controlled by adjusting the feed of the lower hydrocarbon and correspondingly the feed of the other gases within the range to obtain a desired mixture of lower hydrocarbon, carbon dioxide and/or steam in the specified stoichiometric ratio:

(1) when pure lower carbon hydrocarbons are used as the reducing gas, oxygen permeable membrane materials that may be selected include: ZrO having fluorite structure₂、Bi₂O₃Base doping material, composite oxide having pyrochlore structure, composite oxide material having perovskite and perovskite-like structure, ion and electron conductor two-phase composite material, and sandwich compound Sr having layered structure₄Fe_6-xCo_xO_13-xA system, a single-phase composite oxide having both oxygen ion and electron channels, andand a composite film material composed of the above material, ceramic, metal and inorganic high-temperature oxide; the molar ratio CH of the individual species in the mixture obtained₄/H₂O/CO₂＝3/2/1；

(2) When using lower hydrocarbons and H₂When the synthesis gas with the molar ratio of 2 to CO is used as the reducing mixed gas, part of the synthesis gas product is circulated and mixed with the low-carbon hydrocarbonfor feeding, and the synthesis gas and the permeated oxygen generate deep oxidation reaction; the circulation ratio of the synthesis gas is 0.4-0.6; the molar ratio CH of the individual species in the mixture obtained₄/H₂O/CO ₂3/2/1; alternative oxygen permeable membrane materials include: ZrO having fluorite structure₂、Bi₂O₃Base doping material, composite oxide having pyrochlore structure, composite oxide material having perovskite and perovskite-like structure, ion and electron conductor two-phase composite material, and sandwich compound Sr having layered structure₄Fe_6-xCo_xO_13-xA system, a single-phase composite oxide simultaneously having an oxygen ion channel and an electron channel, and a composite film material formed by the material and ceramic, metal and inorganic high-temperature oxide;

(3) when using lower hydrocarbons and H₂As a reducing gas mixture, it is meant that a portion of the synthesis gas product is passed over H₂After separation of the membrane, H₂Circularly feeding the mixture with low-carbon hydrocarbon; h₂The cyclic ratio of (A) to (B) is 0.4 to 0.6, CH₄/H ₂1 is ═ 1; alternative oxygen permeable membrane materials include: ZrO having fluorite structure₂、Bi₂O₃Base doping material, composite oxide having pyrochlore structure, composite oxide material having perovskite and perovskite-like structure, ion and electron conductor two-phase composite material, and sandwich compound Sr having layered structure₄Fe_6-xCo_xO_13-xA system, a single-phase composite oxide simultaneously having an oxygen ion channel and an electron channel, and a composite film material formed by the material and ceramic, metal and inorganic high-temperature oxide;

(4) when using lower hydrocarbons and CO as reducing mixtureWhen gas is synthesized, it is meant that a portion of the synthesis gas product is passed through H₂After separating the membrane, feeding the CO circularly with the mixture of the low-carbon hydrocarbon and the water vapor; CH (CH)₄/H₂O ratio of 1.4 to 1.6, CH₄The ratio of/CO is 2.8-3.2; alternative oxygen permeable membrane materials include: ZrO having fluorite structure₂、Bi₂O₃Base doping material, composite oxide having pyrochlore structure, composite oxide material having perovskite and perovskite-like structure, ion and electron conductor two-phase composite material, and sandwich compound Sr having layered structure₄Fe_6-xCo_xO_13-xA system, a single-phase composite oxide simultaneously having an oxygen ion channel and an electron channel, and a composite film material formed by the material and ceramic, metal and inorganic high-temperature oxide;

the feed ratios described in the above processes are all to produce H₂The synthesis gas of/CO 2 (actually, the range of 1.8-2.1) is used as a target product. By adjusting the feed ratio, different H's can also be obtained₂Syngas in a/CO ratio.

The invention relates to an inorganic compact oxygen-permeable membrane reactor, which comprises an oxygen-permeable zone 1 and a deep oxidation reaction zone 3 which are formed by separating a reaction container 9 by an oxygen-permeable membrane component 2, and a catalyst bed layer 4 which is used as a combined catalytic reforming zone; the method is characterized in that a catalyst bed layer is separated from an oxygen permeable membrane component, and a deep oxidation reaction zone 3 is formed by a space between the catalyst bed layer 4 and the oxygen permeable membrane component 2; an oxygen-enriched gas inlet 5 is arranged on the wall of the oxygen permeation area 1 near the oxygen permeation membrane component 2, and an air outlet 6 is arranged at the far end; a reducing gas inlet 7 is arranged on the wall of the deep oxidation zone 3 between the oxygen permeable membrane component 2 and the catalyst bed layer 4 near the oxygen permeable membrane component, and a product synthesis gas outlet 8 is arranged on the other side of the catalyst bed layer 4.

When the reactor is used for preparing hydrogen and carbon monoxide synthesis gas from low-carbon hydrocarbon, hot air or hot oxygen-enriched combustion gas with the temperature of 800-1000 ℃ and the pressure of 0.1-1 MPa is introduced into the oxygen-permeable area 1at one side of the oxygen-permeable membrane 2 from the air inlet 5, oxygen-poor gas is discharged from the air outlet 6, and the low-carbon hydrocarbon or the low-carbon hydrocarbon and CO or/and H are discharged from the air outlet 6₂The reducing mixed gas is composed of intake gasThe port 7 enters the deep oxidation reaction zone 3 at the other side of the oxygen permeable membrane 2 and is inorganicThe oxygen permeating through the compact oxygen permeable membrane component 2 reacts, and the input of reducing gas is adjusted to obtain a mixture of low-carbon hydrocarbon, carbon dioxide and/or water vapor with required specified metering ratio; the mixture immediately enters a catalytic reforming reaction zone 4, a combined reforming reaction is carried out at the temperature of 800-1000 ℃ and under the pressure of 0.1-1 MPa, and the obtained synthesis gas product is discharged from an outlet 8.

The inorganic oxygen permeable membrane material in the method can be used for manufacturing the inorganic compact oxygen permeable membrane component 2 in the inorganic compact oxygen permeable membrane reactor. The geometrical configuration of the inorganic compact oxygen permeable membrane module 2 can be flat plate, corrugated, tubular and honeycomb.

Compared with the prior art, the method has the following characteristics and advantages:

the method of the invention is characterized in that: the oxygen permeation complete oxidation reaction process and the combined reforming reaction process are respectively carried out in two areas in the same reactor cavity; 2. the oxygen transmission in the oxygen permeable membrane is realized by coupling the complete oxidation reactions of different reducing gases, wherein the reducing gases can adopt CH₄、CO+H₂CO or H₂(ii) a 3. Introducing air or oxygen-enriched combustion gas into one side of the inorganic compact oxygen-permeable membrane, and introducing reducing gas into the other side of the membrane to completely oxidize part of the reducing gas to generate CO₂、H₂O。

The method has the advantages that: 1. the oxygen permeation process is coupled with the deep oxidation reaction, so that the initiation time of the oxygen permeation of the membrane material is shortened, the oxygen permeation quantity per unit area of the membrane material is greatly improved, and the synthesis gas yield per unit area of the membrane of the whole process is improved. 2. The oxygen permeation process is separated from the reforming process, the reaction section of the inorganic oxygen permeation membrane only generates deep oxidation reaction, the reaction degree is limited by the oxygen supply rate of the membrane, the temperature runaway phenomenon caused by severe deep oxidation reaction is avoided, the temperature gradient of the membrane material is effectively controlled, the mechanical stability of the membrane is protected, the service life of the membrane is prolonged, and the range of the membrane material capable of being applied to the reaction is enlarged. 3. Separate oxygen permeation from reforming, reactionThe process is easy to control. The reaction degree of the deep oxidation reaction zone is controlled by adjusting the feeding amount of the reducing gas, the geometric dimension and the temperature of the membrane tube and the selection of the catalyst (the catalyst can be modified or not according to specific membrane materials), and then the aim of controlling the whole reaction is achieved. 4. The energy utilization in the reaction system is reasonable, and the requirement on energy consumption is low. The whole reaction is exothermic, the deep oxidation reaction in the first step of the reaction is exothermic, and the generated heat is carried to the catalytic reaction zone by the product and is required by the endothermic heat of the reforming reaction, so that the heat required by the subsequent reforming reaction can be maintained. 5. The oxygen permeation process is separated from the reforming process, which is beneficial to the protection of the catalyst.(1) The oxygen permeation process and the combined reforming process are separated, the catalytic combined reforming reaction generated on the catalyst is an endothermic reaction, and the temperature runaway phenomenon of a catalyst bed layer caused by the heat release of the oxidation reaction in other processes is avoided, so that the inactivation of the catalyst due to high-temperature sintering caused by temperature runaway is avoided. (2) In the prior art, the carbon deposition of the hydrocarbon by pyrolysis is an important reason for the inactivation of the catalyst, and particularly, the carbon number of the hydrocarbon more than 2 is obviously cracked at the temperature of more than 650 ℃. The process provided by the invention leads part of the multi-carbon hydrocarbon to be cracked in the membrane reaction zone and finally generates CO₂And H₂The O enters the reforming zone, so that the carbon deposition rate on the reforming catalyst is slowed down, and the service life of the catalyst is prolonged. (3) H produced by deep oxidation₂O takes part in thereaction in the reforming reaction zone, H₂The presence of O is advantageous for carbon elimination of the catalyst. Therefore, carbon deposition on the catalyst can be reduced, and the service life of the catalyst is prolonged. 6. The invention separates the oxygen permeation process from the reforming process, the catalyst is better protected, and the service life of the catalyst is prolonged, so the reaction can be carried out at high airspeed and large concentration, even under the condition of pure methane gas inlet by using the Ni-based catalyst. The preparation of synthesis gas in inorganic membrane reactors using expensive Rh-based catalysts is reported in the catalysts of Today (Balachandran, U.S., Dusek, J.T., Maiya, P.S., et al, Catalysis Today36(1997) 265-file 272). A disadvantage of the relatively inexpensive Ni-based catalysts for the partial oxidation of methane is their tendency to deactivate, Applied Catalysis (A. Slagter. Unni Olsbye, Applied Catalysis A: General110(1994)99-108)It is pointed out that the Ni-based catalyst was deactivated in the partial oxidation reaction of methane for only 17 hours; the same conclusion was also obtained in Journal of Catalysis (V.A. Tsipouriari, Z.Zhang, and X.E. Verykios, Journal of Catalysis179(1998), 283-. Under the condition of pure methane inlet gas, the Ni-based catalyst is adopted, and the activity of the catalyst is not obviously reduced after 400 hours of reaction. And the oxygen permeation process is separated from the reforming process, and once the catalyst is deactivated, the catalyst is convenient to replace. Not only reduces the cost of the catalyst, but also reduces the compression power consumption caused by using a large amount of inert components, reduces the operation energy consumption to the minimum, and greatly reduces the operation cost. 7. The method has wide application range. Among the low carbon hydrocarbons, methane has the highest chemical stability, and for other light hydrocarbons with carbon number greater than 2, themethod can be used for producing the synthesis gas.

Compared with the prior art, the inorganic compact oxygen-permeable membrane reactor has the following characteristics and advantages: 1. the inorganic compact oxygen-permeable membrane reactor combines the oxygen permeation process and the reforming process in one reactor cavity, has compact structure, realizes the intensification of reaction, and reduces the equipment investment and the operating cost. 2. The inorganic compact oxygen-permeable membrane reactor is adopted, the heat generated by the oxidation reaction in the membrane reaction section is carried to the catalytic reforming reaction zone by the product for heat absorption of the combined reforming reaction, the heat exchange process is not needed, and the process is simplified. 3. The oxygen permeation process and the reforming process are separated in the inorganic compact oxygen-permeable membrane reactor, so that the catalyst is favorably replaced.

The attached drawings and their description:

FIG. 1 is a schematic view of an inorganic dense oxygen-permeable membrane reactor;

FIG. 2 is a schematic view of a single-tube fixed bed inorganic dense oxygen-permeable membrane reactor;

FIG. 3 is a schematic flow diagram of a process for producing syngas from methane using a fixed bed reactor;

FIG. 4 is a schematic view of a single-tube fluidized bed inorganic dense oxygen-permeable membrane reactor;

FIG. 5 is a schematic flow diagram of the production of syngas from methane using a syngas circulating fixed bed reactor;

FIG. 6 is a graph using H₂A schematic flow diagram of a CO circulating fixed bed reactor forproducing synthesis gas from methane;

the specific implementation mode is as follows:

the following description of the embodiments of the present invention is provided in connection with the accompanying drawings. Example 1 Synthesis gas production from Natural gas (methane) Using a tubular fixed bed reactor

Natural gas is the largest reserve of lower hydrocarbons, the major constituent of which is methane. In this example, a tubular fixed bed combined reactor was used to produce synthesis gas from natural gas (methane). FIG. 2 shows a schematic diagram of the single-tube fixed-bed inorganic dense oxygen-permeable membrane reactor used in this example. Comprises a shell 9, a gathering end 10, an inorganic compact oxygen permeable membrane component 2, a gas distribution plate 12 and a catalyst support plate 13. The housing 9 is made of a quartz tube. The round gathering end 10 is made of corundum material, a round groove is arranged in the middle, the diameter of the round groove is slightly larger than that of the inorganic compact oxygen permeable membrane tube, a small hole for reducing gas to enter and exit is arranged in the middle of the groove, and the aperture of the small hole is smaller than the inner diameter of the inorganic compact oxygen permeable membrane tube 2. First, a circular catalyst support plate 13, a catalyst and a circular gas distribution plate 12 are fixed in the lower half part of the quartz tube in sequence to form a catalytic reforming reaction zone 4. Two ends of an inorganic compact oxygen-permeable membrane tube 2 are respectively fixed in grooves of an upper collecting end 10 and a lower collecting end 10 by using an inorganic sealant 11, then the two collecting ends 10 are fixed in the upper half part of a quartz tube in a sealing way by using inorganic glue, and the distance between the lower collecting end and a gasdistribution plate is about 5-10 cm. The oxygen permeable area 1 is formed by the space between the quartz tube and the outer surface of the inorganic compact oxygen permeable membrane tube, and the space in the inorganic compact oxygen permeable membrane tube is a deep oxidation reaction area 3. The side surface of the reactor shell 9 between the upper and lower two collection ends is respectively provided with an air inlet 5 and an air outlet 6, and the position of the air inlet 5 is lower. Thermocouple jacks 14 and 15 are respectively arranged in the middle parts of the oxygen permeation zone and the catalytic reforming reaction zone. High-temperature oxygen-enriched gas 16 enters the oxygen permeation area 1 outside the membrane from the gas inlet 5, is changed into oxygen-deficient gas 17 after oxygen exchange, and is discharged from the gas outlet 6; the hydrocarbon or/and other reducing reaction gas 18 enters from the gas inlet 7 (upper nozzle)The deep oxidation reaction zone 3 on the inner side of the membrane reacts with permeated oxygen to generate a mixed gas intermediate product with a stoichiometric ratio, and then the mixed gas intermediate product enters the catalytic reforming reaction zone 4 to generate synthesis gas 19 which is discharged from a gas outlet 8 (a lower pipe orifice). Selecting tubular SrFe_0.5CoO_3-yThe composite oxide is used as the material of the oxygen permeable membrane reactor, the length of the tube is 20mm, the diameter of the tube is 9mm, the wall thickness is 1mm, and a single tube combined reactor is formed, as shown in figure 2. The membrane module in the reactor may also be a multi-tube. 0.5g of Ni/gamma-Al₂O₃The (40-60 mesh) catalyst is filled in the catalytic bed layer.

Figure 3 shows a schematic of a process for producing synthesis gas from methane using a combined reactor. The reactor was first heated to 800 ℃ to cure the sealing inorganic glue. Air with a flow rateof 100ml/min is introduced through the air inlet 5 by the flow meter 20, and oxygen-deficient gas is discharged through the flow meter 6. 40ml/min 5% H is introduced from the gas inlet 7₂He + H of (1)₂The Ni-based catalyst was reduced in situ at 800 ℃ for 2 hours by mixing the gases, and the temperature was maintained at 800 ℃ and was switched to 10ml/min of 100% methane. The product concentration is detected on line by gas chromatography, and the methane flow is gradually increased until the methane flow is 40 ml/min. In the inorganic mixed conductor oxygen permeable membrane reaction zone, oxygen passes through the membrane material from the oxygen permeable zone in the form of oxygen ions and undergoes a deep oxidation reaction with methane:

unreacted 75% methane with CO₂And H₂And O enters an adjacent catalytic reforming reaction zone to carry out reforming reaction:

the total package reaction is as follows:

the thermochemical equation for the system is as follows:

ΔH＝-801.7kJ/mol

ΔH＝247.0kJ/mol

Δ H205.7 kJ/mol Total envelope reaction Δ H ═ 35.5kJ/mol the entire reaction system was an exothermic reaction, and it was energetically favorable.

The reaction is carried out at the temperature of 800-1000 ℃ and the pressure of 1atm, and the space velocity is 8000h^-1And the reaction product is detected on line by gas chromatography. During the reaction operation at 900 ℃ for 400 hours, the yield of the synthesis gas reaches 300m calculated by the area of the membrane per square meter³Day. Conversion of methane 98%, CO selectivity greater than 95%, H₂the/CO is 1.9-2.0, and is very suitable for H required by F-T reaction and methanol synthesis₂The ratio of/CO. Therefore, the product can be directly subjected to downstream reaction after being cooled by the heat exchanger without being subjected to ratio adjustment, and the operation unit and the operation cost are reduced.

The deep oxidation reaction zone and the catalytic reforming reaction zone of the reactor are separated, and the same purpose can be achieved by adopting a mode of connecting an inorganic compact oxygen-permeable membrane reactor and a reforming reactor in series. The inorganic oxygen permeable membrane tube and the collective end form a membrane reactor, the corundum tube is used as a reforming reactor, and the connecting tube of the two reactors is insulated by a heating zone. In the membrane reactor, the gas pressure on both sides of the membrane was 1MPa, the remaining reaction conditions were the same as in example 1, and the conversion of methaneThe conversion rate is 98 percent, the selectivity of CO is more than 95 percent, and H₂/CO＝1.9～2.0。

The following materials were used in place of SrFe_0.5CoO_3-yAs a membrane reactor material, the purpose of preparing synthesis gas from methane can be realized.

When using (ZrO)₂)_1-x-y-(CeO₂)_x-(CaO)_y(x＝0.05～0.20，y＝0.05～0.20)、(ZrO₂)_1-x-y-(TiO₂)_x-(Y₂O₃)_y(x＝0.05～0.20，y＝0.05～0.20)、(ZrO₂)_1-x-(Tb₂O_3.5)_x(x＝0.1～0.4)、(ZrO₂)_1-x-y-(Tb₂O_3.5)_x-(Y₂O₃)_y(x is 0.05 to 0.20 and y is 0.05 to 0.20) or (Bi)₂O₃)_1-x-(Tb₂O_3.5)_x(x is 0.1 to 0.4), CH is introduced per square centimeter of the membrane module₄The amount is 1.0X 10^-3～5.0×10^-2ml·cm^-2·min^-1：

When Ln is adopted_1-xA_xCo_1-yB_yO_3-δ(Ln＝La、Ga、Sm、Nd、Pr，A＝Na、Ca、Ba、Sr，B＝Cr、Mn、Fe、Co、Ni、Cu，x＝1.0～0，y＝0～1.0)、SrCo_1-xM_xO_3-δ(M＝Ti、Cr、Mn、Fe、Ni、Cu，x＝0～0.8)、SrCo_1-x-yFe_xCu_yO_3-δ(x＝0～0.5，y＝0～0.3)、Ln_1-xM_xCoO_3-δ(Ln＝La、Pr、Nd、Sm、Ga，M＝Sr、Ca、Bi、Pb，x＝0～0.9)、La_1-xM_xCrO_3-δ(M＝Ca、Sr、Mg，x＝0.1～0.9)、Y_0.05BaCo_0.95O_3-δ、Y_0.1Ba_0.9CoO_3-δOr CaTi_1-xM_xO_3-δ(M is Fe, Co, Ni, x is 0.1-0.3) and CH is introduced per square centimeter of membrane module₄The amount of the surfactant is 0.3 to 30 ml/cm^-2·min^-1；

When YSZ-A (A ═ Pd, Pt, In) is used_0.9Pr_0.1，In_0.95Pr_0.025Zr_0.025The volume ratio of the two phases is 0.4 to 2), Bi_1.5Y_0.5O₃-Ag_0.7Pd_0.3(volume ratio of two phases is 0.4 to 2) and Bi_1.5Y_0.5O₃Ag (volume ratio of two phases: 0.4-2) and Bi_1.5Er_0.5O₃Ag (volume ratio of two phases of 0.4 to 2) or Bi_1.5Er_0.5O₃CH introduced per square centimeter of membrane component when Au (the volume ratio of two phases is 0.4-2)₄An amount of 0.3&30ml·cm^-2·min^-1；

When Bi is used₂Sr₂Ca_n-1Cu_nO_2n+4(n is 1-3, including partially replacing Bi with Pb and Sb, partially replacing Sr with Ba or rare earth elements, partially replacing Ca with rare earth elements Y, and replacing Cu with transition metals Fe, Co and Ni), Bi₂Sr₂(R_1-xCe_x)₂Cu₂O₁₀(R is a rare earth element, x is 0 to 0.3), (Pb)₂Cu)Sr₂A_n-1Cu_nO_2n+4(A ═ rare earth element, Ca, n ═ 1, 2), RBa_2-xM_xCu_3-yM′_yO_6+δ(R ═ rare earth element, M ═ Sr, Ca, Mg, M ═ Fe, Co, Ni, Al, Ga, Zn, x, y ═ 0 to 0.5) or RBa_2-xM_xCu_4-yM′_yO_8-δ(R is rare earth element, M is Sr, Ca, Mg, M' is Fe, Co, Ni, Al, Ga, Zn, x, y is 0-0.5), CH is introduced into each square centimeter of membrane component₄The amount is 0.3 to 3 ml/cm^-2·min^-1；

When using Sr_1-xBi_xFeO_3-δ(x＝0.1～0.9)、BaBi_xCo_yFe_1-x-yO_3-δ(x＝0.1～0.9，y＝0.1～0.9)、Ba_xSr_1-xCo_yFe_1-yO_3-δ(x＝0.1～0.9，y=0.1～0.9)、BaCo_1-x-yFe_xM_yO_3-δ(M＝Ti、Zr，x＝0.1～0.9，y＝0.1～0.9)、La₂NiO_4+δOr La_2-xA_xNi_1-yB_yO_4+δ(A＝Sr、Zr、Ca、Mg，B＝Co、Fe、Cu)When in CH introduction₄The amount is1 to 40 ml/cm^-2·min^-1；

When YBa is adopted₂Cu₃O_6+δ、Y_1-xZr_xBa₂Cu_3-yM_yO_6+δ(M＝Fe，Ni，Al，Sn，x＝0.1～0.6)、Y_1-xZr_xBa₂Cu₃O_6+δ，YBa₂Cu_3-xFe_xO_6+δ、LaGa_1-x-yA_xB_yO_3-δ(A＝Co、Ni，B＝Mg、Fe，x＝0.1～0.8，y＝0～0.5)、La_1-xA_xGa_1-yB_yO_3-δ(A ═ Sr, B ═ Co, Fe, Cu, Ni, x ═ 0 to 0.8, y ═ 0.2 to 1) or LaCo_1-x-yA_xB_yO_3-δ(A ═ Fe, W, Ga, B ═ Ni, Mg) CH is introduced per square centimeter of membrane module₄The amount of the surfactant is 0.3 to 35 ml/cm^-2·min^-1. Example 2 Synthesis gas production from Natural gas Using a fluidized bed inorganic dense oxygen-permeable Membrane reactor

In this example, a single tube fluidized bed inorganic dense oxygen permeable membrane reactor as shown in FIG. 4 was used. The catalytic reforming reaction zone 4 is composed of a catalyst support plate 21, a catalyst retainer plate 22 and a catalyst, and is disposed in the upper half of the quartz tube. For large-diameter reactors, a gas guiding device can be installed. Two ends of an inorganic compact oxygen permeable membrane tube 2 are respectively fixed in grooves of an upper collecting end 10 and a lower collecting end 10 by using an inorganic sealant 11, then the two collecting ends 10 are fixed in the lower half part of a quartz tube in a sealing way by using inorganic glue, and the distance between the upper collecting end and a catalyst support plate 21 is about 5-10 cm. Reducing gas is introduced from a lower pipe orifice (an air inlet 7) of the reactor, after deep oxidation is carried out by an inorganic compact oxygen permeable membrane tube, a mixed gas intermediate product is introduced from the lower part of a catalyst bed layer to form a fluidized bed catalytic reforming reaction zone 4, a product synthetic gas 19 is discharged from an outlet 8 (an upper pipe orifice), and other gas paths are the same. Selecting tubular SrFe_0.5CoO_3-yThe composite oxide is used as the oxygen permeable membrane reactor material to form a single tube combined reactor. The tube length is 30mm, the tube diameter is 9mm, and the wall thickness is1 mm. Ni/gamma-Al₂O₃1g of (160-200 mesh) catalyst was packed in the catalyst support plate. The procedure and operating method of example 1 were used. The raw material is desulfurized natural gas. The reaction is carried out at 800 ℃ and 1 atm. The natural gas inflow rate is 30-120 ml/min, the conversion rate is 80-95%, the CO selectivity is 90-95%, and H is₂and/CO is 1.8-2.1. Example 3 Synthesis gas production from methane Using a syngas recycle-type Combined reactor

For some constructions, stability is better, but under methane feed conditions,the ion conductor membrane with lower oxygen permeability can not realize high production capacity by adopting the process of example 1, and can adopt a circulating reactor mode to deprive oxygen from the reaction side of the membrane through the circulation of a synthesis gas product with strong oxygen deprivation capacity, namely CO and H are carried out in the reaction section of the inorganic compact oxygen permeable membrane₂Oxidation reaction of (3). The methane hardly undergoes deep oxidation reaction in the reaction section of the inorganic compact oxygen permeable membrane and reacts with CO in the reforming reaction zone₂、H₂And performing combined reforming reaction on the O to generate synthesis gas.

Figure 5 shows a schematic flow diagram of a process forproducing synthesis gas from methane using synthesis gas recycle. The reactor shown in FIG. 2 was used. Select Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δThe oxygen permeable membrane tubes form a circulating single-tube reactor, the length of the tube is 20mm, the diameter of the tube is 9mm, the wall thickness is 1mm, and Ni/gamma-Al₂O₃0.5g of (40-60 mesh) catalyst. First, example 1 was carried outAfter the catalyst is reduced and switched to pure methane, the gas inflow of methane is adjusted under the reaction condition of 900 ℃ and 1atm until the synthesis gas with the concentration of 90 percent is obtained. Then the circulating fan 23 is opened to circulate part of the synthesis gas and mix the synthesis gas with methane, the ratio of the synthesis gas to the methane is kept at 1, the air input of the methane and the circulating synthesis gas is gradually increased, the product concentration is detected on line by a gas chromatograph until the methane flow is 40ml/min, the circulation ratio R is 0.5, the conversion rate of the methane is 98 percent, the CO selectivity is more than 95 percent, and the H content is higher than 95 percent₂and/CO is 1.9-2.0. The reaction equation is as follows:

an oxidation area:

a reforming zone:

and (3) total package reaction:

the following materials were used in place of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δAs a membrane reactor material, the purpose of preparing synthesis gas from methane can be realized.

When YSZ-A (A ═ Pd, Pt, In) is used_0.9Pr_0.1，In_0.95Pr_0.025Zr_0.025The volume ratio of the two phases is 0.4 to 2), Bi_1.5Y_0.5O₃-Ag_0.7Pd_0.3(volume ratio of two phases is 0.4 to 2) and Bi_1.5Y_0.5O₃Ag (volume ratio of two phases: 0.4-2) and Bi_1.5Er_0.5O₃Ag (volume ratio of two phases of 0.4 to 2) or Bi_1.5Er_0.5O₃CH introduced per square centimeter of membrane component when Au (the volume ratio of two phases is 0.4-2)₄The amount of the surfactant is 0.3 to 30 ml/cm^-2·min^-1；

When Bi is used₂Sr₂Ca_n-1Cu_nO_2n+4(n is 1-3, including partial replacement of Bi by Pb, Sb, Ba or rare earth elementPartial substitution of Sr by soil element, substitution of Ca by rare earth element Y, substitution of Cu by transition metals Fe, Co and Ni), and Bi₂Sr₂(R_1-xCe_x)₂Cu₂O₁₀(R is a rare earth element, x is 0 to 0.3), (Pb)₂Cu)Sr₂A_n-1Cu_nO_2n+4(A ═ rare earth element, Ca, n ═ 1, 2), RBa_2-xM_xCu_3-yM′_yO_6+δ(R ═ rare earth element, M ═ Sr, Ca, Mg, M ═ Fe, Co, Ni, Al, Ga, Zn, x, y ═ 0 to 0.5) or RBa_2-xM_xCu_4-yM′_yO_8-δ(R is rare earth element, M is Sr, Ca, Mg, M' is Fe, Co, Ni, Al, Ga, Zn, x, y is 0-0.5), CH is introduced into each square centimeter of membrane component₄The amount is 0.3 to 3 ml/cm^-2·min^-1；

When using Sr_1-xBi_xFeO_3-δ(x＝0.1～0.9)、BaBi_xCo_yFe_1-x-yO_3-δ(x＝0.1～0.9，y＝0.1～0.9)、Ba_xSr_1-xCo_yFe_1-yO_3-δ(x＝0.1～0.9，y=0.1～0.9)、BaCo_1-x-yFe_xM_yO_3-δ(M＝Ti、Zr，x＝0.1～0.9，y＝0.1～0.9)、La₂NiO_4+δOr La_2-xA_xNi_1-yB_yO_4+δ(A＝Sr、Zr、Ca、MgAnd B is Co, Fe, Cu), CH is introduced₄The amount is1 to 40 ml/cm^-2·min^-1；

When YBa is adopted₂Cu₃O_6+δ、Y_1-xZr_xBa₂Cu_3-yM_yO_6+δ(M＝Fe，Ni，Al，Sn，x＝0.1～0.6)、Y_1-xZr_xBa₂Cu₃O_6+δ，YBa₂Cu_3-xFe_xO_6+δ、LaGa_1-x-yA_xB_yO_3-δ(A＝Co、Ni，B＝Mg、Fe，x＝0.1～0.8，y＝0～0.5)、La_1-xA_xGa_1-yB_yO_3-δ(A ═ Sr, B ═ Co, Fe, Cu, Ni, x ═ 0 to 0.8, y ═ 0.2 to 1) or LaCo_1-x-yA_xB_yO_3-δ(A ═ Fe, W, Ga, B ═ Ni, Mg) CH is introduced per square centimeter of membrane module₄The amount of the surfactant is 0.3 to 35 ml/cm^-2·min^-1. Example 4 Using H₂Circulating inorganic compact oxygen-permeable membrane reactor for preparing synthesis gas from methane

FIG. 6 shows H₂The principle flow chart of the process for preparing synthesis gas by methane in the circulating inorganic compact oxygen-permeable membrane reactor is shown in H₂The oxidation reaction of (2) is coupled to the oxygen permeation process. Part of the synthesis gas is separated by a membrane separator 24 to give H₂，H₂The circulation ratio of (A) is 0.3 to 0.7. Adopting the reactor shown in FIG. 2, tubular SrFe is selected_0.5CoO_3-yThe composite oxide is used as an oxygen permeable membrane material to form a single-tube inorganic compact oxygen permeable membrane fixed bed reactor. The length of the tube is 20mm, the diameter of the tube is 9mm, the wall thickness is 1mm, and the tube is Ni/gamma-Al₂O₃0.5g of (40-60 mesh) catalyst. High purity H used in the Experimental procedures₂Steel cylinder gas simulation H₂And (6) circulating. The reaction of example 1 is first carried out, and when the reaction has stabilized, H is introduced₂And CH₄Mixing, feeding into reactor, and keeping H₂The ratio to methane is1, the methane and the circulation H are gradually increased₂The gas chromatography detects the product concentration on line until the methane flow is 40ml/min, the conversion rate of methane is 98 percent, the selectivity of CO is more than 95 percent, and H is added₂/CO＝1.9～2.0。

When using (ZrO)₂)_1-x-y-(CeO₂)_x-(CaO)_y(x＝0.05～0.20，y＝0.05～0.20)、(ZrO₂)_1-x-y-(TiO₂)_x-(Y₂O₃)_y(x＝0.05～0.20，y＝0.05～0.20)、(ZrO₂)_1-x-(Tb₂O_3.5)_x(x＝0.1～0.4)、(ZrO₂)_1-x-y-(Tb₂O_3.5)_x-(Y₂O₃)_y(x is 0.05 to 0.20 and y is 0.05 to 0.20) or (Bi)₂O₃)_1-x-(Tb₂O_3.5)_x(x is 0.1 to 0.4), CH is introduced per square centimeter of the membrane module₄The amount is 1.0X 10^-3～5.0×10^-1ml·cm^-2·min^-1；

When Ln is adopted_1-xA_xCo_1-yB_yO_3-δ(Ln＝La、Ga、Sm、Nd、Pr，A＝Na、Ca、Ba、Sr，B＝Cr、Mn、Fe、Co、Ni、Cu，x＝1.0～0，y＝0～1.0)、SrCo_1-xM_xO_3-δ(M＝Ti、Cr、Mn、Fe、Ni、Cu，x＝0～0.8)、SrCo_1-x-yFe_xCu_yO_3-δ(x＝0～0.5，y＝0～0.3)、Ln_1-xM_xCoO_3-δ(Ln＝La、Pr、Nd、Sm、Ga，M＝Sr、Ca、Bi、Pb，x＝0～0.9)、La_1-xM_xCrO_3-δ(M＝Ca、Sr、Mg，x＝0.1～0.9)、Y_0.05BaCo_0.95O_3-δ、Y_0.1Ba_0.9CoO_3-δOr CaTi_1-xM_xO_3-δ(M is Fe, Co, Ni, x is 0.1-0.3) and CH is introduced per square centimeter of membrane module₄The amount of the surfactant is 0.3 to 80 ml/cm^-2·min^-1；

When YSZ-A (A ═ Pd, Pt, In) is used_0.9Pr_0.1，In_0.95Pr_0.025Zr_0.025The volume ratio of the two phases is 0.4 to 2), Bi_1.5Y_0.5O₃-Ag_0.7Pd_0.3(volume ratio of two phases is 0.4 to 2) and Bi_1.5Y_0.5O₃Ag (volume ratio of two phases: 0.4-2) and Bi_1.5Er_0.5O₃Ag (volume ratio of two phases of 0.4 to 2) or Bi_1.5Er_0.5O₃CH introduced per square centimeter of membrane component when Au (the volume ratio of two phases is 0.4-2)₄The amount of the surfactant is 0.3 to 50 ml/cm^-2·min^-1；

When Bi is used₂Sr₂Ca_n-1Cu_nO_2n+4(n is 1-3, including partially replacing Bi with Pb and Sb, partially replacing Sr with Ba or rare earth elements, partially replacing Ca with rare earth elements Y, and replacing Cu with transition metals Fe, Co and Ni), Bi₂Sr₂(R_1-xCe_x)₂Cu₂O₁₀(R is a rare earth element, x is 0 to 0.3), (Pb)₂Cu)Sr₂A_n-1Cu_nO_2n+4(A ═ rare earth element, Ca, n ═ 1, 2), RBa_2-xM_xCu_3-yM′_yO_6+δ(R ═ rare earth element, M ═ Sr, Ca, Mg, M ═ Fe, Co, Ni, Al, Ga, Zn, x, y ═ 0 to 0.5) or RBa_2-xM_xCu_4-yM′_yO_8-δ(R is rare earth element, M is Sr, Ca, Mg, M' is Fe, Co, Ni, Al, Ga, Zn, x, y is 0-0.5), CH is introduced into each square centimeter of membrane component₄The amount is 0.3 to 40 ml/cm^-2·min^-1；

When using Sr_1-xBi_xFeO_3-δ(x＝0.1～0.9)、BaBi_xCo_yFe_1-x-yO_3-δ(x＝0.1～0.9，y＝0.1～0.9)、BaSr_1-xCo_yFe_1-yO_3-δ(x＝0.1～0.9，y＝0.1～0.9)、BaCo_1-x-yFe_xM_yO_3-δ(M＝Ti、Zr，x＝0.1～0.9，y＝0.1～0.9)、La₂NiO_4+δOr La_2-xA_xNi_1-yB_yO_4+δ(A ═ Sr, Zr, Ca, Mg, B ═ Co, Fe, Cu) introducedCH₄The amount is1 to 60 ml/cm^-2·min^-1；

When YBa is adopted₂Cu₃O_6+δ、Y_1-xZr_xBa₂Cu_3-yM_yO_6+δ(M＝Fe，Ni，Al，Sn，x＝0.1～0.6)、Y_1-xZr_xBa₂Cu₃O_6+δ，YBa₂Cu_3-xFe_xO_6+δ、LaGa_1-x-yA_xB_yO_3-δ(A＝Co、Ni，B＝Mg、Fe，x＝0.1～0.8，y＝0～0.5)、La_1-xA_xGa_1-yB_yO_3-δ(A ═ Sr, B ═ Co, Fe, Cu, Ni, x ═ 0 to 0.8, y ═ 0.2 to 1) or LaCo_1-x-yA_xB_yO_3-δ(A ═ Fe, W, Ga, B ═ Ni, Mg) CH is introduced per squarecentimeter of membrane module₄The amount of the surfactant is 0.3 to 35 ml/cm^-2·min^-1. Example 5 Synthesis gas production from methane Using a CO circulating inorganic dense oxygen-permeable Membrane reactor

Due to H₂Has a certain reduction effect on the inorganic compact oxygen permeable membrane at high temperature, and keeps high-concentration H in the membrane reaction zone for a long time₂And may result in damage to certain membrane structures. H in the product synthesis gas₂After separation, the CO gas is recycled to react with the oxygen permeated through the membrane, so that H can be avoided₂Influence on the membrane structure. While adding a certain amount of H to the feed₂And O participates in the reforming reaction in the reforming zone, so that the C/H ratio of a reaction system can be adjusted, the carbon elimination effect can be achieved, and the carbon deposition of the catalyst is reduced. The principle flow diagram of the process is the same as that of FIG. 6, with CO being recycled. Part of the synthesis gas is separated by a membrane separator 24 to give H₂CO passes through the circulating fan 23 and CH₄、H₂Mixing O and then entering a reactor 16, CH₄/H₂O ratio of 1.4 to 1.6, CH₄The ratio of/CO is 2.8 to 3.2. . Selecting tubular SrFe_0.5CoO_3-yThe composite oxide is used as an oxygen permeable membrane material to form a single-tube inorganic compact oxygen permeable membrane reactor. The tube length is 20mm, the tube diameter is 9mm, and the wall thickness is1 mm. Ni/gamma-Al₂O₃(40-60 mesh) catalyst0.5g of the oxidizing agent. In the experimental operation, high-purity CO steel cylinder gas is used for simulating CO circulation. The reaction of example 1 was first carried out, and after the reaction was stabilized, the methane and H were gradually increased₂The gas chromatographic process of detecting the gas inflow of O and circulating CO includes the on-line detection of the product concentration until the methane flow rate is 40ml/min, the methane conversion rate is 98%, the CO selectivity is over 95%, and H content is high₂/CO＝1.9～2.0。

When using (ZrO)₂)_1-x-y-(CeO₂)_x-(CaO)_y(x＝0.05～0.20，y＝0.05～0.20)、(ZrO₂)_1-x-y-(TiO₂)_x-(Y₂O₃)_y(x＝0.05～0.20，y＝0.05～0.20)、(ZrO₂)_1-x-(Tb₂O_3.5)_x(x＝0.1～0.4)、(ZrO₂)_1-x-y-(Tb₂O_3.5)_x-(Y₂O₃)_y(x is 0.05 to 0.20 and y is 0.05 to 0.20) or (Bi)₂O₃)_1-x-(Tb₂O_3.5)_x(x is 0.1 to 0.4), CH is introduced per square centimeter of the membrane module₄The amount is 1.0X 10^-3～1.0×10^-1ml·cm^-2·min^-1；

When Ln is adopted_1-xA_xCo_1-yB_yO_3-δ(Ln＝La、Ga、Sm、Nd、Pr，A＝Na、Ca、Ba、Sr，B＝Cr、Mn、Fe、Co、Ni、Cu，x＝1.0～0，y＝0～1.0)、SrCo_1-xM_xO_3-δ(M＝Ti、Cr、Mn、Fe、Ni、Cu，x＝0～0.8)、SrCo_1-x-yFe_xCu_yO_3-δ(x＝0～0.5，y＝0～0.3)、Ln_1-xM_xCoO_3-δ(Ln＝La、Pr、Nd、Sm、Ga，M＝Sr、Ca、Bi、Pb，x＝0～0.9)、La_1-xM_xCrO_3-δ(M＝Ca、Sr、Mg，x＝0.1～0.9)、Y_0.05BaCo_0.95O_3-δ、Y_0.1Ba_0.9CoO_3-δOr CaTi_1-xM_xO_3-δ(M is Fe, Co, Ni, x is 0.1-0.3) and CH is introduced per square centimeter of membrane module₄The amount of the surfactant is 0.3 to 50 ml/cm^-2·min^-1；

When YSZ-A (A ═ Pd, Pt, In) is used_0.9Pr_0.1，In_0.95Pr_0.025Zr_0.025The volume ratio of the two phases is 0.4-2),Bi_1.5Y_0.5O₃-Ag_0.7Pd_0.3(volume ratio of two phases is 0.4 to 2) and Bi_1.5Y_0.5O₃Ag (volume ratio of two phases: 0.4-2) and Bi_1.5Er_0.5O₃Ag (volume ratio of two phases of 0.4 to 2) or Bi_1.5Er_0.5O₃CH introduced per square centimeter of membrane component when Au (the volume ratio of two phases is 0.4-2)₄The amount of the surfactant is 0.3 to 30 ml/cm^-2·min^-1；

When Bi is used₂Sr₂Ca_n-1Cu_nO_2n+4(n is 1-3, including partially replacing Bi with Pb and Sb, partially replacing Sr with Ba or rare earth elements, partially replacing Ca with rare earth elements Y, and replacing Cu with transition metals Fe, Co and Ni), Bi₂Sr₂(R_1-xCe_x)₂Cu₂O₁₀(R is a rare earth element, x is 0 to 0.3), (Pb)₂Cu)Sr₂A_n-1Cu_nO_2n+4(A ═ rare earth element, Ca, n ═ 1, 2), RBa_2-xM_xCu_3-yM′_yO_6+δ(R ═ rare earth element, M ═ Sr, Ca, Mg, M ═ Fe, Co, Ni, Al, Ga, Zn, x, y ═ 0 to 0.5) or RBa_2-xM_xCu_4-yM′_yO_8-δ(R is rare earth element, M is Sr, Ca, Mg, M' is Fe, Co, Ni, Al, Ga, Zn, x, y is 0-0.5), CH is introduced into each square centimeter of membrane component₄The amount of the surfactant is 0.3 to 10 ml/cm^-2·min^-1；

When using Sr_1-xBi_xFeO_3-δ(x＝0.1～0.9)、BaBi_xCo_yFe_1-x-yO_3-δ(x＝0.1～0.9，y＝0.1～0.9)、Ba_xSr_1-xCo_yFe_1-yO_3-δ(x＝0.1～0.9，y＝0.1～0.9)、BaCo_1-x-yFe_xM_yO_3-δ(M＝Ti、Zr，x＝0.1～0.9，y＝0.1～0.9)、La₂NiO_4+δOr La_2-xA_xNi_1-yB_yO_4+δ(A ═ Sr, Zr, Ca, Mg, B ═ Co, Fe, Cu), introduction of CH₄The amount is1 to 40 ml/cm^-2·min^-1；

When YBa is adopted₂Cu₃O_6+δ、Y_1-xZr_xBa₂Cu_3-yM_yO_6+δ(M＝Fe，Ni，Al，Sn，x＝0.1～0.6)、Y_1-xZr_xBa₂Cu₃O_6+δ，YBa₂Cu_3-xFe_xO_6+δ、LaGa_1-x-yA_xB_yO_3-δ(A＝Co、Ni，B＝Mg、Fe，x＝0.1～0.8，y＝0～0.5)、La_1-xA_xGa_1-yB_yO_3-δ(A ═ Sr, B ═ Co, Fe, Cu, Ni, x ═ 0 to 0.8, y ═ 0.2 to 1) or LaCo_1-x-yA_xB_yO_3-δ(A ═ Fe, W, Ga, B ═ Ni, Mg) CH is introduced per square centimeter of membrane module₄The amount of the surfactant is 0.3 to 35 ml/cm^-2·min^-1。

Claims

1. A process for producing a synthesis gas of hydrogen and carbon monoxide from natural gas or lower carbon hydrocarbons, characterized by: hot air or oxygen-enriched combustion gas is introduced into the oxygen-permeable side of the inorganic compact oxygen-permeable membrane, natural gas or low-carbon hydrocarbon is introduced into the reaction side of the membrane, or low-carbon hydrocarbon and CO or/and H are introduced₂The amount of the reducing mixed gas is adjusted to be 1.0 x 10 per square centimeter of the surface area of the membrane material^-3～80ml·cm^-2·min^-1Carrying out deep oxidation reaction at the temperature of 800-1000 ℃ and the pressure of 0.1-1 MPa to obtain a mixture of low-carbon hydrocarbon, carbon dioxide and/or water vapor with the required specified metering ratio; then steaming the low carbon hydrocarbon, carbon dioxide and/or waterIntroducing the mixture of steam into a reforming catalyst in another region, and reacting the hydrocarbon and CO at 800-1000 ℃ and 0.1-1 MPa₂、H₂And performing combined catalytic reforming reaction on the O to prepare the synthesis gas.

2. A process for producing hydrogen and carbon monoxide synthesis gas from natural gas or lower hydrocarbons as claimed in claim 1, wherein: when pure lower carbon hydrocarbons are used as the reducing gas, oxygen permeable membrane materials that may be selected include: ZrO having fluorite structure₂、Bi₂O₃Base doping material, composite oxide having pyrochlore structure, composite oxide material having perovskite and perovskite-like structure, ion and electron conductor two-phase composite material, and sandwich compound Sr having layered structure₄Fe_6-xCo_xO_13-xA system, a single-phase composite oxide simultaneously having an oxygen ion channel and an electron channel, and a composite film material formed by the material and ceramic, metal and inorganic high-temperature oxide; the molar ratio CH of the individual species in the mixture obtained₄/H₂O/CO₂＝3/2/1。

3. A process for producing hydrogen and carbon monoxide synthesis gas from natural gas or lower hydrocarbons as claimed in claim 1, wherein: when low-carbon hydrocarbon and H with the circulation ratio of 0.4-0.6 are adopted₂When the oxygen-permeable membrane is mixed with a synthesis gas product with a CO molar ratio of 2 and fed as a reducing gas, the oxygen-permeable membrane can be selected from the following oxygen-permeable membrane materials: ZrO having fluorite structure₂、Bi₂O₃Base doping material, composite oxide having pyrochlore structure, composite oxide material having perovskite and perovskite-like structure, ion and electron conductor two-phase composite material, and sandwich compound Sr having layered structure₄Fe_6-xCo_xO_13-xA system, a single-phase composite oxide simultaneously having an oxygen ion channel and an electron channel, and a composite film material formed by adopting the material and ceramic, metal and inorganic high-temperature oxide.

4. From natural gas or as claimed in claim 1The method for preparing hydrogen and carbon monoxide synthesis gas from low-carbon hydrocarbon is characterized by comprising the following steps: when using lower hydrocarbons and H₂As reducing gas, part of the synthesis gas product is passed through H₂After separating the membrane, H is₂Recycle and mixed feed of lower hydrocarbons from H₂Oxidation reaction with permeated oxygen; h₂The cyclic ratio of (A) to (B) is 0.4 to 0.6, CH₄/H₂1 is ═ 1; alternative oxygen permeable membrane materials include: ZrO having fluorite structure₂、Bi₂O₃Base doping material, composite oxide having pyrochlore structure, composite oxide material having perovskite and perovskite-like structure, ion and electron conductor two-phase composite material, and sandwich compound Sr having layered structure₄Fe_6-xCo_xO_13-xSystem, single-phase composite oxide having both oxygen ion and electron channels, and ceramic composition using the same,A composite film material composed of metal and inorganic high-temperature oxide.

5. A process for producing hydrogen and carbon monoxide synthesis gas from natural gas or lower hydrocarbons as claimed in claim 1, wherein: when using lower hydrocarbons and CO as reducing gases, part of the synthesis gas product is passed over H₂After separating the membrane, circularly feeding CO, low-carbon hydrocarbon and water vapor, and carrying out oxidation reaction on CO and permeated oxygen; CH (CH)₄/H₂O ratio of 1.4 to 1.6, CH₄The ratio of/CO is 2.8-3.2; alternative oxygen permeable membrane materials include: ZrO having fluorite structure₂、Bi₂O₃Base doping material, composite oxide having pyrochlore structure, composite oxide material having perovskite and perovskite-like structure, ion and electron conductor two-phase composite material, and sandwich compound Sr having layered structure₄Fe_6-xCo_xO_13-xA system, a single-phase composite oxide simultaneously having an oxygen ion channel and an electron channel, and a composite film material formed by adopting the material and ceramic, metal and inorganic high-temperature oxide.

6. An inorganic compact oxygen-permeable membrane reactor comprises an oxygen-permeable zone 1 and a deep oxidation reaction zone 3 which are formed by separating a reaction vessel 9 by an oxygen-permeable membrane component 2, and a catalyst bed layer 4 which is used as a combined catalytic reforming zone; the method is characterized in that a catalyst bed layer is separated from an oxygen permeable membrane component, and a deep oxidation reaction zone 3 is formed by a space between the catalyst bed layer 4 and the oxygen permeable membrane component 2; an oxygen-enriched gas inlet 5 is arranged on the wall of the oxygen permeation area 1 near the oxygen permeation membrane component 2, and an air outlet 6 is arranged at the far end; a reducing gas inlet 7 is arranged on the wall of the deep oxidation zone 3 between the oxygen permeable membrane component 2 and the catalyst bed layer 4 near the oxygen permeable membrane component, and a product synthesis gas outlet 8 is arranged on the other side of the catalyst bed layer 4.