CN1227154C - Method for producing synthesis gas from low-carbon hydrocarbons and inorganic dense oxygen-permeable membrane reactor - Google Patents

Abstract

The present invention relates to a method for preparing synthetic gas of hydrogen and carbon monoxide from natural gas or low-carbon hydrocarbon and an inorganic compact oxygen penetrating membrane reactor, which is characterized in that a catalyst bed is separated from an oxygen penetrating membrane assembly; hot air or oxygen-enriched burning gas is introduced into the oxygen penetrating side of the membrane; the natural gas or the low-carbon hydrocarbon is introduced into the reacting side of the membrane, or reducing mixed gas composed of the low-carbon hydrocarbon and CO or/and H2 is used to regulate the inlet amount of the reducing mixed gas; deep oxidation reaction is applied to the reducing mixed gas at the temperature of 800 to 1000DEG C and the pressure of 0.1 to 1MPa to obtain the mixture of the low-carbon hydrocarbon, carbon dioxide and/or steam; the mixture is introduced into a reforming catalyst in another area; under the conditions of 800 to 1000DEGC and 0.1 to 1MPa, the hydrocarbon carries out combined catalytic reforming reaction with CO2 and H2O to prepare the synthetic gas. The method separates the oxygen penetrating process and the reforming process, extends the service life of the oxygen penetrating membrane and the catalyst and enlarges the range of the applicable membrane material. The reaction can be carried out under the conditions of high space rate, high concentration and even pure methane intake by using a Ni base catalyst. The energy is reasonably used in the reaction system.

Description

Method for producing synthesis gas from low-carbon hydrocarbons and inorganic dense oxygen-permeable membrane reactor

Technical field:

The invention relates to a method for producing hydrogen and carbon monoxide synthesis gas from natural gas or low-carbon hydrocarbons and an inorganic dense oxygen-permeable membrane reactor in which catalyst beds are separated from oxygen-permeable membrane components.

Background technique:

The mixture of hydrogen and carbon monoxide is called synthesis gas, which is an important raw material for the production of liquid fuels, olefins (C ₂ ~C ₄ ), methanol, dimethyl ether and other chemical products. Synthesis of low-carbon hydrocarbons, especially natural gas, and subsequent synthesis of liquid fuels, olefins (C ₂ -C ₄ ), methanol and other chemical products is a comprehensive utilization path with industrial prospects. Natural gas is the low-carbon hydrocarbon with the largest reserves, and its main component is methane. Natural gas will be an important carbon source for chemical products after petroleum and coal. U.S. "Chemical News" (Haggin, Chicago CE, Chem.Eng.News, 70(17): 33(1992)) pointed out that in the process of using natural gas to produce syngas and then synthesizing liquid fuels and chemicals, the production of syngas The cost accounts for about 50% to 60% of the total cost, and the high cost is the biggest obstacle to the development and utilization of natural gas. Therefore, reducing the cost of syngas production is of great significance to the development and utilization of natural gas.

At present, the industrial process for producing synthesis gas from natural gas and other low-carbon hydrocarbons is mainly steam reforming, such as steam methane reforming (SMR). American Journal of Physical Chemistry (Choudhary, VR, Rajput, AM, Rane, VH, J.Phys.Chem., 96, 8686 (1992)), American Journal of Catalysis (Bharadwaj, SS, and Schmidt, LD, Journal of Catalysis 146, 11-21 (1994)) pointed out that because the reaction is a strong endothermic reaction, equipment investment and energy consumption are high; and CO/H ₂ is relatively high, and the product must be adjusted before it can be used in subsequent processes. In recent years, newly developed processes include non-catalytic partial oxidation (POX), combined reforming process (SMR/O ₂ R), autothermal reforming (ATR) and so on. "Catalysis Today" (Balachandran, U., Dusek, JT, Maiya, PS, et al., Catalysis Today 36(1997) 265-272), "China Science Bulletin" (Dong Hui, Xiong Guoxing, Shao Zongping, et al ., Chinese Science Bulletin 45 (3) 224-226 (2000)), U.S. Patent 6048472, etc. pointed out that these new processes have improved compared with SMR in terms of reducing energy consumption and equipment investment, but they all involve the supply of pure oxygen question. In order to avoid the existence of _N2 , it is necessary to use pure oxygen as a reactant, which requires a large investment in equipment and high operating costs. As pointed out in US Patent No. 6,048,472, the ATR process requires an oxygen concentration of 95-99.9%, and the equipment investment and operating costs for oxygen production account for a large proportion of the cost. Therefore, reducing the cost of oxygen production has become the primary factor for reducing the cost of syngas.

Inorganic dense oxygen-permeable membrane is a kind of ion conductor membrane, "Fast Ion Conductor-Basic, Material, Application" by Lin Zuxiang et al. (Shanghai Science Press, 1983), "Solid Ionology" by Dimu Hexiong (translated by Dong Zhichang, etc., Beijing Science Press, 1984) made a detailed discussion on the principle of this kind of material. There are currently two types of ion conductors that can be used for oxygen separation: one is ion conductors with no (or very low) electronic conductivity, under the action of an external electric field, or with an external electrode, under the action of an oxygen concentration gradient, the use of materials The lattice defects or gaps in the crystal conduct oxygen ion conduction, realize the selective permeation of oxygen, and achieve the purpose of oxygen separation; another type of material that has been widely studied is the mixed ion conductor, that is, the material itself has both ion conduction and electron conduction capabilities. , under the action of oxygen concentration gradient, oxygen ions migrate from the side with high oxidation potential (high oxygen concentration) to the side with low oxidation potential (low oxygen concentration) through oxygen vacancies or gaps, while electrons (electron holes) reverse Directional movement, membrane separation of oxygen can be achieved without external circuit. Inorganic dense oxygen permeable membrane has a theoretical oxygen permeability selectivity of 100%. It is a suitable material for oxygen separators and membrane reactors, especially for some medium and high temperature oxygen-related processes. way. Under certain oxygen permeability temperature and reaction conditions, improving the oxygen permeability, mechanical stability and chemical stability of such materials is still the focus of current research.

The use of inorganic dense oxygen-permeable membrane reactors for the production of synthesis gas and the in-situ use of oxygen sources in the air are effective methods to solve the problem of economical oxygen supply. Such as the process proposed in US Patent 6,048,472. In fact, this process is still a combined reforming process, and the inorganic oxygen-permeable membrane plays the role of oxygen supply in the secondary reforming. The whole process still needs two reactors, and the problems of high energy consumption and high investment have not been solved. US Patent No. 6,077,323 proposes a process mode in which the catalyst is coated on the surface of the membrane, and the mixture of methane and water vapor is passed into the reaction side of the membrane to react with the permeated oxygen to obtain synthesis gas. This process has high requirements on the membrane material. It is necessary to consider the matching of the thermal properties of the membrane material and the catalyst, and it is also required that the catalyst has no effect on the chemical structure of the membrane at high temperature. Once the carbon on the surface of the catalyst is deactivated, the membrane material must be replaced; On the other hand, the reaction process is complex and difficult to control. We have proposed an oxygen permeable membrane separator (Chinese Patent Application No. 99124427.3), which mentioned that the device can be used as an oxygen-related chemical membrane reactor, but the catalyst is also on the surface of the membrane, and the coating of the catalyst and the contact with the membrane material Technical requirements such as matching limit its application range.

"Catalysis Today" (Balachandran, U., Dusek, J.T., Maiya, P.S., et al., Catalysis Today36 (1997) 265-272) reported the use of expensive Rh-based catalysts for synthesis gas production in inorganic membrane reactors . The disadvantage of relatively cheap Ni-based catalysts for the partial oxidation of methane is that they are prone to deactivation. "Applied Catalysis" (A.Slagtern, Unni Olsbye, Applied Catalysis A: General 110 (1994) 99-108 pages) once pointed out that Ni The base catalyst was deactivated in only 17 hours in the partial oxidation of methane; "Journal of Catalysis" (V.A.Tsipouriari, Z.Zhang, and X.E.Verykios, Journal of Catalysis 179(1998), 283-291) also obtained the same conclusion.

Technical content:

The present invention proposes a method for producing hydrogen and carbon monoxide synthesis gas from natural gas or low-carbon hydrocarbons based on an inorganic dense oxygen-permeable membrane reactor, and an inorganic dense oxygen-permeable membrane reactor in which the catalyst bed is separated from the oxygen-permeable membrane assembly, to The above-mentioned problems of the prior art are overcome.

The method for producing hydrogen and carbon monoxide synthesis gas from natural gas or low-carbon hydrocarbons of the present invention is characterized in that hot air or oxygen-enriched combustion gas is passed into the oxygen-permeable side of the inorganic dense oxygen-permeable membrane, and natural gas or Low-carbon hydrocarbons, or a reducing mixed gas composed of low-carbon hydrocarbons and CO or _H2 , or a reducing mixed gas composed of low-carbon hydrocarbons, CO and _H2 , to adjust the amount of reducing mixed gas 1.0×10 ^-3 ~ 80ml·cm ^-2 ·min ^-1 (calculated by the surface area of membrane material per square centimeter), under the conditions of temperature of 800~1000℃ and pressure of 0.1~1MPa, oxidation reaction to combined catalytic reforming reaction A mixture of low-carbon hydrocarbons and carbon dioxide and/or water vapor in the desired stoichiometric ratio; then this mixture is introduced onto the reforming catalyst, under the conditions of a temperature of 800-1000°C and a pressure of 0.1-1MPa, hydrocarbons and CO ₂ and/or Or H ₂ O undergoes joint catalytic reforming reaction to produce synthesis gas.

The adjustment of the amount of reducing mixed gas to carry out the oxidation reaction to the mixture of low-carbon hydrocarbons and carbon dioxide and/or water vapor in the stoichiometric ratio required for the combined catalytic reforming reaction refers to the inorganic dense oxygen-permeable membrane material selected according to the specific , the geometric dimensions of the membrane module, and the temperature of the oxygen permeable oxidation zone, calculated by the surface area of the membrane material per square centimeter, adjust the amount of low-carbon hydrocarbons in the range of 1.0×10 ^-3 ~ 80ml·cm ^-2 ·min ^-1 and correspondingly Adjust the intake of other gases to control the degree of reaction, so as to obtain the mixture of low-carbon hydrocarbons and carbon dioxide and/or water vapor in the stoichiometric ratio required by the combined catalytic reforming reaction:

(1) When pure low-carbon hydrocarbons are used as the reducing gas, the film materials include: ZrO ₂ or Bi ₂ O ₃ based dopant materials with fluorite structure, composite oxides with pyrochlore structure, Composite oxide materials of perovskite and perovskite-like structures, dual-phase composite materials of ionic and electronic conductors, layered interlayer compound Sr ₄ Fe _6-x Co _x O _13-x system, with both oxygen ions and electrons Channel single-phase composite oxide, or a composite membrane material composed of the above materials and ceramics, metals and inorganic high-temperature oxides; the molar ratio of each species in the obtained mixture is CH ₄ /H ₂ O/CO ₂ =3 /2/1;

(2) When low-carbon hydrocarbons and synthesis gas with a molar ratio of _H2 and CO of 2 are used as the reducing mixed gas, it means that part of the synthesis gas product is recycled and mixed with low-carbon hydrocarbons, and the synthesis gas is mixed with the permeated Oxygen undergoes an oxidation reaction; the circulation ratio of the synthesis gas is 0.4 to 0.6; the molar ratio of each species in the obtained mixture is CH ₄ /H ₂ O/CO ₂ =3/2/1; the membrane material includes: ZrO ₂ or Bi ₂ O ₃ -based doped materials with fluorite structure, composite oxides with pyrochlore structure, composite oxide materials with perovskite and perovskite-like structures, dual-phase composite materials for ionic and electronic conductors , a layered interlayer compound Sr ₄ Fe _6-x Co _x O _13-x system, a single-phase composite oxide with both oxygen ion and electron channels, or a combination of the above materials and ceramics, metals and inorganic high-temperature oxides Composite membrane materials;

(3) When low-carbon hydrocarbons and _H2 are used as the reducing mixed gas, it means that after part of the synthesis gas product passes through the _H2 separation membrane, _H2 is circulated and mixed with low-carbon hydrocarbons; the circulation ratio of _H2 is 0.4 ~0.6, CH ₄ /H ₂ molar ratio is 1; the membrane materials include: ZrO ₂ or Bi ₂ O ₃ based doping materials with fluorite structure, composite oxides with pyrochlore structure, perovskite Composite oxide materials with ore and perovskite-like structures, dual-phase composite materials for ion and electron conductors, interlayer compound Sr ₄ Fe _6-x Co _x O _13-x system with layered structure, and oxygen ion and electron channels at the same time Single-phase composite oxides, or composite membrane materials composed of the above materials, ceramics, metals and inorganic high-temperature oxides;

(4) When low-carbon hydrocarbons and CO are used as the reducing mixed gas, it means that after part of the synthesis gas product passes through the H ₂ separation membrane, CO is circulated and mixed with low-carbon hydrocarbons and water vapor; CH ₄ /H ₂ O The molar ratio is 1.4 to 1.6, and the molar ratio of CH ₄ /CO is 2.8 to 3.2; the membrane materials include: ZrO ₂ or Bi ₂ O ₃ based doping materials with fluorite structure, composite oxide with pyrochlore structure materials, composite oxide materials with perovskite and perovskite-like structures, dual-phase composite materials for ion and electron conductors, interlayer compound Sr ₄ Fe _6-x Co _x O _13-x system with layered structure, and oxygen Single-phase composite oxides for ion and electron channels, or composite membrane materials composed of the above materials and ceramics, metals and inorganic high-temperature oxides;

The feed ratios mentioned in the above methods all take the synthesis gas with H ₂ /CO=2 (actually within the range of 1.8-2.1) as the target product. Syngas with different H ₂ /CO ratios can also be obtained by adjusting the feed ratio.

An inorganic dense oxygen-permeable membrane reactor of the present invention includes an oxygen-permeable zone 1 and a deep oxidation reaction zone 3 separated by an oxygen-permeable membrane assembly 2 to form a reaction vessel 9, and a catalyst bed as a combined catalytic reforming zone 4; It is characterized in that the catalyst bed is separated from the oxygen-permeable membrane assembly, and the deep oxidation reaction zone 3 is formed by the space between the catalyst bed 4 and the oxygen-permeable membrane assembly 2; in the oxygen-permeable area 1 near the oxygen-permeable membrane assembly 2 There is an air inlet 5 for oxygen-rich gas on the wall of the device, and a gas outlet 6 is provided at the far end; the deep oxidation reaction zone 3 between the oxygen-permeable membrane assembly 2 and the catalyst bed 4 is close to the device near the oxygen-permeable membrane assembly An inlet 7 for reducing gas is opened on the wall, and an outlet 8 for product synthesis gas is opened on the other side of the catalyst bed 4 .

When the above-mentioned reactor is used to produce hydrogen and carbon monoxide synthesis gas from low-carbon hydrocarbons, hot air or hot oxygen-enriched combustion gas with a temperature of 800-1000 ° C and a pressure of 0.1-1 MPa is passed into the permeable gas through the inlet 5. Oxygen-permeable zone 1 on one side of the oxygen membrane 2, the oxygen-poor gas is discharged from the gas outlet 6, and low-carbon hydrocarbons or reducing mixed gases composed of low-carbon hydrocarbons and CO or/and _H2 enter the oxygen-permeable zone through the inlet 7 The deep oxidation reaction zone 3 on the other side of the membrane 2 reacts with the oxygen permeated by the inorganic dense oxygen-permeable membrane module 2, adjusts the intake of reducing gas, and obtains the required specified stoichiometric ratio of low-carbon hydrocarbons, carbon dioxide and/or A mixture of water vapor; the mixture then enters the catalytic reforming reaction zone 4, where a combined reforming reaction occurs at a temperature of 800-1000°C and a pressure of 0.1-1 MPa, and the obtained synthesis gas product is discharged from outlet 8.

The inorganic oxygen-permeable membrane material described in the method of the present invention can be used to manufacture the inorganic dense oxygen-permeable membrane module 2 in the inorganic dense oxygen-permeable membrane reactor of the present invention. The geometric configuration of the inorganic dense oxygen-permeable membrane module 2 may be flat, corrugated, tubular, or honeycomb.

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

The inventive method is characterized in that:

1. The complete oxygen permeation oxidation reaction process and the combined reforming reaction process are carried out in two regions in the same reactor chamber respectively;

2. The transmission of oxygen in the oxygen permeable membrane is realized by the complete oxidation reaction coupling of different reducing gases, and the reducing gases can be CH ₄ , CO+H ₂ , CO or H ₂ ;

3. Air or oxygen-enriched combustion gas is fed into one side of the inorganic dense oxygen-permeable membrane, and reducing gas is fed into the other side of the membrane to completely oxidize part of the reducing gas to generate CO ₂ and H ₂ O.

The advantage of the inventive method is:

1. The oxygen permeation process is coupled with the deep oxidation reaction, which shortens the initiation time of oxygen permeation of the membrane material, greatly increases the oxygen permeation per unit area of the membrane material, thereby increasing the synthesis gas output per unit area of the membrane in the entire process.

2. The oxygen permeation process is separated from the reforming process. Only the deep oxidation reaction occurs in the reaction section of the inorganic oxygen permeable membrane. The degree of reaction is limited by the oxygen supply rate of the membrane, which avoids the phenomenon of flying temperature caused by the severe deep oxidation reaction and effectively controls The temperature gradient of the membrane material is reduced, the mechanical stability of the membrane is protected, the life of the membrane is prolonged, and the range of membrane materials that can be applied to this reaction is expanded.

3. The oxygen permeation process is separated from the reforming process, and the reaction process is easy to control. By adjusting the amount of reducing gas, the geometric size of the membrane tube, the temperature and the choice of catalyst (the catalyst can be modified or not modified according to the specific membrane material) to control the degree of reaction in the deep oxidation reaction zone, and then achieve the purpose of controlling the entire reaction .

4. The energy utilization in the reaction system is reasonable, and the requirement for energy consumption is low. The whole reaction is an exothermic reaction, and the first deep oxidation reaction in the reaction is an exothermic reaction, and the heat generated is carried by the product to the catalytic reaction zone, which is required for the endothermic reaction of the reforming reaction and is sufficient to maintain the energy required for the subsequent reforming reaction. heat.

5. Separate the oxygen permeation process from the reforming process, which is beneficial to the protection of the catalyst.

(1) The oxygen permeation process is separated from the combined reforming process. The catalytic combined reforming reaction on the catalyst is an endothermic reaction, and there is no catalyst bed overheating phenomenon caused by the heat release of the oxidation reaction in other processes, thereby avoiding the catalyst due to Inactivation due to high temperature sintering caused by runaway temperature.

(2) In the prior art, high-temperature pyrolysis of hydrocarbons and carbon deposition is an important reason for catalyst deactivation, especially the cracking of hydrocarbons with a carbon number greater than 2 is obvious above 650°C. The process proposed by the invention cracks part of the multi-carbon hydrocarbons in the membrane reaction zone, and finally generates CO ₂ and H ₂ O into the reforming zone, slows down the rate of carbon deposition on the reforming catalyst, and prolongs the service life of the catalyst.

(3) H ₂ O produced by deep oxidation participates in the reaction in the reforming reaction zone, and the presence of H ₂ O is beneficial to the carbon removal of the catalyst. Therefore, the carbon deposition on the catalyst can be reduced, and the service life of the catalyst can be prolonged.

6. The present 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 use Ni-based under the conditions of high space velocity, large concentration, and even pure methane intake. Catalyst proceeds. "Catalysis Today" (Balachandran, U., Dusek, J.T., Maiya, P.S., et al., Catalysis Today 36(1997) 265-272) reported the use of expensive Rh-based catalysts for synthesis gas production in inorganic membrane reactors . The shortcoming of relatively cheap Ni-based catalysts for partial oxidation of methane is that they are prone to deactivation. Only 17 hours in the methane partial oxidation reaction is just deactivated; "Journal of Catalysis" (V.A.Tsipouriari, Z.Zhang, and X.E.Verykios, Journal of Catalysis179 (1998), 283-291) also obtains the same conclusion. We used a Ni-based catalyst under the condition of pure methane gas intake, and the catalyst activity did not decrease significantly after 400 hours of reaction. Moreover, the oxygen permeation process is separated from the reforming process, and once the catalyst is deactivated, it is also convenient to replace the catalyst. It not only reduces the cost of the catalyst, but also reduces the compression power consumption caused by the large use of inert components, so that the operating energy consumption is minimized, and the operating cost is also greatly reduced.

7. The method of the present invention has a wide range of applications. Among low-carbon hydrocarbons, methane has the highest chemical stability. For other light hydrocarbons with carbon number greater than 2, this method can also be used to produce synthesis gas.

Compared with the existing technology, the inorganic dense oxygen-permeable membrane reactor of the present invention has the following characteristics and advantages:

1. The inorganic dense oxygen-permeable membrane reactor of the present invention combines the oxygen-permeable process and the reforming process in one reactor cavity, has a compact structure, realizes intensive reaction, and reduces equipment investment and operating costs.

2. The inorganic dense oxygen-permeable membrane reactor is adopted, and the heat generated by the oxidation reaction in the membrane reaction section is carried by the product to the catalytic reforming reaction zone, which is required for the combined reforming reaction to absorb heat, without the need for heat exchange process, and the process is simplified.

3. In the inorganic dense oxygen-permeable membrane reactor, the oxygen-permeable process is separated from the reforming process, which is beneficial to the replacement of the catalyst.

Attached drawings and descriptions:

Accompanying drawing 1 is the schematic diagram of inorganic dense oxygen-permeable membrane reactor;

Accompanying drawing 2 is a schematic diagram of a single-tube fixed-bed inorganic dense oxygen-permeable membrane reactor;

Accompanying drawing 3 is the schematic flow sheet of utilizing fixed-bed reactor to make syngas process by methane;

Accompanying drawing 4 is a schematic diagram of a single-tube fluidized bed inorganic dense oxygen-permeable membrane reactor;

Accompanying drawing 5 is the principle flowchart of utilizing syngas circulation fixed-bed reactor to produce syngas by methane;

Accompanying drawing 6 is the principle flowchart of utilizing _H2 /CO circulation fixed-bed reactor to produce synthesis gas by methane;

Detailed ways:

The specific implementation manners of the present invention will be described below with reference to the accompanying drawings.

Embodiment 1, adopt tubular fixed-bed reactor to make synthetic gas with natural gas (methane)

Natural gas is the low-carbon hydrocarbon with the largest reserves, and its main component is methane. In this example, a tubular fixed-bed combined reactor is used to produce synthesis gas from natural gas (methane). Accompanying drawing 2 has provided the schematic diagram of single-tube fixed-bed inorganic dense oxygen-permeable membrane reactor adopted in this embodiment. It includes a casing 9, a collection end 10, an inorganic dense oxygen-permeable membrane assembly 2, a gas distribution plate 12, and a catalyst support plate 13. The housing 9 is made of quartz tube. The circular collection end 10 is made of corundum material, and there is a circular groove in the middle, the diameter of which is slightly larger than that of the inorganic dense oxygen-permeable membrane tube. The inner diameter of the membrane tube 2. Firstly, fix the circular catalyst support plate 13 , the catalyst and the circular gas distribution plate 12 in the lower half of the quartz tube to form the catalytic reforming reaction zone 4 . Use inorganic sealant 11 to fix the two ends of the inorganic dense oxygen-permeable membrane tube 2 in the grooves of the upper and lower collection ends 10 respectively, and then use inorganic glue to seal and fix the two collection ends 10 in the upper half of the quartz tube. Part, the lower collection end is about 5-10cm away from the gas distribution plate. The space between the quartz tube and the outer surface of the inorganic dense oxygen-permeable film tube constitutes an oxygen-permeable zone 1 , and the space inside the inorganic dense oxygen-permeable film tube is a deep oxidation reaction zone 3 . On the side of the reactor shell 9 between the upper and lower collection ends, an air inlet 5 and an air outlet 6 are oppositely opened, and the air inlet 5 is located at a lower position. There are thermocouple sockets 14 and 15 in the middle of the oxygen permeable zone and the catalytic reforming reaction zone respectively. The high-temperature oxygen-enriched gas 16 enters the oxygen-permeable zone 1 outside the membrane from the inlet 5, and becomes an oxygen-depleted gas 17 after oxygen exchange and is discharged from the gas outlet 6; hydrocarbon or/and other reducing reaction gases 18 are discharged from the inlet 7 (upper nozzle) enters the deep oxidation reaction zone 3 inside the membrane, reacts with the permeated oxygen to generate a stoichiometric mixed gas intermediate product, and then enters the catalytic reforming reaction zone 4 to generate synthesis gas 19 from the gas outlet 8 (lower tube mouth) out. The tubular SrFe _0.5 CoO _3-y composite oxide is selected as the material of the oxygen permeable membrane reactor, with a tube length of 20 mm, a tube diameter of 9 mm, and a wall thickness of 1 mm to form a single-tube composite reactor, as shown in Figure 2. The membrane module in the reactor can also be multi-tube. 0.5g Ni/γ-Al ₂ O ₃ (40-60 mesh) catalyst is filled in the catalyst bed.

Figure 3 shows a schematic flow chart of producing synthesis gas from methane using a combined reactor. Firstly, the reactor is heated to 800°C to cure the sealing inorganic glue. Through the flow meter 20, the air with a flow rate of 100ml/min is passed through the air inlet 5, and the oxygen-depleted gas is discharged through 6. 40ml/min 5% H ₂ mixed gas of He+H ₂ is fed through the gas inlet 7 to reduce the Ni-based catalyst in situ at 800°C for 2 hours, keep the temperature at 800°C, and switch to 10ml/min 100% methane. The product concentration was detected online by gas chromatography, and the methane flow was gradually increased until the methane flow was 40ml/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:

            

The unreacted 75% methane enters the adjacent catalytic reforming reaction zone with CO ₂ and H ₂ O, and the reforming reaction occurs:

             

             

The total package response is:

             

The thermochemical equation of the system is as follows:

ΔH=-801.7kJ/mol

ΔH=247.0kJ/mol

ΔH=205.7kJ/mol

turnkey response ΔH=-35.5kJ/mol

The whole reaction system is an exothermic reaction, which is favorable in terms of energy.

The reaction is carried out under the conditions of 800-1000°C and 1 atm, and the space velocity is 8000h ^-1 , and the reaction product is detected online by gas chromatography. During the reaction operation at 900°C and 400 hours, the production of synthesis gas can reach 300m ³ ·day calculated on the basis of membrane area per square meter. The conversion rate of methane is 98%, the selectivity of CO is greater than 95%, and H ₂ /CO=1.9-2.0, which is very suitable for the H ₂ /CO ratio required by FT reaction and methanol synthesis. Therefore, the product does not need to be adjusted, and the downstream reaction can be directly carried out after being cooled by the heat exchanger, which reduces the operating unit and operating costs.

The same purpose can be achieved by separating the deep oxidation reaction zone of the above reactor from the catalytic reforming reaction zone, and adopting the method of connecting the inorganic dense oxygen-permeable membrane reactor and the reforming reactor in series. The inorganic oxygen-permeable membrane tube and the collection end are used to form a membrane reactor, the corundum tube is used as a reforming reactor, and the connecting pipe of the two reactors is kept warm with a heating tape. In the membrane reactor, the gas pressure on both sides of the membrane is 1MPa, and the rest of the reaction conditions are the same as in Example 1. The conversion rate of methane is 98%, the selectivity of CO is greater than 95%, and H ₂ /CO=1.9-2.0.

Using the following materials to replace SrFe _0.5 CoO _3-y as the membrane reactor material can also achieve the purpose of producing synthesis gas from methane.

When using (ZrO ₂ ) _1-xy -(CeO ₂ ) _x -(CaO) _y (x=0.05～0.20, y=0.05～0.20), (ZrO ₂ ) _1-xy -(TiO ₂ ) _x -(Y ₂ O ₃ ) _y (x=0.05～0.20, y=0.05～0.20), (ZrO ₂ ) _1-x -(Tb ₂ O _3.5 ) _x (x=0.1～0.4), (ZrO ₂ ) _1-xy - (Tb ₂ O _3.5 ) _x -(Y ₂ O ₃ ) _y (x=0.05～0.20, y=0.05～0.20) or (Bi ₂ O ₃ ) _1-x -(Tb ₂ O _3.5 ) _x (x=0.1 ～0.4), the amount of CH ₄ introduced per square centimeter membrane module is 1.0×10 ^-3 ～5.0×10 ^-2 ml·cm ^-2 ·min ^-1 ;

When using Ln _1-x A _x Co _{1-y By y} O _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-x M _x O _3-δ ^- (M=Ti, Cr, Mn, Fe, Ni, Cu, x=0~0.8) , SrCo _1-xy F _x Cu _y O _3-δ (x=0~0.5, y=0~0.3), Ln _1-x M _x CoO _3-δ (Ln=La, Pr, Nd, Sm, Ga, M=Sr, Ca, Bi, Pb, x=0~0.9), La _1-x M _x CrO _3-δ (M=Ca, Sr, Mg, x=0.1~0.9), Y _0.05 BaCo _0.95 O _{3- δ} , Y _0.1 Ba _0.9 CoO _3-δ or CaTi _1-x M _x O _3-δ (M=Fe, Co, Ni, x=0.1～0.3), the amount of CH ₄ fed into the membrane module per square centimeter is 0.3～30ml cm ^-2 min ^-1 ;

When using YSZ-A (A=Pd, Pt, In _0.9 Pr _0.1 , In _0.95 Pr _0.025 Zr _0.025 , the volume ratio of the two phases is 0.4~2), Bi _1.5 Y _0.5 O ₃ -Ag _0.7 Pd _0.3 (two-phase The volume ratio is 0.4~2), Bi _1.5 Y _0.5 O ₃ -Ag (the volume ratio of the two phases is 0.4~2), Bi _1.5 Er _0.5 O ₃ -Ag (the volume ratio of the two phases is 0.4~2) or Bi _1.5 When Er _0.5 O ₃ -Au (the volume ratio of the two phases is 0.4~2), the amount of CH ₄ passed into the membrane module per square centimeter is 0.3~30ml·cm ^-2 ·min ^-1 ;

When using Bi ₂ Sr ₂ Ca _n-1 Cu _n O _2n+4 (n=1~3, including partially replacing Bi with Pb and Sb, partially replacing Sr with Ba or rare earth elements, replacing Ca with rare earth element Y, and using transition Metal Fe, Co, Ni instead of Cu), Bi ₂ Sr ₂ (R _{1-x Cex} ) ₂ Cu ₂ O ₁₀ (R=rare earth element, x=0～0.3), (Pb ₂ Cu)Sr ₂ A _{n- 1} Cu _n O _2n+4 (A=rare earth element, Ca, n=1, 2), RBa _2-x M _x Cu _3-y M′ _y O _6+δ (R=rare earth element, M=Sr, Ca , Mg, M'=Fe, Co, Ni, Al, Ga, Zn, x, y=0～0.5) or RBa _2-x M _x Cu _4-y M' _y O _8-δ (R=rare earth element, When M=Sr, Ca, Mg, M'=Fe, Co, Ni, Al, Ga, Zn, x, y=0~0.5), the amount of CH ₄ passing through the membrane module per square centimeter is 0.3~3ml·cm ^-2 min ^-1 ;

When using Sr _1-x Bi _x FeO _3-δ (x=0.1～0.9), BaBi _x Co _y Fe _1-xy O _3-δ (x=0.1～0.9, y=0.1～0.9), Ba _x Sr _{1 -x} Co _y Fe _1-y O _3-δ (x=0.1～0.9, y=0.1～0.9), BaCo _1-xy Fe _x M _y O _3-δ (M=Ti, Zr, x=0.1～0.9 , y=0.1～0.9), La ₂ NiO _4+δ or La _2-x A _x Ni _1-y By _y O _4+δ (A=Sr, Zr, Ca, Mg, B=Co, Fe, Cu) , the amount of CH ₄ introduced is 1-40ml·cm ^-2 ·min ^-1 ;

When using YBa ₂ Cu ₃ O _6+δ , Y _1-x Zr _x Ba ₂ Cu _3-y M _y O _6+δ (M=Fe, Ni, Al, Sn, x=0.1～0.6), Y _{1- x} Zr _x Ba ₂ Cu ₃ O _6+δ , YBa ₂ Cu _3-x Fe _x O _6+δ , LaGa _1-xy A _{x By} O _3-δ (A=Co, Ni, B=Mg, Fe, x=0.1～0.8, y=0～0.5), La _1-x A _x Ga _1-y By _y O _3-δ (A=Sr, B=Co, Fe, Cu, Ni, x=0～0.8, y=0.2~1) or LaCo _1-xy A _{x By} O _3-δ (A=Fe, W, Ga, B=Ni, Mg), the amount of CH ₄ passed through per square centimeter membrane module is 0.3~ 35ml·cm ^-2 ·min ^-1 .

Example 2: Using a Fluidized Bed Inorganic Dense Oxygen-permeable Membrane Reactor to Produce Syngas from Natural Gas

In this embodiment, the single-tube fluidized bed inorganic dense oxygen-permeable membrane reactor shown in FIG. 4 is used. The catalytic reforming reaction zone 4 is composed of a catalyst support plate 21, a catalyst baffle 22 and a catalyst, and is placed in the upper half of the quartz tube. For large-diameter reactors, gas guide devices can be installed. Use inorganic sealant 11 to fix the two ends of the inorganic dense oxygen-permeable membrane tube 2 respectively in the grooves of the upper and lower collection ends 10, and then use inorganic glue to seal and fix the two collection ends 10 in the lower half of the quartz tube. Part, the upper assembly end is about 5-10 cm away from the catalyst support plate 21. The reducing gas is introduced from the lower nozzle (inlet 7) of the reactor, and after being deeply oxidized through the inorganic dense oxygen-permeable membrane tube, the mixed gas intermediate product is introduced from the lower part of the catalyst bed to form a fluidized bed catalytic reactor. In the whole reaction zone 4, the product synthesis gas 19 is discharged from the outlet 8 (upper nozzle), and the other gas paths are the same. The tubular SrFe _0.5 CoO _3-y composite oxide was selected as the material of the oxygen-permeable membrane reactor to form a single-tube composite reactor. The tube length is 30mm, the tube diameter is 9mm, and the wall thickness is 1mm. 1 g of Ni/γ-Al ₂ O ₃ (160-200 mesh) catalyst was filled on the catalyst support plate. Adopt the technological process and operation method of embodiment 1. The raw material is desulfurized natural gas. The reaction was carried out at 800° C. and 1 atm. The gas intake flow rate is 30-120ml/min, the conversion rate is 80-95%, the CO selectivity is 90-95%, and H ₂ /CO=1.8-2.1.

Embodiment 3, using the syngas circulation combined reactor to produce syngas from methane

For some ion conductor membranes with good structural stability but low oxygen permeability under the condition of methane gas intake, the process in Example 1 cannot achieve high production capacity, and a circulating reactor method can be used. Oxygen is extracted from the reaction side of the membrane through the circulation of syngas products with strong oxygen-absorbing ability, that is, the oxidation reaction of CO and _H2 is carried out in the reaction section of the inorganic dense oxygen-permeable membrane. Methane hardly undergoes a deep oxidation reaction in the inorganic dense oxygen-permeable membrane reaction section, and undergoes a combined reforming reaction with CO ₂ and H ₂ O in the reforming reaction zone to generate synthesis gas.

Figure 5 shows the principle flow of the synthesis gas production process from methane using the synthesis gas cycle. The reactor shown in Figure 2 was used. Ba _0.5 Sr _0.5 Co _0.8 Fe _0.2 O _3-δ oxygen-permeable film tubes are used to form a circulating single-tube reactor, with a tube length of 20 mm, a tube diameter of 9 mm, and a wall thickness of 1 mm. Ni/γ-Al ₂ O ₃ (40-60 mesh ) Catalyst 0.5g. First, carry out the operation of Example 1, carry out the reduction of the catalyst, and after switching to pure methane, adjust the intake of methane under the reaction conditions of 900° C. and 1 atm until the synthesis gas with a concentration of 90% is obtained. Then turn on the circulation fan 23 to circulate part of the synthesis gas and mix it with methane, keep the ratio of synthesis gas and methane at 1, gradually increase the intake of methane and circulating synthesis gas, and detect the product concentration on-line by gas chromatography until the methane flow rate 40ml/min, circulation ratio R=0.5, conversion rate of methane is 98%, selectivity of CO is greater than 95%, H ₂ /CO=1.9-2.0. The reaction equation is as follows:

Oxidation zone:

          

Reformation area:

          

Total Package Response:

Using the following materials to replace Ba _0.5 Sr _0.5 Co _0.8 Fe _0.2 O _3-δ as the membrane reactor material can also achieve the purpose of producing synthesis gas from methane.

When using (ZrO ₂ ) _1-xy -(CeO ₂ ) _x -(CaO) _y (x=0.05～0.20, y=0.05～0.20), (ZrO ₂ ) _1-xy -(TiO ₂ ) _x -(Y ₂ O ₃ ) _y (x=0.05～0.20, y=0.05～0.20), (ZrO ₂ ) _1-x -(Tb ₂ O _3.5 ) _x (x=0.1～0.4), (ZrO ₂ ) _1-xy - (Tb ₂ O _3.5 ) _x -(Y ₂ O ₃ ) _y (x=0.05～0.20, y=0.05～0.20) or (Bi ₂ O ₃ ) _1-x -(Tb ₂ O _3.5 ) _x (x=0.1 ～0.4), the amount of CH ₄ introduced per square centimeter membrane module is 1.0×10 ^-3 ～5.0×10 ^-2 ml·cm ^-2 ·min ^-1 ;

When using Ln _1-x A _x Co _{1-y By y} O _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-x M _x O _3-δ (M=Ti, Cr, Mn, Fe, Ni, Cu, x=0~0.8), SrCo _1-xy F _x Cu _y O _3-δ (x=0~0.5, y=0~0.3), Ln _1-x M _x CoO _3-δ (Ln=La, Pr, Nd, Sm, Ga, M =Sr, Ca, Bi, Pb, x=0~0.9), La _1-x M _x CrO _3-δ (M=Ca, Sr, Mg, x=0.1~0.9), Y _0.05 BaCo _0.95 O _3-δ , Y _0.1 Ba _0.9 CoO _3-δ or CaTi _1-x M _x O _3-δ (M=Fe, Co, Ni, x=0.1～0.3), the amount of CH ₄ per square centimeter membrane module is 0.3 ~30ml·cm ^-2 ·min ^-1 ;

When using YSZ-A (A=Pd, Pt, In _0.9 Pr _0.1 , In _0.95 Pr _0.025 Zr _0.025 , the volume ratio of the two phases is 0.4~2), Bi _1.5 Y _0.5 O ₃ -Ag _0.7 Pd _0.3 (two-phase The volume ratio is 0.4~2), Bi _1.5 Y _0.5 O ₃ -Ag (the volume ratio of the two phases is 0.4~2), Bi _1.5 Er _0.5 O ₃ -Ag (the volume ratio of the two phases is 0.4~2) or Bi _1.5 When Er _0.5 O ₃ -Au (the volume ratio of the two phases is 0.4~2), the amount of CH ₄ passed into the membrane module per square centimeter is 0.3~30ml·cm ^-2 ·min ^-1 ;

When using Bi ₂ Sr ₂ Ca _n-1 Cu _n O _2n+4 (n=1~3, including partially replacing Bi with Pb and Sb, partially replacing Sr with Ba or rare earth elements, replacing Ca with rare earth element Y, and using transition Metal Fe, Co, Ni instead of Cu), Bi ₂ Sr ₂ (R _{1-x Cex} ) ₂ Cu ₂ O ₁₀ (R=rare earth element, x=0～0.3), (Pb ₂ Cu)Sr ₂ A _{n- 1} Cu _n O _2n+4 (A=rare earth element, Ca, n=1, 2), RBa _2-x M _x Cu _3-y M′ _y O _6+δ (R=rare earth element, M=Sr, Ca , Mg, M'=Fe, Co, Ni, Al, Ga, Zn, x, y=0～0.5) or RBa _2-x M _x Cu _4-y M' _y O _8-δ (R=rare earth element, When M=Sr, Ca, Mg, M'=Fe, Co, Ni, Al, Ga, Zn, x, y=0~0.5), the amount of CH ₄ passing through the membrane module per square centimeter is 0.3~3ml·cm ^-2 min ^-1 ;

When using Sr _1-x Bi _x FeO _3-δ (x=0.1～0.9), BaBi _x Co _y Fe _1-xy O _3-δ (x=0.1～0.9, y=0.1～0.9), Ba _x Sr _{1 -x} Co _y Fe _1-y O _3-δ (x=0.1～0.9, y=0.1～0.9), BaCo _1-xy Fe _x M _y O _3-δ (M=Ti, Zr, x=0.1～0.9 , y=0.1～0.9), La ₂ NiO _4+δ or La _2-x A _x Ni _1-y By _y O _4+δ (A=Sr, Zr, Ca, Mg, B=Co, Fe, Cu) , the amount of CH ₄ introduced is 1-40ml·cm ^-2 ·min ^-1 ;

When using YBa ₂ Cu ₃ O _6+δ , Y _1-x Zr _x Ba ₂ Cu _3-y M _y O _6+δ (M=Fe, Ni, Al, Sn, x=0.1～0.6), Y _{1- x} Zr _x Ba ₂ Cu ₃ O _6+δ , YBa ₂ Cu _3-x Fe _x O _6+δ , LaGa _1-xy A _{x By} O _3-δ (A=Co, Ni, B=Mg, Fe, x=0.1～0.8, y=0～0.5), La _1-x A _x Ga _1-y By _y O _3-δ (A=Sr, B=Co, Fe, Cu, Ni, x=0～0.8, y=0.2~1) or LaCo _1-xy A _{x By} O _3-δ (A=Fe, W, Ga, B=Ni, Mg), the amount of CH ₄ passed through per square centimeter membrane module is 0.3~ 35ml·cm ^-2 ·min ^-1 .

Embodiment 4, using H Circulating _type inorganic dense oxygen-permeable membrane reactor to produce synthesis gas from methane

Figure 6 shows the principle flow chart of the H ₂ circulating inorganic dense oxygen-permeable membrane reactor process from methane to synthesis gas, that is, the oxidation reaction of H ₂ is used to couple the oxygen-permeable process. Part of the synthesis gas is passed through a membrane separator 24 to separate H ₂ , and the circulation ratio of H ₂ is 0.3-0.7. The reactor shown in Figure 2 is used, and the tubular SrFe _0.5 CoO _3-y composite oxide is selected as the oxygen-permeable membrane material to form a single-tube inorganic dense oxygen-permeable membrane fixed-bed reactor. Tube length 20mm, tube diameter 9mm, wall thickness 1mm, Ni/γ-Al ₂ O ₃ (40-60 mesh) catalyst 0.5g. In the experimental operation, high-purity H ₂ cylinder gas was used to simulate the H ₂ cycle. First carry out the reaction of Example 1, when the reaction is stable, feed H ₂ mix with CH ₄ and enter the reactor, keep the ratio of H ₂ and methane to be 1, gradually increase the intake of methane and circulating H ₂ , from the gas phase The product concentration was detected online by chromatography until the methane flow rate was 40ml/min, the conversion rate of methane was 98%, the selectivity of CO was greater than 95%, and H ₂ /CO=1.9-2.0.

Using the following materials to replace SrFe _0.5 CoO _3-y as the membrane reactor material can also achieve the purpose of producing synthesis gas from methane.

When using (ZrO ₂ ) _1-xy -(CeO ₂ ) _x -(CaO) _y (x=0.05～0.20, y=0.05～0.20), (ZrO ₂ ) _1-xy -(TiO ₂ ) _x -(Y ₂ O ₃ ) _y (x=0.05～0.20, y=0.05～0.20), (ZrO ₂ ) _1-x -(Tb ₂ O _3.5 ) _x (x=0.1～0.4), (ZrO ₂ ) _1-xy - (Tb ₂ O _3.5 ) _x -(Y ₂ O ₃ ) _y (x=0.05～0.20, y=0.05～0.20) or (Bi ₂ O ₃ ) _1-x -(Tb ₂ O _3.5 ) _x (x=0.1 ～0.4), the amount of CH ₄ introduced per square centimeter membrane module is 1.0×10 ^-3 ～5.0×10 ^-1 ml·cm ^-2 ·min ^-1 ;

When using Ln _1-x A _x Co _{1-y By y} O _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-x M _x O _3-δ (M=Ti, Cr, Mn, Fe, Ni, Cu, x=0~0.8), SrCo _1-xy F _x Cu _y O _3-δ (x=0~0.5, y=0~0.3), Ln _1-x M _x CoO _3-δ (Ln=La, Pr, Nd, Sm, Ga, M =Sr, Ca, Bi, Pb, x=0~0.9), La _1-x M _x CrO _3-δ (M=Ca, Sr, Mg, x=0.1~0.9), Y _0.05 BaCo _0.95 O _3-δ , Y _0.1 Ba _0.9 CoO _3-δ or CaTi _1-x M _x O _3-δ (M=Fe, Co, Ni, x=0.1～0.3), the amount of CH ₄ per square centimeter membrane module is 0.3 ~80ml·cm ^-2 ·min ^-1 ;

When using YSZ-A (A=Pd, Pt, In _0.9 Pr _0.1 , In _0.95 Pr _0.025 Zr _0.025 , the volume ratio of the two phases is 0.4~2), Bi _1.5 Y _0.5 O ₃ -Ag _0.7 Pd _0.3 (two-phase The volume ratio is 0.4~2), Bi _1.5 Y _0.5 O ₃ -Ag (the volume ratio of the two phases is 0.4~2), Bi _1.5 Er _0.5 O ₃ -Ag (the volume ratio of the two phases is 0.4~2) or Bi _1.5 When Er _0.5 O ₃ -Au (the volume ratio of the two phases is 0.4~2), the amount of CH ₄ passed into the membrane module per square centimeter is 0.3~50ml·cm ^-2 ·min ^-1 ;

When using Bi ₂ Sr ₂ Ca _n-1 Cu _n O _2n+4 (n=1~3, including partially replacing Bi with Pb and Sb, partially replacing Sr with Ba or rare earth elements, replacing Ca with rare earth element Y, and using transition Metal Fe, Co, Ni instead of Cu), Bi ₂ Sr ₂ (R _{1-x Cex} ) ₂ Cu ₂ O ₁₀ (R=rare earth element, x=0～0.3), (Pb ₂ Cu)Sr ₂ A _{n- 1} Cu _n O _2n+4 (A=rare earth element, Ca, n=1, 2), RBa _2-x M _x Cu _3-y M′ _y O _6+δ (R=rare earth element, M=Sr, Ca , Mg, M'=Fe, Co, Ni, Al, Ga, Zn, x, y=0～0.5) or RBa _2-x M _x Cu _4-y M' _y O _8-δ (R=rare earth element, When M=Sr, Ca, Mg, M'=Fe, Co, Ni, Al, Ga, Zn, x, y=0~0.5), the amount of CH ₄ passing through the membrane module per square centimeter is 0.3~40ml·cm ^-2 min ^-1 ;

When using Sr _1-x Bi _x FeO _3-δ (x=0.1～0.9), BaBi _x Co _y Fe _1-xy O _3-δ (x=0.1～0.9, y=0.1～0.9), Ba _x Sr _{1 -x} Co _y Fe _1-y O _3-δ (x=0.1～0.9, y=0.1～0.9), BaCo _1-xy Fe _x M _y O _3-δ (M=Ti, Zr, x=0.1～0.9 , y=0.1～0.9), La ₂ NiO _4+δ or La _2-x A _x Ni _1-y By _y O _4+δ (A=Sr, Zr, Ca, Mg, B=Co, Fe, Cu) , the amount of CH ₄ introduced is 1-60ml·cm ^-2 ·min ^-1 ;

When using YBa ₂ Cu ₃ O _6+δ , Y _1-x Zr _x Ba ₂ Cu _3-y M _y O _6+δ (M=Fe, Ni, Al, Sn, x=0.1～0.6), Y _{1- x} Zr _x Ba ₂ Cu ₃ O _6+δ , YBa ₂ Cu _3-x Fe _x O _6+δ , LaGa _1-xy A _{x By} O _3-δ (A=Co, Ni, B=Mg, Fe, x=0.1～0.8, y=0～0.5), La _1-x A _x Ga _1-y By _y O _3-δ (A=Sr, B=Co, Fe, Cu, Ni, x=0～0.8, y=0.2~1) or LaCo _1-xy A _{x By} O _3-δ (A=Fe, W, Ga, B=Ni, Mg), the amount of CH ₄ passed through per square centimeter membrane module is 0.3~ 35ml·cm ^-2 ·min ^-1 .

Example 5, Using CO cyclic inorganic dense oxygen-permeable membrane reactor to produce synthesis gas from methane

Since H ₂ has a certain reducing effect on the inorganic dense oxygen-permeable membrane at high temperature, maintaining a high concentration of H ₂ in the membrane reaction zone for a long time may lead to the destruction of some membrane structures. After the _H2 in the product synthesis gas is separated, the CO gas circulation is used to react with the oxygen permeated through the membrane, which can avoid the influence of _H2 on the membrane structure. At the same time, a certain amount of H ₂ O is added to the feed to participate in the reforming reaction in the reforming zone, which can not only adjust the C/H ratio of the reaction system, but also play a role in carbon elimination and reduce the carbon deposition of the catalyst. The principle flow chart of this process is the same as that shown in Figure 6, and CO is recycled. Part of the synthesis gas is separated from H ₂ through the membrane separator 24, CO is mixed with CH ₄ and H ₂ O through the circulation fan 23, and then enters the reactor 16, the ratio of CH ₄ /H ₂ O is 1.4-1.6, and the ratio of CH ₄ /CO 2.8 to 3.2. . The tubular SrFe _0.5 CoO _3-y composite oxide is selected as the oxygen-permeable membrane material to form a single-tube inorganic dense oxygen-permeable membrane reactor. The tube length is 20mm, the tube diameter is 9mm, and the wall thickness is 1mm. Ni/γ-Al ₂ O ₃ (40-60 mesh) catalyst 0.5g. In the experimental operation, high-purity CO cylinder gas was used to simulate the CO cycle. First carry out the reaction of Example 1, when the reaction is stable, gradually increase the intake of methane, H ₂ O and circulating CO, and detect the product concentration on-line by gas chromatography until the methane flow rate is 40ml/min, and the conversion rate of methane is 98% %, the selectivity of CO is greater than 95%, and H ₂ /CO=1.9-2.0.

Using the following materials to replace SrFe _0.5 CoO _3-y as the membrane reactor material can also achieve the purpose of producing synthesis gas from methane.

When using (ZrO ₂ ) _1-xy -(CeO ₂ ) _x -(CaO) _y (x=0.05～0.20, y=0.05～0.20), (ZrO ₂ ) _1-xy -(TiO ₂ ) _x -(Y ₂ O ₃ ) _y (x=0.05～0.20, y=0.05～0.20), (ZrO ₂ ) _1-x -(Tb ₂ O _3.5 ) _x (x=0.1～0.4), (ZrO ₂ ) _1-xy - (Tb ₂ O _3.5 ) _x -(Y ₂ O ₃ ) _y (x=0.05～0.20, y=0.05～0.20) or (Bi ₂ O ₃ ) _1-x -(Tb ₂ O _3.5 ) _x (x=0.1 ～0.4), the amount of CH ₄ introduced per square centimeter membrane module is 1.0×10 ^-3 ～1.0×10 ^-1 ml·cm ^-2 ·min ^-1 ;

When using Ln _1-x A _x Co _{1-y By y} O _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-x M _x O _3-δ (M=Ti, Cr, Mn, Fe, Ni, Cu, x=0~0.8), SrCo _1-xy F _x Cu _y O _3-δ (x=0~0.5, y=0~0.3), Ln _1-x M _x CoO _3-δ (Ln=La, Pr, Nd, Sm, Ga, M =Sr, Ca, Bi, Pb, x=0~0.9), La _1-x M _x CrO _3-δ (M=Ca, Sr, Mg, x=0.1~0.9), Y _0.05 BaCo _0.95 O _3-δ , Y _0.1 Ba _0.9 CoO _3-δ or CaTi _1-x M _x O _3-δ (M=Fe, Co, Ni, x=0.1～0.3), the amount of CH ₄ per square centimeter membrane module is 0.3 ~50ml·cm ^-2 ·min ^-1 ;

When using YSZ-A (A=Pd, Pt, In _0.9 Pr _0.1 , In _0.95 Pr _0.025 Zr _0.025 , the volume ratio of the two phases is 0.4~2), Bi _1.5 Y _0.5 O ₃ -Ag _0.7 Pd _0.3 (two-phase The volume ratio is 0.4~2), Bi _1.5 Y _0.5 O ₃ -Ag (the volume ratio of the two phases is 0.4~2), Bi _1.5 Er _0.5 O ₃ -Ag (the volume ratio of the two phases is 0.4~2) or Bi _1.5 When Er _0.5 O ₃ -Au (the volume ratio of the two phases is 0.4~2), the amount of CH ₄ passed into the membrane module per square centimeter is 0.3~30ml·cm ^-2 ·min ^-1 ;

When using Bi ₂ Sr ₂ Ca _n-1 Cu _n O _2n+4 (n=1~3, including partially replacing Bi with Pb and Sb, partially replacing Sr with Ba or rare earth elements, replacing Ca with rare earth element Y, and using transition Metal Fe, Co, Ni instead of Cu), Bi ₂ Sr ₂ (R _{1-x Cex} ) ₂ Cu ₂ O ₁₀ (R=rare earth element, x=0～0.3), (Pb ₂ Cu)Sr ₂ A _{n- 1} Cu _n O _2n+4 (A=rare earth element, Ca, n=1, 2), RBa _2-x M _x Cu _3-y M′ _y O _6+δ (R=rare earth element, M=Sr, Ca , Mg, M'=Fe, Co, Ni, Al, Ga, Zn, x, y=0～0.5) or RBa _2-x M _x Cu _4-y M' _y O _8-δ (R=rare earth element, When M=Sr, Ca, Mg, M'=Fe, Co, Ni, Al, Ga, Zn, x, y=0~0.5), the amount of CH ₄ passing through the membrane module per square centimeter is 0.3~10ml·cm ^-2 min ^-1 ;

When using Sr _1-x Bi _x FeO _3-δ (x=0.1～0.9), BaBi _x Co _y Fe _1-xy O _3-δ (x=0.1～0.9, y=0.1～0.9), Ba _x Sr _{1 -x} Co _y Fe _1-y O _3-δ (x=0.1～0.9, y=0.1～0.9), BaCo _1-xy Fe _x M _y O _3-δ (M=Ti, Zr, x=0.1～0.9 , y=0.1～0.9), La ₂ NiO _4+δ or La _2-x A _x Ni _1-y By _y O _4+δ (A=Sr, Zr, Ca, Mg, B=Co, Fe, Cu) , the amount of CH ₄ introduced is 1-40ml·cm ^-2 ·min ^-1 ;

When using YBa ₂ Cu ₃ O _6+δ , Y _1-x Zr _x Ba ₂ Cu _3-y M _y O _6+δ (M=Fe, Ni, Al, Sn, x=0.1～0.6), Y _{1- x} Zr _x Ba ₂ Cu ₃ O _6+δ , YBa ₂ Cu _3-x Fe _x O _6+δ , LaGa _1-xy A _{x By} O _3-δ (A=Co, Ni, B=Mg, Fe, x=0.1～0.8, y=0～0.5), La _1-x A _x Ga _1-y By _y O _3-δ (A=Sr, B=Co, Fe, Cu, Ni, x=0～0.8, y=0.2~1) or LaCo _1-xy A _{x By} O _3-δ (A=Fe, W, Ga, B=Ni, Mg), the amount of CH ₄ passed through per square centimeter membrane module is 0.3~ 35ml·cm ^-2 ·min ^-1 .

Claims (6)

1, a kind of method by Sweet natural gas or lower carbon number hydrocarbons hydrogen manufacturing and carbon monoxide synthetic gas, it is characterized in that: with the oxygen permeable side of warm air or oxygen-enriched combusting gas feeding inorganic compact oxygen permeable film, reaction side at film feeds Sweet natural gas or lower carbon number hydrocarbons, or feeds by lower carbon number hydrocarbons and CO or H ₂The reductibility mixed gas of forming, or feed by lower carbon number hydrocarbons, CO and H ₂The reductibility mixed gas of forming is regulated the input of reductibility mixed gas and is counted 1.0 * 10 with every square centimeter of mould material surface-area ^-3～80mlcm ^-2Min ^-1, under 800～1000 ℃ of temperature and 0.1～1MPa pressure condition, carry out the mixture of oxidizing reaction to the lower carbon number hydrocarbons of uniting the required stoichiometric ratio of catalytic reforming reaction and carbonic acid gas and/or water vapor; Then this mixture is introduced on reforming catalyst, under the condition of 800～1000 ℃ and 0.1～1MPa pressure, hydrocarbon and CO ₂Or/and H ₂The associating catalytic reforming reaction takes place in O, makes synthetic gas.

2, according to claim 1 by the method for Sweet natural gas or lower carbon number hydrocarbons hydrogen manufacturing and carbon monoxide synthetic gas, it is characterized in that: when adopting pure lower carbon number hydrocarbons as reducing gas, described mould material comprises: the ZrO with fluorite structure ₂Or Bi ₂O ₃The lamellar compound Sr of base and doped material, composite oxides, composite oxide material, ion and electronic conductor two-phase matrix material, laminate structure with uhligite and perovskite-like structure with pyrochlore constitution ₄Fe _6-xCo _xO _13-xSystem, have the single-phase composite oxides of oxonium ion and electron channel or a composite film material that adopts above-mentioned materials and pottery, metal and inorganic high-temp oxide compound to be constituted simultaneously; The ratio CH of the mole number of each species in the mixture that obtains ₄/ H ₂O/CO ₂=3/2/1.

3, according to claim 1 by the method for Sweet natural gas or lower carbon number hydrocarbons hydrogen manufacturing and carbon monoxide synthetic gas, it is characterized in that: when adopting lower carbon number hydrocarbons and recycle ratio is 0.4～0.6 H ₂With the CO mol ratio be 2 syngas product parallel feeding during as reducing gas, described mould material comprises: the ZrO with fluorite structure ₂Or Bi ₂O ₃The lamellar compound Sr of base and doped material, composite oxides, composite oxide material, ion and electronic conductor two-phase matrix material, laminate structure with uhligite and perovskite-like structure with pyrochlore constitution ₄Fe _6-xCo _xO _13-xSystem, have the single-phase composite oxides of oxonium ion and electron channel or a composite film material that adopts above-mentioned materials and pottery, metal and inorganic high-temp oxide compound to be constituted simultaneously.

4, according to claim 1 by the method for Sweet natural gas or lower carbon number hydrocarbons hydrogen manufacturing and carbon monoxide synthetic gas, it is characterized in that: when adopting lower carbon number hydrocarbons and H ₂During as reducing gas, be that partial synthesis gas product is passed through H ₂Behind the separatory membrane, with H ₂Circulation and lower carbon number hydrocarbons parallel feeding are by H ₂Oxygen generation oxidizing reaction with infiltration; H ₂Recycle ratio be 0.4～0.6, CH ₄/ H ₂Mol ratio is 1; Described mould material comprises: the ZrO with fluorite structure ₂Or Bi ₂O ₃The lamellar compound Sr of base and doped material, composite oxides, composite oxide material, ion and electronic conductor two-phase matrix material, laminate structure with uhligite and perovskite-like structure with pyrochlore constitution ₄Fe _6-xCo _xO _13-xSystem, have the single-phase composite oxides of oxonium ion and electron channel or a composite film material that adopts above-mentioned materials and pottery, metal and inorganic high-temp oxide compound to be constituted simultaneously.

5, according to claim 1 by the method for Sweet natural gas or lower carbon number hydrocarbons hydrogen manufacturing and carbon monoxide synthetic gas, it is characterized in that: when adopting lower carbon number hydrocarbons and CO, be that partial synthesis gas product is passed through H as reducing gas ₂Behind the separatory membrane, with CO circulation and lower carbon number hydrocarbons and water vapor parallel feeding, by the oxygen generation oxidizing reaction of CO and infiltration; CH ₄/ H ₂The O mol ratio is 1.4～1.6, CH ₄/ CO mol ratio is 2.8～3.2; Described mould material comprises: the ZrO with fluorite structure ₂Or Bi ₂O ₃The lamellar compound Sr of base and doped material, composite oxides, composite oxide material, ion and electronic conductor two-phase matrix material, laminate structure with uhligite and perovskite-like structure with pyrochlore constitution ₄Fe _6-xCo _xO _13-xSystem, have the single-phase composite oxides of oxonium ion and electron channel or a composite film material that adopts above-mentioned materials and pottery, metal and inorganic high-temp oxide compound to be constituted simultaneously.

6, a kind of inorganic compact oxygen-permeable membrane reactor of method according to claim 1 that is used for, comprise the oxygen flow district (1) and the deep oxidation reaction zone (3) that reaction vessel (9) are separated by oxygen permeable film assembly (2), and as the beds (4) of uniting catalytic reforming zone; It is characterized in that beds and oxygen permeable film components apart, deep oxidation reaction zone (3) is made of the folded space of beds (4) and oxygen permeable film assembly (2); Have the inlet mouth (5) of oxygen rich gas near the wall oxygen flow district (1) close oxygen permeable film assembly (2), far-end has air outlet (6); On near the wall the close oxygen permeable film assembly of the deep oxidation reaction zone (3) between oxygen permeable film assembly (2) and the beds (4), have the inlet mouth (7) of reducing gas, and have the outlet (8) of product synthetic gas at the opposite side of beds (4).

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