CN1227154C - Method for producing synthetic gas from low carbon hydrocarbon and inorganic compact oxygen permeatable membrane reactor - Google Patents

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

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CN1227154C
CN1227154C CN 01127228 CN01127228A CN1227154C CN 1227154 C CN1227154 C CN 1227154C CN 01127228 CN01127228 CN 01127228 CN 01127228 A CN01127228 A CN 01127228A CN 1227154 C CN1227154 C CN 1227154C
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gas
oxygen
carbon number
reaction
lower carbon
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CN1408637A (en
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陈初升
冯绍杰
冉申
朱德春
江国顺
刘卫
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University of Science and Technology of China USTC
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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 and inorganic compact oxygen-permeable membrane reactor by the lower carbon number hydrocarbons preparing synthetic gas
Technical field:
The present invention relates to inorganic compact oxygen-permeable membrane reactor by method and the beds and the oxygen permeable film components apart of Sweet natural gas or lower carbon number hydrocarbons hydrogen manufacturing and carbon monoxide synthetic gas.
Background technology:
The mixture of hydrogen and carbon monoxide is called synthetic gas, is to produce liquid fuel, alkene (C 2～C 4), the important source material of Chemicals such as methyl alcohol, dme.By lower carbon number hydrocarbons, particularly Sweet natural gas preparing synthetic gas, synthetic liquid fuel, alkene (C then 2～C 4), Chemicals such as methyl alcohol are the comprehensive Utilization Ways that industrial prospect is arranged.Sweet natural gas is the lower carbon number hydrocarbons of reserves maximum, and its main component is a methane.Sweet natural gas will be the important carbon source of Chemicals after oil, coal.U.S.'s " chemical industry news " (Haggin, Chicago C.E., Chem.Eng.News, 70 (17): 33 (1992)) point out, utilize at present in the technology of Sweet natural gas preparing synthetic gas resynthesis liquid fuel and chemical, the production cost of synthetic gas accounts for about 50%～60% of total cost, and cost is too high to be the biggest obstacle that the construction of natural gas fields utilizes.Therefore, reduce the synthetic gas production cost, significant to the development and use of Sweet natural gas.
The industrialized technology by lower carbon number hydrocarbons preparing synthetic gas such as Sweet natural gases that generally adopts mainly is vapour reforming at present, as methane steam reformation (SMR).U.S.'s " physical chemistry magazine " (Choudhary, V.R., Rajput, A.M., Rane, V.H., J.Phys.Chem., 96,8686 (1992)), U.S.'s " catalysis magazine " (Bharadwaj, S.S., and Schmidt, L.D., Journal of Catalysis 146, point out that 11-21 (1994)) because this reaction is a strong endothermic reaction, facility investment and energy consumption are all very high; And CO/H 2Than higher, product must can be used for subsequent technique through transferring analogy.In recent years, technology newly developed has non-catalytic partial oxidation (POX), associating reforming process (SMR/O 2R), self-heating recapitalization (ATR) etc." catalysis today " (Balachandran, U., Dusek, J.T., Maiya, P.S., et al., Catalysis Today 36 (1997) 265-272), " Chinese science circular " (Dong Hui, Xiong Guoxing, Shao Zongping, et al., Chinese Science Bulletin 45 (3) 224-226 (2000)), United States Patent (USP) 6048472 etc. is pointed out that these novel procesies improve to some extent than SMR at aspects such as cutting down the consumption of energy, reduce facility investment, but is all related to the supply problem of pure oxygen.For avoiding N 2Existence, need with pure oxygen as reactant, facility investment is big, operation running cost height.Point out that as United States Patent (USP) 6048472 concentration of ATR processing requirement oxygen is 95～99.9%, it is very big that the facility investment of system oxygen and working cost account for the cost ratio.Therefore, reduce system oxygen cost and become the primary factor that reduces the synthetic gas cost.
The inorganic compact oxygen permeable film is a kind of ionophore film, " fast-ionic conductor-basis, material, application " (Shanghai Science Press of work such as Lin Zuxiang, 1983), (Dong Zhichang etc. translate " solid state ionics " of flute wood and male work, Beijing Science Press, 1984) principle of such material has been done detailed argumentation.Can be used for the isolating ionophore of oxygen at present two big classes are arranged: a class is the ionophore that does not have (or very low) electron conduction, under the effect of extra electric field, perhaps additional electrodes, under the effect of oxygen concentration gradient, utilize lattice imperfection or gap in the material to carry out the conduction of oxonium ion, realize the selective permeation of oxygen, reach the isolating purpose of oxygen; The another kind of material that is widely studied is a mixed ion conductor, be that material itself has ionic conduction and electronic conduction ability simultaneously, under the effect of oxygen concentration gradient, oxonium ion moves to a side of oxidation degree low (oxygen concn is low) by oxygen room or gap from a side of oxidation degree height (oxygen concn height), electronics (electron hole) motion in the other direction simultaneously need not the membrane sepn that external circuit can be realized oxygen.The inorganic compact oxygen permeable film permselective property of oxygen in theory is 100%, is the suitable material of oxygen separator, membrane reactor, and especially pyritous in some being related to the oxygen process can oxygen supply on the throne, is the effective way of economic oxygen supply.Under certain oxygen flow temperature and reaction conditions, the oxygen penetrating power, mechanical stability and the chemical stability that improve such material are still present research emphasis.
Adopt the inorganic compact oxygen-permeable membrane reactor to carry out the production of synthetic gas, on the throne to utilize airborne oxygen source be the effective ways that solve economic oxygen supply.Technology as United States Patent (USP) 6048472 propositions.In fact this technology be still the associating reforming process, and inorganic oxygen permeable film plays the oxygen supply effect in secondary reformed.Whole technology still needs two reactors, and high energy consumption, problem with high investment are still unresolved.A kind of technology pattern that United States Patent (USP) 6077323 proposes covers with paint, lacquer, colour wash, etc. catalyzer on the surface of film, and the mixture of methane and water vapor feeds the reaction side of film, and the oxygen reaction with infiltration is come obtains synthetic gas.This technology requires very high to the film material, should consider the thermal characteristics matching problem of mould material and catalyzer, requires at high temperature catalyzer to the not influence of chemical structure of film again, in case catalyst surface carbon distribution inactivation, must the replacing mould material; On the other hand, the reaction process complexity, restive.We had once proposed a kind of oxygen permeable membrane separator (Chinese patent application number 99124427.3), wherein mentioning this device can be used as and relate to the oxidation membrane reactor, but catalyzer also is on the surface of film, the covering with paint of catalyzer and limited its range of application with the technical requirementss such as coupling of mould material.
" catalysis today " (Balachandran, U., Dusek, J.T., Maiya, P.S., et al., Catalysis Today36 (1997) 265-272) reported and adopted the catalyst based preparation of carrying out synthetic gas in the inorganic film reactor of expensive Rh.The catalyst based shortcoming that is used for partial oxidation reaction of methane of the Ni of relative low price is to be easy to inactivation, " applied catalysis " (A.Slagtern, Unni Olsbye, Applied Catalysis A:General 110 (1994) 99-108 pages or leaves) once pointed out, Ni catalyst based in partial oxidation reaction of methane only 17 hours with regard to inactivation; " catalysis magazine " (V.A.Tsipouriari, Z.Zhang, and X.E.Verykios, Journal of Catalysis 179 (1998) 283-291) also obtains identical conclusion.
Technology contents:
The present invention proposes a kind of based on the method for inorganic compact oxygen-permeable membrane reactor by Sweet natural gas or lower carbon number hydrocarbons hydrogen manufacturing and carbon monoxide synthetic gas, and the inorganic compact oxygen-permeable membrane reactor of a kind of beds and oxygen permeable film components apart, to overcome the problems referred to above of prior art.
The present invention is by the method for 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, the input of regulating the reductibility mixed gas is 1.0 * 10 -3～80mlcm -2Min -1(in every square centimeter of mould material surface-area) under 800～1000 ℃ of temperature and 0.1～1MPa pressure condition, carries 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 the reforming catalyst, under the condition of 800～1000 ℃ of temperature and 0.1～1MPa pressure, hydrocarbon and CO 2And/or H 2The associating catalytic reforming reaction takes place in O, makes synthetic gas.
The input of described adjusting reductibility mixed gas is carried 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, be meant according to the inorganic compact oxygen permeable film material of specifically selecting for use, the geometrical dimension of membrane module, the temperature of oxygen flow oxidation zone, in every square centimeter of mould material surface-area, 1.0 * 10 -3～80mlcm -2Min -1Regulate the input of lower carbon number hydrocarbons and the input of corresponding other gas of adjusting in the scope, thus the control level of response, with the lower carbon number hydrocarbons that obtains the required stoichiometric ratio of associating catalytic reforming reaction and the mixture of carbonic acid gas and/or water vapor:
(1) 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;
(2) when adopting lower carbon number hydrocarbons and H 2With the CO mol ratio be 2 synthetic gas during as the reductibility mixed gas, be meant the circulation of partial synthesis gas product, with the lower carbon number hydrocarbons parallel feeding, the oxygen generation oxidizing reaction that synthetic gas and infiltration are come; The recycle ratio of synthetic gas is 0.4～0.6; The ratio CH of the mole number of each species in the mixture that obtains 4/ H 2O/CO 2=3/2/1; 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;
(3) when adopting lower carbon number hydrocarbons and H 2During as the reductibility mixed gas, be meant partial synthesis gas product is passed through H 2Behind the separatory membrane, H 2Circulation and lower carbon number hydrocarbons parallel feeding; 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;
(4) when adopting lower carbon number hydrocarbons and CO, be meant partial synthesis gas product is passed through H as the reductibility mixed gas 2Behind the separatory membrane, CO circulation and lower carbon number hydrocarbons, water vapor parallel feeding; 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;
Charge proportion described in the aforesaid method is all with preparation H 2The synthetic gas of/CO=2 (reality can in 1.8～2.1 scopes) is the purpose product.Adjust charge proportion, also can obtain different H 2The synthetic gas of/CO ratio.
A kind of inorganic compact oxygen-permeable membrane reactor of the present invention comprises 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 beds 4 and oxygen permeable film assembly 2 folded spaces; Have the inlet mouth 5 of oxygen rich gas near the wall the oxygen flow district 1 close oxygen permeable film assembly 2, far-end has air outlet 6; On near the wall the 3 close oxygen permeable film assemblies of the deep oxidation reaction zone 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.
When being used for above-mentioned this reactor by lower carbon number hydrocarbons hydrogen manufacturing and carbon monoxide synthetic gas, is temperature that 800～1000 ℃, pressure are the oxygen-enriched combusting gas of the warm air of 0.1～1MPa or heat is fed oxygen permeable films 2 one sides by inlet mouth 5 oxygen flow district 1, Poor oxygen gas then 6 is discharged from the air outlet, lower carbon number hydrocarbons or by lower carbon number hydrocarbons and CO or/and H 2The reductibility mixed gas of forming is entered the deep oxidation reaction zone 3 of oxygen permeable film 2 opposite sides by inlet mouth 7, with the oxygen reaction that sees through by inorganic compact oxygen permeable film assembly 2, regulate the input of reducing gas, obtain the mixture of lower carbon number hydrocarbons, carbonic acid gas and/or the water vapor of required appointment metering ratio; Mixture enters catalytic reforming reaction zone 4 immediately, under 800～1000 ℃ of temperature, 0.1～1MPa pressure condition, the associating reforming reaction takes place, and the syngas product that obtains is discharged by outlet 8.
Inorganic oxygen permeable film material described in the inventive method all can be used for making the inorganic compact oxygen permeable film assembly 2 in the inorganic compact oxygen-permeable membrane reactor of the present invention.The geometric configuration of inorganic compact oxygen permeable film assembly 2 can be flat board, ripple, tubulose, cellular.
Compared with prior art, the inventive method has following characteristics and advantage:
The characteristics of the inventive method are:
1. described oxygen flow complete oxidation process is carried out in intravital two zones of same reactor cavity respectively with associating reforming reaction process;
2. the transmission of oxygen in oxygen permeable film is coupled by the complete oxidation of different reducing gas and realizes that described reducing gas can adopt CH 4, CO+H 2, CO or H 2
3. at inorganic compact oxygen permeable film one side bubbling air or oxygen-enriched combusting gas, the opposite side feeding reducing gas at film makes partial reduction gas complete oxidation, generates CO 2, H 2O.
The advantage of the inventive method is:
1. the initiation time that mould material oxygen permeates has been shortened in oxygen flow process and deep oxidation reaction coupling, the unit surface oxygen permeating amount of mould material is improved greatly, thereby improved the synthesis gas yield of the unit surface film of whole technology.
2. oxygen flow process and reforming process are separated; the deep oxidation reaction only takes place in inorganic oxygen permeable film conversion zone; level of response is subjected to the oxygen supply rate limiting of film; the temperature runaway phenomenon of having avoided violent deep oxidation reaction to bring; effectively controlled the thermograde of mould material; protect the mechanical stability of film, prolonged the life-span of film, and allowed to be applied to the mould material range extension of this reaction.
3. oxygen flow process and reforming process are separated, reaction process is easy to control.The level of response that input by regulating reducing gas, geometrical dimension, temperature and the selection of catalysts of film pipe (but according to concrete film material modified catalyst or do not modify) are come the controlling depth oxidation reaction zone reaches the purpose of control entire reaction then.
4. reasonable energy utilization in the reaction system, to energy consumption require low.Entire reaction is thermopositive reaction, and the reaction of the first step deep oxidation is thermopositive reaction in the reaction, and the heat that is produced is carried into catalytic reaction zone by product, and is required for endothermic reforming reaction, is enough to keep the required heat of follow-up reforming reaction.
5. oxygen flow process and reforming process are separated, help the protection of catalyzer.
(1) oxygen flow process and associating reforming process are separated, the catalytic association reforming reaction that takes place on the catalyzer is thermo-negative reaction, there is not the beds temperature runaway phenomenon that the oxidizing reaction heat release causes in other technologies, thus the high temperature sintering inactivation of having avoided catalyzer to cause because of temperature runaway.
(2) the Pintsch process carbon distribution of hydrocarbon is that the major reason of catalyst deactivation, particularly carbon number are obvious in cracking more than 650 ℃ greater than 2 hydrocarbon in the prior art.The technology that the present invention proposes makes many carbon of part hydrocarbon in the cracking of film reaction district, and finally generates CO 2And H 2O enters reformer section, has slowed down carbon distribution speed on the reforming catalyst, has prolonged life of catalyst.
(3) H of deep oxidation generation 2O participates in reaction, H in the reforming reaction district 2The existence of O is favourable to the carbon that disappears of catalyzer.Therefore can reduce the carbon distribution on the catalyzer, prolong the work-ing life of catalyzer.
Therefore 6. the present invention separates oxygen flow process and reforming process, and catalyzer obtains better protecting, has prolonged the work-ing life of catalyzer, and reaction can be in high-speed, big concentration, even uses under the condition of pure methane air inlet that Ni is catalyst based to carry out." catalysis today " (Balachandran, U., Dusek, J.T., Maiya, P.S., et al., Catalysis Today 36 (1997) 265-272) report adopts the catalyst based preparation of carrying out synthetic gas in the inorganic film reactor of expensive Rh.The catalyst based shortcoming that is used for partial oxidation reaction of methane of the Ni of relative low price is to be easy to inactivation, " applied catalysis " (A.Slagtern, Unni Olsbye, Applied Catalysis A:General110 (1994) 99-108) once point out Ni catalyst based in partial oxidation reaction of methane 17 hours inactivations only; " catalysis magazine " (V.A.Tsipouriari, Z.Zhang, and X.E.Verykios, Journal of Catalysis179 (1998) 283-291) also obtains identical conclusion.We adopt Ni catalyst based under the condition of pure methane air inlet, and reaction in 400 hours does not see that catalyst activity obviously descends.And oxygen flow process and reforming process separated, in case catalyst deactivation, more catalyst changeout is also convenient.Both reduced the cost of catalyzer, and reduced the compression power consumption that a large amount of use inert components are brought again, it is minimum that operation energy consumption is reduced to, and running cost also reduces greatly.
7. the inventive method is widely applicable.In lower carbon number hydrocarbons, the chemical stability of methane is the highest, and greater than 2 lighter hydrocarbons, same available present method is carried out the production of synthetic gas for other carbon numbers.
Compared with prior art, inorganic compact oxygen-permeable membrane reactor of the present invention has following characteristics and advantage:
1. inorganic compact oxygen-permeable membrane reactor of the present invention is combined in oxygen flow process and reforming process in the reactor cavity, and compact construction has been realized the intensification of reaction, has reduced facility investment and working cost.
2. adopt the inorganic compact oxygen-permeable membrane reactor, the heat that oxidizing reaction produced in the film reaction section is carried into catalytic reforming reaction zone by product, and is required for the associating endothermic reforming reaction, need not heat transfer process, and technological process is simplified.
3. in the inorganic compact oxygen-permeable membrane reactor oxygen flow process and reforming process are separated, help the replacing of catalyzer.
Accompanying drawing and explanation thereof:
Accompanying drawing 1 is an inorganic compact oxygen-permeable membrane reactor synoptic diagram;
Accompanying drawing 2 is single tube fixed bed inorganic compact oxygen-permeable membrane reactor synoptic diagram;
Accompanying drawing 3 is to utilize the schematic flow sheet of fixed-bed reactor by the methane process for preparing synthetic gas;
Accompanying drawing 4 is single tube fluidized-bed inorganic compact oxygen-permeable membrane reactor synoptic diagram;
Accompanying drawing 5 is to utilize the principle flow chart of the circulating fixed bed reactor of synthetic gas by the methane production synthetic gas;
Accompanying drawing 6 is to utilize H 2The circulating fixed bed reactor of/CO is by the principle flow chart of methane production synthetic gas;
Embodiment:
Illustrate the specific embodiment of the present invention below in conjunction with accompanying drawing.
Embodiment 1, employing tubular fixed-bed reactor are with Sweet natural gas (methane) preparing synthetic gas
Sweet natural gas is the lower carbon number hydrocarbons of reserves maximum, and its main component is a methane.Present embodiment adopts tubular fixed-bed combined reactor with Sweet natural gas (methane) preparing synthetic gas.Accompanying drawing 2 has provided the single tube fixed bed inorganic compact oxygen-permeable membrane reactor synoptic diagram that adopts in the present embodiment.Comprise housing 9, set termination 10, inorganic compact oxygen permeable film assembly 2, gas distribution grid 12, catalyzer back up pad 13.Housing 9 is made by silica tube.Corundum material is adopted in circular set termination 10, and the centre has circular groove, and slightly larger in diameter has the aperture for the reducing gas turnover in the diameter of inorganic compact oxygen permeable film pipe in the middle of the groove, and the aperture is less than the internal diameter of inorganic compact oxygen permeable film pipe 2.At first successively circular catalyzer back up pad 13, catalyzer and circular gas distribution grid 12 are fixed on the lower part in the silica tube, form catalytic reforming reaction zone 4.The two ends of inorganic compact oxygen permeable film pipe 2 are separately fixed in the groove of two set terminations 10 up and down with inorganic sealing agent 11, gather 10 sealing and fixing upper part in silica tube in termination with inorganic glue with two then, following set termination is apart from the about 5～10cm of gas distribution grid.The folded space of silica tube and inorganic compact oxygen permeable film tube outer surface constitutes oxygen flow district 1, and the space in the inorganic compact oxygen permeable film pipe is a deep oxidation reaction zone 3.In reactor shell 9 sides between two set terminations up and down, have inlet mouth 5 and air outlet 6 respectively relatively, inlet mouth 5 positions are lower.Have thermocouple jack 14 and 15 at the middle part of oxygen flow district and catalytic reforming reaction zone.High-temperature oxygen-enriched gas 16 enters the oxygen flow district 1 in the film outside from inlet mouth 5, becomes Poor oxygen gas 17 and discharged by air outlet 6 after the oxygen exchange; Hydrocarbon is or/and other reductibility reactant gasess 18 are entered the deep oxidation reaction zone 3 of film inboard by inlet mouth 7 (upper orifice), the oxygen of coming with infiltration reacts, generate the mixed gas intermediate product of metering ratio, enter catalytic reforming reaction zone 4 then and generate synthetic gas 19 8 (lower nozzles) discharge from the air outlet.Select tubulose SrFe for use 0.5CoO 3-yComposite oxides are as the oxygen-permeable membrane reactor material, pipe range 20mm, and caliber 9mm, wall thickness 1mm forms the single tube combined reactor, as shown in Figure 2.Membrane module also can be a multitube in the reactor.0.5g Ni/ γ-Al 2O 3(40～60 order) catalyzer is filled in catalytic bed.
Fig. 3 has provided and has utilized the schematic flow sheet of combination type reactor by the methane preparing synthetic gas.At first reactor is heated to 800 ℃ and solidifies the sealing inorganic glue.By under meter 20, feeding flow by inlet mouth 5 is the air of 100ml/min, and Poor oxygen gas is discharged by 6.Feed 40ml/min 5%H by inlet mouth 7 2He+H 2Mixed gas makes that Ni is catalyst based to keep 800 ℃ of temperature at 800 ℃ of reductase 12s on the throne hour, switches to the methane of 10ml/min 100%.By the online detection production concentration of gas-chromatography, methane flow improves gradually, is 40ml/min until methane flow.In inorganic composite conductor oxygen-permeating film reaction zone, oxygen reacts from the oxygen flow district by mould material and with methane generation deep oxidation with the form of oxonium ion:
Unreacted 75% methane and CO 2And H 2O enters the catalytic reforming reaction zone that adjoins, and reforming reaction takes place:
Total packet response is:
The thermochemical equation of system is as follows:
ΔH＝-801.7kJ/mol
ΔH＝247.0kJ/mol
ΔH＝205.7kJ/mol
Total packet response ΔH＝-35.5kJ/mol
Whole reaction system is thermopositive reaction, is favourable on energy.
Be reflected under 800～1000 ℃, the condition of 1atm and carry out, air speed is 8000h -1, reaction product is by the online detection of gas-chromatography.In 900 ℃, 400 hours reaction operational process, to calculate with every square metre of membrane area, the output of synthetic gas reaches 300m 3Day.Methane conversion is 98%, and the selectivity of CO is greater than 95%, H 2/ CO=1.9～2.0 are highly suitable for the synthetic required H of F-T reaction and methyl alcohol 2/ CO ratio.Therefore, product need not through the toning ratio, can directly carry out the reaction in downstream after the interchanger cooling, has reduced operating unit and running cost.
The deep oxidation reaction zone of above-mentioned reactor is separated with catalytic reforming reaction zone, adopt inorganic compact oxygen-permeable membrane reactor and the placed in-line mode of reforming reactor, can obtain same purpose.With inorganic oxygen permeable film pipe and set termination component film reactor, alundum tube is as reforming reactor, and the pipe connecting of two reactors is incubated with the heating zone.In the membrane reactor, the gaseous tension of film both sides is 1MPa, and the remaining reaction condition is identical with embodiment 1, and methane conversion is 98%, and the selectivity of CO is greater than 95%, H 2/ CO=1.9～2.0.
Adopt following material to replace SrFe 0.5CoO 3-yAs the membrane reactor material, also can realize purpose by the methane preparing synthetic gas.
When adopting (ZrO 2) 1-x-y-(CeO 2) x-(CaO) y(x=0.05～0.20, y=0.05～0.20), (ZrO 2) 1-x-y-(TiO 2) x-(Y 2O 3) y(x=0.05～0.20, y=0.05～0.20), (ZrO 2) 1-x-(Tb 2O 3.5) x(x=0.1～0.4), (ZrO 2) 1-x-y-(Tb 2O 3.5) x-(Y 2O 3) y(x=0.05～0.20, y=0.05～0.20) or (Bi 2O 3) 1-x-(Tb 2O 3.5) xWhen (x=0.1～0.4), every square centimeter of CH that membrane module feeds 4Amount is 1.0 * 10 -3～5.0 * 10 -2Mlcm -2Min -1
When adopting Ln 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-δWhen (M=Fe, Co, Ni, x=0.1～0.3), every square centimeter of CH that membrane module feeds 4Amount is 0.3～30mlcm -2Min -1
When adopting YSZ-A (A=Pd, Pt, In 0.9Pr 0.1, In 0.95Pr 0.025Zr 0.025, the biphase volume ratio is 0.4～2), Bi 1.5Y 0.5O 3-Ag 0.7Pd 0.3(the biphase volume ratio is 0.4～2), Bi 1.5Y 0.5O 3-Ag (the biphase volume ratio is 0.4～2), Bi 1.5Er 0.5O 3-Ag (the biphase volume ratio is 0.4～2) or Bi 1.5Er 0.5O 3During-Au (the biphase volume ratio is 0.4～2), every square centimeter of CH that membrane module feeds 4Amount is 0.3～30mlcm -2Min -1
When adopting Bi 2Sr 2Ca N-1Cu nO 2n+4(n=1～3 comprise with Pb, Sb partly substituting Bi, partly substitute Sr with Ba or rare earth element, substitute Ca with rare earth element y, substitute Cu with transition-metal Fe, Co, Ni), Bi 2Sr 2(R 1-xCe x) 2Cu 2O 10(R=rare earth element, x=0～0.3), (Pb 2Cu) Sr 2A 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=0～0.5) or RBa 2-xM xCu 4-yM ' yO 8-δWhen (R=rare earth element, M=Sr, Ca, Mg, M '=Fe, Co, Ni, Al, Ga, Zn, x, y=0～0.5), every square centimeter of CH that membrane module feeds 4Amount is 0.3～3mlcm -2Min -1
When adopting 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), La 2NiO 4+ δOr La 2-xA xNi 1-yB yO 4+ δWhen (A=Sr, Zr, Ca, Mg, B=Co, Fe, Cu), the CH of feeding 4Amount is 1～40mlcm -2Min -1
When adopting YBa 2Cu 3O 6+ δ, Y 1-xZr xBa 2Cu 3-yM yO 6+ δ(M=Fe, Ni, Al, Sn, x=0.1～0.6), Y 1-xZr xBa 2Cu 3O 6+ δ, YBa 2Cu 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=0～0.8, y=0.2～1) or LaCo 1-x-yA xB yO 3-δWhen (A=Fe, W, Ga, B=Ni, Mg), every square centimeter of CH that membrane module feeds 4Amount is 0.3～35mlcm -2Min -1
Embodiment 2, employing fluidized-bed inorganic compact oxygen-permeable membrane reactor are with the Sweet natural gas preparing synthetic gas
Adopt single tube fluidized-bed inorganic compact oxygen-permeable membrane reactor shown in Figure 4 in the present embodiment.Catalytic reforming reaction zone 4 is made of catalyzer back up pad 21, catalyzer baffle plate 22 and catalyzer, places upper part of silica tube.For big caliber reactor, air flow guiding device can be installed.The two ends of inorganic compact oxygen permeable film pipe 2 are separately fixed in the groove of two set terminations 10 up and down with inorganic sealing agent 11, gather 10 sealing and fixing lower part in silica tube in termination with inorganic glue with two then, the upper set termination is apart from catalyzer back up pad 21 about 5～10cm.Reducing gas feeds from the lower nozzle (inlet mouth 7) of reactor, after inorganic compact oxygen permeable film pipe carries out deep oxidation, the mixed gas intermediate product feeds from the bottom of beds, form fluidized-bed catalytic reforming reaction zone 4, product synthetic gas 19 is discharged by outlet 8 (upper orifices), and other gas circuits are identical.Select tubulose SrFe for use 0.5CoO 3-yComposite oxides are formed the single tube combined reactor as the oxygen-permeable membrane reactor material.Pipe range 30mm, caliber 9mm, wall thickness 1mm.Ni/ γ-Al 2O 3(160～200 order) catalyzer 1g is filled on the catalyzer back up pad.Adopt technical process and the working method of embodiment 1.Raw material is a desulphurised natural gas.Be reflected at 800 ℃, carry out under the condition of 1atm.The Sweet natural gas charge flow rate is 30～120ml/min, and transformation efficiency is 80～95%, the selectivity 90～95% of CO, H 2/ CO=1.8～2.1.
Embodiment 3, the circulating combined reactor of employing synthetic gas are by the methane preparing synthetic gas
Better for some structural stability, but under the condition of methane air inlet, the ionophore film that its oxygen permeability is lower, adopt the technology of embodiment 1 can't realize high throughput, can adopt the loop reactor mode, come to take oxygen by force from the reaction side of film by the circulation of taking the strong syngas product of oxygen ability by force, that promptly carry out at inorganic compact oxygen permeable film conversion zone is CO and H 2Oxidizing reaction.The deep oxidation reaction takes place at inorganic compact oxygen permeable film conversion zone in methane hardly, at reforming reaction district and CO 2, H 2The associating reforming reaction takes place in O, generates synthetic gas.
Fig. 5 has provided and has utilized the principle process of synthetic gas circulation by the methane production synthesis gas process.Adopt reactor shown in Figure 2.Select Ba for use 0.5Sr 0.5Co 0.8Fe 0.2O 3-δThe oxygen permeable film pipe is formed circulating single tube reactor, pipe range 20mm, caliber 9mm, wall thickness 1mm, Ni/ γ-Al 2O 3(40～60 order) catalyzer 0.5g.At first carry out the operation of embodiment 1, carry out the reduction of catalyzer, switch to pure methane after, at 900 ℃, the reaction conditions of 1atm is regulated down the air input of methane, until the synthetic gas that obtains 90% concentration.Open recirculation blower 23 then, synthetic gas circulation with part, with methane blended, keeping the ratio of synthetic gas and methane is 1, improves the air input of methane and circulation synthetic gas gradually, by the online detection production concentration of gas-chromatography, until methane flow is 40ml/min, recycle ratio R=0.5, and methane conversion is 98%, the selectivity of CO is greater than 95%, H 2/ CO=1.9～2.0.Reaction equation is as follows:
Oxidation zone:
Reformer section:
Total packet response:
Adopt following material to replace Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3-δAs the membrane reactor material, also can realize purpose by the methane preparing synthetic gas.
When adopting (ZrO 2) 1-x-y-(CeO 2) x-(CaO) y(x=0.05～0.20, y=0.05～0.20), (ZrO 2) 1-x-y-(TiO 2) x-(Y 2O 3) y(x=0.05～0.20, y=0.05～0.20), (ZrO 2) 1-x-(Tb 2O 3.5) x(x=0.1～0.4), (ZrO 2) 1-x-y-(Tb 2O 3.5) x-(Y 2O 3) y(x=0.05～0.20, y=0.05～0.20) or (Bi 2O 3) 1-x-(Tb 2O 3.5) xWhen (x=0.1～0.4), every square centimeter of CH that membrane module feeds 4Amount is 1.0 * 10 -3～5.0 * 10 -2Mlcm -2Min -1
When adopting Ln 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-δWhen (M=Fe, Co, Ni, x=0.1～0.3), every square centimeter of CH that membrane module feeds 4Amount is 0.3～30mlcm -2Min -1
When adopting YSZ-A (A=Pd, Pt, In 0.9Pr 0.1, In 0.95Pr 0.025Zr 0.025, the biphase volume ratio is 0.4～2), Bi 1.5Y 0.5O 3-Ag 0.7Pd 0.3(the biphase volume ratio is 0.4～2), Bi 1.5Y 0.5O 3-Ag (the biphase volume ratio is 0.4～2), Bi 1.5Er 0.5O 3-Ag (the biphase volume ratio is 0.4～2) or Bi 1.5Er 0.5O 3During-Au (the biphase volume ratio is 0.4～2), every square centimeter of CH that membrane module feeds 4Amount is 0.3～30mlcm -2Min -1
When adopting Bi 2Sr 2Ca N-1Cu nO 2n+4(n=1～3 comprise with Pb, Sb partly substituting Bi, partly substitute Sr with Ba or rare earth element, substitute Ca with rare earth element y, substitute Cu with transition-metal Fe, Co, Ni), Bi 2Sr 2(R 1-xCe x) 2Cu 2O 10(R=rare earth element, x=0～0.3), (Pb 2Cu) Sr 2A 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=0～0.5) or RBa 2-xM xCu 4-yM ' yO 8-δWhen (R=rare earth element, M=Sr, Ca, Mg, M '=Fe, Co, Ni, Al, Ga, Zn, x, y=0～0.5), every square centimeter of CH that membrane module feeds 4Amount is 0.3～3mlcm -2Min -1
When adopting 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), La 2NiO 4+ δOr La 2-xA xNi 1-yB yO 4+ δWhen (A=Sr, Zr, Ca, Mg, B=Co, Fe, Cu), the CH of feeding 4Amount is 1～40mlcm -2Min -1
When adopting YBa 2Cu 3O 6+ δ, Y 1-xZr xBa 2Cu 3-yM yO 6+ δ(M=Fe, Ni, Al, Sn, x=0.1～0.6), Y 1-xZr xBa 2Cu 3O 6+ δ, YBa 2Cu 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=0～0.8, y=0.2～1) or LaCo 1-x-yA xB yO 3-δWhen (A=Fe, W, Ga, B=Ni, Mg), every square centimeter of CH that membrane module feeds 4Amount is 0.3～35mlcm -2Min -1
Embodiment 4, employing H 2Circulating inorganic compact oxygen-permeable membrane reactor is by the methane preparing synthetic gas
Fig. 6 has provided H 2Circulating inorganic compact oxygen-permeable membrane reactor is promptly used H by the principle flow chart of methane process for preparing synthetic gas 2Oxidizing reaction coupling oxygen flow process.Partial synthesis gas is isolated H by membrane separation apparatus 24 2, H 2Recycle ratio be 0.3～0.7.Adopt reactor shown in Figure 2, select tubulose SrFe for use 0.5CoO 3-yComposite oxides are formed single tube inorganic compact oxygen permeable film fixed-bed reactor as oxygen permeable film material.Pipe range 20mm, caliber 9mm, wall thickness 1mm, Ni/ γ-Al 2O 3(40～60 order) catalyzer 0.5g.Use high-purity H in the experimental implementation 2Steel cylinder gas simulation H 2Circulation.At first carry out the reaction of embodiment 1, after stable reaction, feed H 2With CH 4Enter reactor after the mixing, keep H 2With the ratio of methane be 1, improve methane and circulation H gradually 2Air input, by the online detection production concentration of gas-chromatography, be 40ml/min until methane flow, methane conversion is 98%, the selectivity of CO is greater than 95%, H 2/ CO=1.9～2.0.
Adopt following material to replace SrFe 0.5CoO 3-yAs the membrane reactor material, also can realize purpose by the methane preparing synthetic gas.
When adopting (ZrO 2) 1-x-y-(CeO 2) x-(CaO) y(x=0.05～0.20, y=0.05～0.20), (ZrO 2) 1-x-y-(TiO 2) x-(Y 2O 3) y(x=0.05～0.20, y=0.05～0.20), (ZrO 2) 1-x-(Tb 2O 3.5) x(x=0.1～0.4), (ZrO 2) 1-x-y-(Tb 2O 3.5) x-(Y 2O 3) y(x=0.05～0.20, y=0.05～0.20) or (Bi 2O 3) 1-x-(Tb 2O 3.5) xWhen (x=0.1～0.4), every square centimeter of CH that membrane module feeds 4Amount is 1.0 * 10 -3～5.0 * 10 -1Mlcm -2Min -1
When adopting Ln 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-δWhen (M=Fe, Co, Ni, x=0.1～0.3), every square centimeter of CH that membrane module feeds 4Amount is 0.3～80mlcm -2Min -1
When adopting YSZ-A (A=Pd, Pt, In 0.9Pr 0.1, In 0.95Pr 0.025Zr 0.025, the biphase volume ratio is 0.4～2), Bi 1.5Y 0.5O 3-Ag 0.7Pd 0.3(the biphase volume ratio is 0.4～2), Bi 1.5Y 0.5O 3-Ag (the biphase volume ratio is 0.4～2), Bi 1.5Er 0.5O 3-Ag (the biphase volume ratio is 0.4～2) or Bi 1.5Er 0.5O 3During-Au (the biphase volume ratio is 0.4～2), every square centimeter of CH that membrane module feeds 4Amount is 0.3～50mlcm -2Min -1
When adopting Bi 2Sr 2Ca N-1Cu nO 2n+4(n=1～3 comprise with Pb, Sb partly substituting Bi, partly substitute Sr with Ba or rare earth element, substitute Ca with rare earth element y, substitute Cu with transition-metal Fe, Co, Ni), Bi 2Sr 2(R 1-xCe x) 2Cu 2O 10(R=rare earth element, x=0～0.3), (Pb 2Cu) Sr 2A 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=0～0.5) or RBa 2-xM xCu 4-yM ' yO 8-δWhen (R=rare earth element, M=Sr, Ca, Mg, M '=Fe, Co, Ni, Al, Ga, Zn, x, y=0～0.5), every square centimeter of CH that membrane module feeds 4Amount is 0.3～40mlcm -2Min -1
When adopting 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), La 2NiO 4+ δOr La 2-xA xNi 1-yB yO 4+ δWhen (A=Sr, Zr, Ca, Mg, B=Co, Fe, Cu), the CH of feeding 4Amount is 1～60mlcm -2Min -1
When adopting YBa 2Cu 3O 6+ δ, Y 1-xZr xBa 2Cu 3-yM yO 6+ δ(M=Fe, Ni, Al, Sn, x=0.1～0.6), Y 1-xZr xBa 2Cu 3O 6+ δ, YBa 2Cu 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=0～0.8, y=0.2～1) or LaCo 1-x-yA xB yO 3-δWhen (A=Fe, W, Ga, B=Ni, Mg), every square centimeter of CH that membrane module feeds 4Amount is 0.3～35mlcm -2Min -1
Embodiment 5, the circulating inorganic compact oxygen-permeable membrane reactor of employing CO are by the methane preparing synthetic gas
Because H 2At high temperature the inorganic compact oxygen permeable film there is certain reductive action, the medium-term and long-term H that keeps higher concentration in the film reaction district 2, the destruction that may cause some membrane structure.With the H in the product synthetic gas 2After the separation,, can avoid H with CO gas circulation and the oxygen reaction of coming by membrane permeation 2Influence to membrane structure.In charging, add simultaneously certain amount of H 2O participates in reforming reaction in reformer section, both can regulate the C/H ratio of reaction system, can play the carbon effect that disappears again, reduces the carbon distribution of catalyzer.The principle flow chart of this technology is identical with Fig. 6, and round-robin is CO.Partial synthesis gas is isolated H by membrane separation apparatus 24 2, CO is through recirculation blower 23 and CH 4, H 2O enters reactor 16, CH after mixing 4/ H 2The O ratio is 1.4～1.6, CH 4/ CO ratio is 2.8～3.2.。Select tubulose SrFe for use 0.5CoO 3-yComposite oxides are formed single tube inorganic compact oxygen-permeable membrane reactor as oxygen permeable film material.Pipe range 20mm, caliber 9mm, wall thickness 1mm.Ni/ γ-Al 2O 3(40～60 order) catalyzer 0.5g.Circulate with high-purity CO steel cylinder gas simulation CO in the experimental implementation.At first carry out the reaction of embodiment 1, after stable reaction, improve methane, H gradually 2The air input of O and circulation CO by the online detection production concentration of gas-chromatography, is 40ml/min until methane flow, and methane conversion is 98%, and the selectivity of CO is greater than 95%, H 2/ CO=1.9～2.0.
Adopt following material to replace SrFe 0.5CoO 3-yAs the membrane reactor material, also can realize purpose by the methane preparing synthetic gas.
When adopting (ZrO 2) 1-x-y-(CeO 2) x-(CaO) y(x=0.05～0.20, y=0.05～0.20), (ZrO 2) 1-x-y-(TiO 2) x-(Y 2O 3) y(x=0.05～0.20, y=0.05～0.20), (ZrO 2) 1-x-(Tb 2O 3.5) x(x=0.1～0.4), (ZrO 2) 1-x-y-(Tb 2O 3.5) x-(Y 2O 3) y(x=0.05～0.20, y=0.05～0.20) or (Bi 2O 3) 1-x-(Tb 2O 3.5) xWhen (x=0.1～0.4), every square centimeter of CH that membrane module feeds 4Amount is 1.0 * 10 -3～1.0 * 10 -1Mlcm -2Min -1
When adopting Ln 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-δWhen (M=Fe, Co, Ni, x=0.1～0.3), every square centimeter of CH that membrane module feeds 4Amount is 0.3～50mlcm -2Min -1
When adopting YSZ-A (A=Pd, Pt, In 0.9Pr 0.1, In 0.95Pr 0.025Zr 0.025, the biphase volume ratio is 0.4～2), Bi 1.5Y 0.5O 3-Ag 0.7Pd 0.3(the biphase volume ratio is 0.4～2), Bi 1.5Y 0.5O 3-Ag (the biphase volume ratio is 0.4～2), Bi 1.5Er 0.5O 3-Ag (the biphase volume ratio is 0.4～2) or Bi 1.5Er 0.5O 3During-Au (the biphase volume ratio is 0.4～2), every square centimeter of CH that membrane module feeds 4Amount is 0.3～30mlcm -2Min -1
When adopting Bi 2Sr 2Ca N-1Cu nO 2n+4(n=1～3 comprise with Pb, Sb partly substituting Bi, partly substitute Sr with Ba or rare earth element, substitute Ca with rare earth element y, substitute Cu with transition-metal Fe, Co, Ni), Bi 2Sr 2(R 1-xCe x) 2Cu 2O 10(R=rare earth element, x=0～0.3), (Pb 2Cu) Sr 2A 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=0～0.5) or RBa 2-xM xCu 4-yM ' yO 8-δWhen (R=rare earth element, M=Sr, Ca, Mg, M '=Fe, Co, Ni, Al, Ga, Zn, x, y=0～0.5), every square centimeter of CH that membrane module feeds 4Amount is 0.3～10mlcm -2Min -1
When adopting 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), La 2NiO 4+ δOr La 2-xA xNi 1-yB yO 4+ δWhen (A=Sr, Zr, Ca, Mg, B=Co, Fe, Cu), the CH of feeding 4Amount is 1～40mlcm -2Min -1
When adopting YBa 2Cu 3O 6+ δ, Y 1-xZr xBa 2Cu 3-yM yO 6+ δ(M=Fe, Ni, Al, Sn, x=0.1～0.6), Y 1-xZr xBa 2Cu 3O 6+ δ, YBa 2Cu 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=0～0.8, y=0.2～1) or LaCo 1-x-yA xB yO 3-δWhen (A=Fe, W, Ga, B=Ni, Mg), every square centimeter of CH that membrane module feeds 4Amount is 0.3～35mlcm -2Min -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).
CN 01127228 2001-09-18 2001-09-18 Method for producing synthetic gas from low carbon hydrocarbon and inorganic compact oxygen permeatable membrane reactor Expired - Fee Related CN1227154C (en)

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