CN1623890A - Method for preparing synthesis gas using carbon dioxide as oxygen resource and its reaction apparatus - Google Patents
Method for preparing synthesis gas using carbon dioxide as oxygen resource and its reaction apparatus Download PDFInfo
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- CN1623890A CN1623890A CN 200410065196 CN200410065196A CN1623890A CN 1623890 A CN1623890 A CN 1623890A CN 200410065196 CN200410065196 CN 200410065196 CN 200410065196 A CN200410065196 A CN 200410065196A CN 1623890 A CN1623890 A CN 1623890A
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Abstract
A process for preparing synthetic gas from Co2 as oxygen source includes such steps as decomposing CO2 at 800-1000 deg.C to generate O2, penetrating O2 through a membrane made up of perovskite-type conductor mixture, and catalytic reaction on methane to obtain synthetic gas. Its reactor system is composed of an external reactor with CO2 inlet tube and the outlet tube of unreacted gas, an internal reactor with CH4 inlet tube and synthetic gas outlet tube, and an oxygen permeable membrane fixed to internal reactor.
Description
Technical field
The present invention relates to synthetic gas (CO and H
2) the preparation method, particularly be the method for oxygen source preparing synthetic gas and special-purpose reaction unit thereof with the carbonic acid gas.
Background technology
Synthetic gas is mainly to contain CO and H
2Mixed gas.Traditional is that raw material preparing synthetic gas method is to feed the oxygen that obtains through air separation under the high temperature with methane, and oxygen and methane carry out partial oxidation reaction, produce CO and H
2, this method equipment is huge, the energy consumption height.Though carbonic acid gas also can decompose generation oxygen, because of transformation efficiency is low, reaction is difficult to carry out, and still fails to be used at present the preparation of synthetic gas.
Summary of the invention
The purpose of this invention is to provide a kind of is the method for oxygen source preparing synthetic gas with the carbonic acid gas, and it can pass through the composite conductor oxygen-permeating film technology, solves the problem that the carbonic acid gas decomposition reaction is difficult to carry out and transformation efficiency is low, for the conversion of methane dynamically provides required oxygen.
Another object of the present invention provides the special reaction device of the method for aforesaid method preparing synthetic gas---mineral membrane integrated catalytic reaction preparing synthetic gas reactor, its collection membrane sepn, carbonic acid gas decomposition are one with the conversion of methane process, above three steps are finished in same device, to simplify the operation, reduce facility investment.
The method that the present invention prepares synthetic gas comprises following steps:
Carbonic acid gas is fed in the enclosed space, under 800 ℃-1000 ℃ temperature, decompose, 850 ℃-950 ℃ of preferred temperature, and make the oxygen that decomposes generation constantly see through the perovskite typed composite conductor oxygen-permeating film, the side that sees through at film feeds methane simultaneously, in the presence of catalyzer, make oxygen and methane reaction, get synthetic gas; Said perovskite mixing conductor oxygen-penetrating film is that general formula is A
1-XA '
XB
1-YB '
YO
3-δPerofskite type oxide, wherein δ is the lattice imperfection number, and A, A ' are any one element among Ld, Sm, Nd, Pr, Ba, Ca, Sr, Na, La, the Bi, and B, B ' are element in any among Mn, Cr, Fe, Co, Ni, Cu, the Zr, 0＜X＜1,0＜Y＜1; It is catalyst based or Rh is catalyst based that said catalyzer is selected from Ni, or be selected from the compound catalyst based of at least two kinds of elements among Li, La, Mg, Ca, the Ni or be selected from transition metal Ru,, Os, Rh,, Ir,, Pd, Pt, Cu, Ag or Au catalyzer.
The special reaction device of the inventive method contains inside and outside socket and mutual isolated two reactors, and inside and outside two reactors form inside and outside reaction chamber respectively, and outer reactor is provided with CO
2The outlet pipe of inlet pipe and unreacted ideal gas; The internal reaction device is provided with CH
4Inlet pipe and syngas outlet pipe, the internal reaction device is fixed with perovskite mixing conductor oxygen-penetrating film, and the both sides of this oxygen permeable film are respectively towards inside and outside chamber.
More than said perovskite mixing conductor oxygen-penetrating film can be sheet like membrane, it to be radially being fixed in the end of internal reaction device, and and this reactor between be provided with sealing-ring.
Said perovskite mixing conductor oxygen-penetrating film can also be a tubular membrane, and it is connected with axial with the internal reaction device, becomes the integral part of internal reaction device, and the two junction is filled with sealing material, and is isolated to guarantee inside and outside two Room.
The composite conductor oxygen-permeating film that the present invention adopts is a class new ceramics mould material that has oxide ion conduction and electronic conductivity simultaneously, and this type of material not only has catalytic activity, at high temperature the selectivity oxygen flow.The present invention utilizes the above-mentioned performance of composite conductor oxygen-permeating film, with composite conductor oxygen-permeating film and partial oxidation reaction of methane (POM) PROCESS COUPLING, makes carbonic acid gas at high temperature on the compact oxygen permeable film surface decomposition reaction take place, and generates carbon monoxide and oxygen:
, oxygen is transmitted to the opposite side (calling in the following text through side) of oxygen permeable film with the form of oxonium ion by oxygen permeable film:
In the side that sees through of film, oxygen and methane carry out partial oxidation reaction of methane in the presence of catalyzer, produce hydrogen and carbon monoxide:
。Because the methane of this side and oxygen react the oxygen that sees through constantly are removed, thereby have broken the balance of carbonic acid gas decomposition reaction, impel carbonic acid gas constantly to transform to carbon monoxide.The present invention provides oxygen source with the carbonic acid gas replaces air for partial oxidation reaction of methane, can fundamentally stop NO
XGeneration, can also provide new solution route for the serious environmental problem day by day that the carbonic acid gas excessive emissions is brought.Preparing synthetic gas reactor collection membrane sepn of the present invention, carbonic acid gas decompose and the conversion of methane process is an one, and above three steps are finished in same reactor, invest lower.The present invention produces the work simplification of synthetic gas, and equipment is simple, estimates than traditional oxygen separation plant save operation cost more than 20%.
Description of drawings
Fig. 1 the present invention is the process principle figure of oxygen source preparing synthetic gas with the carbonic acid gas.
Fig. 2 is the process flow diagram of preparing synthetic gas of the present invention.
Fig. 3 and Fig. 4 are two example structure synoptic diagram of the reactor of preparing synthetic gas of the present invention, and Fig. 3 adopts the chip film, and Fig. 4 adopts tubular membrane.
Fig. 5 is temperature of reaction and CO
2The graph of relation of transformation efficiency and oxygen permeation flux.
Fig. 6 is temperature of reaction and CH
4Transformation efficiency, CO selectivity and H
2The graph of relation of/CO.
Rectangle frame is represented composite conductor oxygen-permeating film among Fig. 1, and dash area is represented catalyzer, is the boundary with the oxygen permeable film, in the underside area, and CO
2Be decomposed into CO and O
2, the O of decomposition gained
2In oxygen permeable film with oxonium ion (O
2-) form be transmitted to the upside (portion's reaction formula as follows) of oxygen permeable film, under the katalysis of this side catalyzer, O
2-With CH
4React CO and H
2(seeing the top reaction formula), therefore, the downside of oxygen permeable film is the high keto sectional pressure side, upside is the low oxygen partial pressure side.As shown in Figure 1, oxygen sees through the upside that film enters film from the downside of film, is constantly removed with methane reaction then, thereby impels carbonic acid gas constantly to transform to carbon monoxide.
Fig. 2 is to be the prepared in laboratory flow implementation example of oxygen source preparing synthetic gas with the carbonic acid gas, and each label is expressed as follows among the figure, 1-1-methane steel cylinder, 1-2-argon gas steel cylinder, 1-3-helium steel cylinder, 1-4-carbon dioxide steel cylinder, 2-1～1-5-gas flow dryer, 3-1～3-4-under meter, 4,4 ' mixing valve, the 5-six-way valve, the 6-electrical heater, 7 reactors, 7-1-composite conductor oxygen-permeating film, the 8-gas-chromatography, the 9-soap bubble flowmeter.
Fig. 2 process description is as follows: the argon gas of the methane of steel cylinder 1-1 and steel cylinder 1-2 is drying device 2-1,2-2 respectively, merges the upper end that the back feeds reactor 7 by mixing valve 4 behind under meter 3-1, the 3-2; The helium of the carbonic acid gas of steel cylinder 1-4 and steel cylinder 1-3 is drying device 2-4,2-3 respectively, feed the lower end of reactor 7 by mixing valve 4 ' merging back behind under meter 3-4, the 3-3, temperature in the reactor is by electrical heater 6 controls, carbonic acid gas is decomposed into carbon monoxide and oxygen at the downside of oxygen permeable film, oxygen enters into the top of reactor 7 by composite conductor oxygen-permeating film 7-1, meanwhile, under the effect of catalyzer, carry out the methane portion oxidation synthesis gas reaction.Synthetic gas that methane portion oxidation produces and carbonic acid gas decomposition unreacted gas are completely discharged from upper and lower two vapor pipes of reactor 7 respectively, switch degas respectively chromatography detection or directly collection by six-way valve 5.
Fig. 3 and Fig. 4 represent two kinds of structure examples of mineral membrane integrated catalytic reaction preparing synthetic gas reactor of the present invention, each label is represented among the figure: 70-methane inlet pipe, the outer reactor of 71-, 72-compresses pipe, the 73-spring, 74 carbon dioxide inlet pipes, 75-syngas outlet pipe, 76-internal reaction device, 77-catalyzer, 78 ', 78-sealed picture, 78-1-sealing material, the outer reactor vapor pipe of 79-.
Among Fig. 3, composite conductor oxygen-permeating film 7-1 is the chip film, and 7-1 is a tubular membrane among Fig. 4.
In Fig. 3 embodiment, outer reactor 71 and internal reaction device 76 are made for mutual belled silica tube, and the space is respectively mistress and inner room in the pipe; Outer reactor 71 is provided with CO
2Inlet pipe 74 and vapor pipe 79 (outlet pipe of unreacted ideal gas in the outer reactor), internal reaction device 76 is provided with CH
4Inlet pipe 70 and syngas outlet pipe 75, the lower end of internal reaction device 76 are fixed with perovskite mixing conductor chip oxygen permeable film 7-1, and the upper and lower both sides face of this oxygen permeable film is respectively towards inner room and mistress's (can be described as chamber and following chamber in this example).Be provided with sealing-ring 78 between diaphragm 7-1 and the internal reaction device 76, the downside of diaphragm 7-1 compresses pipe 72 by one and spring 73 is fixing, compress install additional between pipe and the diaphragm sealing-ring 78 '.
This reactor is by the heating of peripheral hardware electric furnace, by lower end inlet pipe 74 outside reactor 71 input CO
2, CO
2In compact oxygen permeable film 7-1 downside surface generation decomposition reaction, it is indoor that the oxygen that generates is transmitted to oxygen permeable film 7-1 upside with the form of oxonium ion, methane by 70 inputs of upper end inlet pipe reacts at catalyst layer 77 and the oxygen that sees through, and the hydrogen of generation and carbon monoxide synthetic gas and unreacted methane blended gas are discharged from vapor pipe 75.
Fig. 4 is a horizontal type device, outer reactor 71 and the 76 horizontal sockets of internal reaction device, and outer reactor 71 is a silica tube, internal reaction device 76 is made for the compact aluminum oxide pipe; Perovskite mixing conductor oxygen-penetrating film 7-1 is tubular film (calling the film pipe in the following text), and it axially is connected in the stage casing of internal reaction device 76, becomes the integral part of internal reaction device, and the two junction is filled with sealing material 78-1, and catalyzer 77 places in the pipe of film pipe 7-1.Oxygen penetrates the inboard of film pipe from the outside of film pipe 7-1, and the methane reaction that feeds with left end pipe 70 in the presence of film pipe inner catalyst 77.Methane portion oxidation generates gas and discharges from right-hand member pipe 75.All the other are identical with Fig. 3.
Sealing-ring 78,78 among Fig. 3 ' and Fig. 4 in sealing material 78-1 or adopt high temperature materials such as precious metal, glass or pottery.
Mineral membrane integrated catalytic of the present invention reaction preparing synthetic gas reactor can also be promoted the oxidizing reaction bonded application scenario of hydrocarbon compounds such as being used for carbonic acid gas decomposition reaction and ethane, propane.
Embodiment
Embodiment
Present embodiment adopts the reactor preparing synthetic gas of Fig. 3 structure, and wherein composite conductor oxygen-permeating film 7-1 adopts SrCo
0.4Fe
0.5Zr
0.1O
3-δOxide compound chip film.
Adopt 78 sealings of gold ring sealing-ring between the internal reaction device 76 that diaphragm 7-1 and silica tube are made, effective oxygen flow area of diaphragm 7-1 is 0.283cm
2CO
2The film downside that feeds in the reactors by a thin silica tube 74 with the gas mixture of He, wherein CO
2Flow: 6ml/min; He flow: 24ml/min, and CH
4The film upside that feeds in the reactors by the thin silica tube 70 of another root with the gas mixture of Ar, wherein, CH
4Flow: 3ml/min; Ar flow: 17ml/min is at the upside filling NiO/Al of reactor
2O
3Catalyzer 0.1g, temperature of reaction is controlled at 800 ℃-1000 ℃.Reaction product gas is by two gas-chromatographies (Model Shimadzu GC-7A andModel SP-6800) on-line analysis, and analytical results is seen Fig. 5 and Fig. 6.
Argon and helium is respectively as the thinner of carbonic acid gas and methane in the present embodiment, avoids the reaction feed excessive concentration and influences reaction effect, and help reaction product and in time discharge.This programme only uses for lab setup, does not need thinner in the relatively large device.
When Fig. 5 represented that temperature of reaction is 850 ℃～950 ℃, temperature was to CO
2The influence of transformation efficiency and oxygen permeability.As can be seen from the figure CO
2Transformation efficiency and oxygen permeation flux all increase along with the rising of temperature, from 2.3% to 14.9%, the speed of response that the oxygen that diaphragm-operated oxygen transmission rate and methane and infiltration are come is described is accelerated with the temperature rising, and promptly high temperature can promote the infiltration of oxygen at film body, and this process of osmosis has been broken CO
2The balance of decomposition reaction.
Fig. 6 represents that temperature of reaction is for the influence of methane conversion, carbon monoxide selective and hydrogen-carbon ratio in the present embodiment system.Diagram as seen, methane conversion and carbon monoxide selective all increase with the rising of temperature, methane conversion increases to 30% from 4.2%, carbon monoxide selective is all more than 86%.The ratio of hydrogen and carbon monoxide remains on about 1.82.
Claims (6)
1. be the method for oxygen source preparing synthetic gas with the carbonic acid gas, it is characterized in that comprising following steps:
Carbonic acid gas is fed in the enclosed space, under 800 ℃-1000 ℃ temperature, decompose, and make the oxygen that decomposes generation constantly see through the perovskite typed composite conductor oxygen-permeating film, the side that sees through at film feeds methane simultaneously, in the presence of said temperature and catalyzer, make oxygen and methane reaction, get synthetic gas; Said perovskite mixing conductor oxygen-penetrating film is that general formula is A
1-XA '
XB
1-YB '
YO
3-δPerofskite type oxide, wherein δ is the lattice imperfection number, and A, A ' are any one element among Ld, Sm, Nd, Pr, Ba, Ca, Sr, Na, La, the Bi, and B, B ' are element in any among Mn, Cr, Fe, Co, Ni, Cu, the Zr, 0＜X＜1,0＜Y＜1.
2. according to claim 1 is the method for oxygen source preparing synthetic gas with the carbonic acid gas, it is catalyst based or Rh is catalyst based to it is characterized in that said catalyzer is selected from Ni, or be selected from the compound catalyst based of at least two kinds of elements among Li, La, Mg, Ca, the Ni or be selected from transition metal Ru,, Os, Rh., Ir,, Pd, Pt, Cu, Ag or Au catalyzer.
3. the special reaction device of the method for a claim 1 is characterized in that containing inside and outside socket and mutual isolated two reactors, and two reactors form internal reaction chamber and outer reaction chamber respectively, and outer reactor is provided with CO
2Inlet pipe and unreacted be the gas outlet pipe fully; The internal reaction device is provided with CH
4Inlet pipe and syngas outlet pipe, the internal reaction device is fixed with perovskite mixing conductor oxygen-penetrating film, and the both sides face of this oxygen permeable film is respectively towards inside and outside two reaction chambers.
4. reaction unit according to claim 3 is characterized in that said perovskite mixing conductor oxygen-penetrating film is a sheet like membrane, and it to be radially being fixed in the internal reaction device, and and this reactor between be provided with seal washer.
5. reaction unit according to claim 3 is characterized in that said perovskite mixing conductor oxygen-penetrating film is a tubular membrane, and it is connected with axial with the internal reaction device, becomes the integral part of internal reaction device, and the two junction is filled with sealing material.
6. according to claim 4 or 5 described reaction units, it is characterized in that said sealing-ring and sealing material adopt precious metal, glass or ceramic high temperature material.
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|---|---|---|---|
| CN200410065196.9A CN1273372C (en) | 2004-11-01 | 2004-11-01 | Method for preparing synthesis gas using carbon dioxide as oxygen resource and its reaction apparatus |
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|---|---|---|---|
| CN200410065196.9A CN1273372C (en) | 2004-11-01 | 2004-11-01 | Method for preparing synthesis gas using carbon dioxide as oxygen resource and its reaction apparatus |
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| CN1623890A true CN1623890A (en) | 2005-06-08 |
| CN1273372C CN1273372C (en) | 2006-09-06 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100490956C (en) * | 2006-06-21 | 2009-05-27 | 中国科学院大连化学物理研究所 | Perovskite type mixed conductor oxygen permeable membrane of cerium contained series, preparation method and application |
| CN102442641A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Application of perovskite structural composite oxide to recycle chemistry chain hydrogen production and preparation thereof |
| CN102862954A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production |
| CN105709594B (en) * | 2016-01-21 | 2018-10-02 | 昆明理工大学 | CO in a kind of power-plant flue gas2The method of recycling |
| CN111389242A (en) * | 2020-03-19 | 2020-07-10 | 上海大学 | Cobalt-free anti-CO2Poisoned high oxygen-permeable biphase oxygen-permeable membrane material, its preparation method and application |
-
2004
- 2004-11-01 CN CN200410065196.9A patent/CN1273372C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100490956C (en) * | 2006-06-21 | 2009-05-27 | 中国科学院大连化学物理研究所 | Perovskite type mixed conductor oxygen permeable membrane of cerium contained series, preparation method and application |
| CN102442641A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Application of perovskite structural composite oxide to recycle chemistry chain hydrogen production and preparation thereof |
| CN102862954A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production |
| CN102862954B (en) * | 2011-07-07 | 2014-10-15 | 中国石油化工股份有限公司 | Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production |
| CN105709594B (en) * | 2016-01-21 | 2018-10-02 | 昆明理工大学 | CO in a kind of power-plant flue gas2The method of recycling |
| CN111389242A (en) * | 2020-03-19 | 2020-07-10 | 上海大学 | Cobalt-free anti-CO2Poisoned high oxygen-permeable biphase oxygen-permeable membrane material, its preparation method and application |
| CN111389242B (en) * | 2020-03-19 | 2022-08-05 | 上海大学 | Cobalt-free anti-CO 2 Poisoned high oxygen-permeable biphase oxygen-permeable membrane material, its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1273372C (en) | 2006-09-06 |
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