CN110844905A - CO realization by using mixed conductor oxygen-permeable membrane reactor2Novel system and method for pre-combustion capture - Google Patents
CO realization by using mixed conductor oxygen-permeable membrane reactor2Novel system and method for pre-combustion capture Download PDFInfo
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Abstract
The invention discloses a method for realizing CO by using a mixed conductor oxygen-permeable membrane reactor2New systems and methods for IGCC capture prior to combustion. The system comprises: a membrane reactor unit; a cooling unit; CO 22A compression capture unit; s and H2A filtration unit (5) of O; a collector unit (6) of S; a vaporization chamber on the water side of the membrane reactor; h at the outlet of the water side2The combustion power generation unit of (1). The invention takes crude synthesis gas obtained by an industrial Integrated Gasification Combined Cycle (IGCC) system as a raw material, hydrogen is obtained at one side in a mixed conductor oxygen-permeable membrane reactor for combustion and power generation, and high-purity CO is obtained at the other side2Compression liquefaction to CO2And (4) capturing before combustion. The mixed conductor oxygen permeable membrane reactor is firstly used with the IGCC system to realizeCO2And (4) capturing before combustion.
Description
Technical Field
The invention relates to the realization of CO by using a mixed conductor oxygen-permeable membrane reactor2New system for pre-combustion capture, particularly relating to CO in IGCC systems2Capture before combustion, effectively reduce energy consumption and improve power generation efficiency, and belongs to the field of fuelIn the technical fields of gas separation and purification, energy conservation and emission reduction.
Technical Field
At present, the global warming problem is becoming more and more serious, and CO2As a main greenhouse gas, the emission reduction of CO is caused in various countries in the world2Concern over the problem. Improving the utilization efficiency of fossil energy and CO in the utilization process2The capture being carried out to reduce CO2Two important measures for venting. The pre-combustion trapping is mainly applied to an integrated gasification combined cycle system (IGCC), coal is gasified by high pressure oxygen enrichment to form coal gas, and CO is generated after water gas shift2And H2. Due to gas pressure and CO2High concentration and easy to be CO2And (4) collecting. The remaining hydrogen can then be used as fuel. The technology has small trapping system, low energy consumption and great potential in the aspects of efficiency and pollutant control. The research and the application of the new unit technology are important ways for further improving the power supply efficiency of the IGCC system and reducing the power generation cost.
Conventional CO recovery2The IGCC system comprises the gasification of coal, cooling, dust removal and then water-gas shift reaction (CO + H)2O＝CO2+H2，ΔH0 R298＝-41.2kJ mol-1) To obtain CO2、H2And H2S, then removing the acid gas, and then removing H in the acid gas2S and CO2Separation is carried out. H remaining after acid gas removal2Entering a gas-steam combined cycle power generation system. This way the energy consumption is high. The temperature of the desulfurization process needs to be reduced from high temperature, and the temperature needs to be increased again after the desulfurization is finished, so that the gas-steam combined cycle power generation system can be obtained.
Sebasian Schiebahn et al combine a proton conducting membrane or Pd membrane or other hydrogen permeable membrane with an IGCC system to achieve pre-combustion CO capture2. The process flow is as follows: gasifying coal, cooling, dedusting, cooling for desulfurizing, heating for water-gas shift reaction (CO + H)2O＝CO2+H2，ΔH0 R298＝-41.2kJ mol-1) Obtaining purified CO2、H2Then the temperature is raised again and the film is enteredReactor, passing CO through hydrogen permeable membrane2And H2And (5) separating. These membrane materials are not H-resistant2S poisoning requires a cooling desulfurization purification unit in the system, and then purified synthesis gas is heated again and enters a membrane reactor, so that the energy consumption is high. And the Pd noble metal film has higher cost.
Disclosure of Invention
The system aims at solving the problems of complexity and high energy consumption that a desulfurization unit is required to be cooled first and then a membrane reactor unit is required to be heated after desulfurization and the like in the systems. We provide a new oxygen permeable membrane reactor for CO production by using mixed conductor2Novel systems and methods for pre-combustion capture.
One of the objects of the present invention is to provide a CO for IGCC2A capture system before combustion uses a mixed conductor oxygen permeable membrane reactor to process synthesis gas, the system comprises:
a syngas supply end;
a steam supply end;
the membrane reactor unit comprises a mixed conductor oxygen permeable membrane; the membrane reactor unit is divided into two parts by the mixed conductor oxygen permeable membrane, one part is a synthesis gas side, and the other part is a water side; to obtain higher CO2The recovery rate is high, catalysts are used on both sides of the membrane reactor unit, and one surface of the mixed conductor oxygen permeable membrane positioned on the synthesis gas side carries a hydrogen oxidation catalyst, such as Fe, Co, Ni, Cu, Ru, Rh, Pd or Pt-based catalyst; one surface of the mixed conductor oxygen permeable membrane positioned at the water side carries a water decomposition catalyst such as Fe, Co, Ni, Cu, Ru, Rh, Pd or Pt-based catalyst; the hydrogen oxidation catalyst and the water decomposition catalyst are respectively and independently selected from Fe, Co, Ni, Cu, Ru, Rh, Pd or Pt-based catalysts; the catalysts on both sides may be the same or different.
The gas supply end of the synthesis gas is communicated with the gas inlet end of the synthesis gas side; the water vapor supply end is communicated with the water side air inlet end.
A cooling unit communicated with the gas outlet end of the synthesis gas side for separating gaseous CO2And S and H in solid-liquid state2O；
CO2CompressionA capture unit for capturing CO discharged from the cooling unit2。
The mixed conductor oxygen permeable membrane of the invention refers to a compact inorganic ceramic membrane with oxygen ion conductivity and electronic conductivity. At high temperature, under the driving of oxygen partial pressure gradient at two sides of the membrane, the mixed conductor oxygen permeable membrane can simultaneously conduct oxygen ions and electrons, and realizes rapid, efficient and 100% selective permeation of oxygen.
In the context of the present disclosure, syngas is a syngas that contains trace amounts of hydrogen sulfide (H)2S) carbon monoxide (CO) and hydrogen (H) as impurities2) A mixture of (a).
The system further comprises:
a filtering unit for collecting S and H discharged from the cooling unit2O, and filtering to separate S and H2O；
Vaporization chamber for collecting the filter unit discharge H2O and H2And introducing the O into the air inlet end of the water side after heating and vaporization.
The system further comprises:
and the S collector unit is used for collecting the S discharged by the filtering unit.
The system further comprises:
a combustion power generation unit communicated with the air outlet end of the water side for collecting H2And (4) combusting to generate electricity.
It is another object of the present invention to provide a CO2Novel system and method for pre-combustion capture, CO achievement using the invention described above2A system for pre-combustion capture comprising the steps of:
① A gasification furnace (A) is charged with H2O and O2Obtaining crude synthesis gas;
②, introducing the crude synthesis gas into a gas cooling unit (B), and performing heat exchange to control the gas temperature at 700-900 ℃;
③, the cooled gas enters a dust removal unit (C) to remove impurities such as dust, alkali metals and the like;
④ introducing the pretreated synthesis gas into one side (synthesis gas side) of the membrane reactor (2);
⑤ the gas at the outlet of the synthesis gas side enters the cooler (3);
⑥ high concentration CO from cooler (3)2Into CO2A compression trap (4);
⑥ H cooled down from the cooler (3)2O and S, entering a filtering unit (5);
⑦ S obtained from the filtering unit (5) enters the S collector unit (6);
⑧ from the filtration unit (5)2O and additionally provided H2O enters a vaporization chamber (7);
⑨ from the vaporization chamber (7)2O (g) enters the other side (H) of the membrane reactor (2)2Side O);
⑩0H2h obtained from the outlet end of the O side2Enters a combustion power generation unit (8).
Mixed oxygen-permeable conductor membrane used in mixed oxygen-permeable conductor membrane reactor2、H2O、CO、CO2And H2Stable in S atmosphere, e.g. stable and CO-resistant in reducing atmosphere2And a dual-phase film comprising a mixed conductor phase and an oxygen ion conductor phase.
Mixed conductor oxygen permeable membranes are a class of dense ceramic membranes that are capable of conducting both electrons and oxygen ions. When an oxygen chemical potential gradient exists on both sides of the membrane, oxygen ions can directionally migrate from the high oxygen chemical potential side to the low oxygen chemical potential side. The mixed conductor oxygen permeable membrane reactor couples reaction and separation, the process is highly strengthened, and the mixed conductor oxygen permeable membrane reactor has obvious advantages in the aspects of energy conservation and consumption reduction. The high-temperature crude synthesis gas obtained after dust removal contains CO and H2And H2S, the temperature is 700-1000 ℃. The reactor is combined with a mixed conductor oxygen-permeable membrane reactor, and the temperature of the reactor can be operated at 600-1000 ℃ without cooling. One side of the membrane reactor unit is H2O and the other side is the raw synthesis gas. Decomposition reaction of water vapor at high temperature (H)2O+2e-→H2+O2-) High purity H is obtained after condensation on the outlet side2And can be used for combustion or power generation. O is2-Through a mixed conducting oxygen-permeable membrane, with synthesis gas on the other side (H)2+O2-→H2O+2e-；CO+O2-→CO2+2e-；H2S+3O2-→SO2+H2O+6e-；H2S+SO2→S+H2O), high concentration CO is obtained after condensation2And then collection capture is performed. H obtained by condensation2Filtering O to obtain S and residual H2O may be passed into H2The vaporization chamber on the O side is recycled.
Compared with the traditional CO recovery method2IGCC System CO of the Integrated System2The purity is higher, the compression cost is reduced, the energy consumption is greatly reduced, and the power generation efficiency is improved. In addition, an acid gas removal unit can be omitted in a purification unit of the synthesis gas, and the synthesis gas directly enters a membrane reactor unit without a cooling and reheating unit, so that the energy is further saved and the consumption is reduced. In the membrane reactor unit, H can be introduced2And S is converted into elemental sulfur, so that high-temperature desulfurization is realized, and an additional desulfurization unit is not required. At H2The combustion power generation unit needs to be additionally added with water vapor to control the temperature and reduce the generation of NOx. Use the present system H2The conversion on the O side does not need to be very high, so that H is obtained2Contains a large amount of water vapor, and can directly enter a combustion unit. Compared with a Pd membrane combined water-gas shift membrane reactor, the membrane reactor does not need desulfurization, and the cost of the membrane material is low. And conventional non-recovered CO2Compared with IGCC systems, CO recovery2The power generation efficiency of the IGCC system of (1) is typically reduced by 5-10 percentage points. The power generation efficiency of the system and the traditional non-recovered CO2Compared with the IGCC system, the improved IGCC system is improved by about 1 percentage point, and is environment-friendly, energy-saving and emission-reducing.
Drawings
The invention is illustrated in figure 2, wherein:
FIG. 1 shows a CO of the present invention2Schematic of a system for pre-combustion capture.
Fig. 2 is an SEM image of the film prepared in example 1, with a1 being the surface, a2 being the cross-section, and a3 being the cross-section of the surface-coated catalyst.
Detailed Description
The invention first providesCO (carbon monoxide)2A system for pre-combustion capture, comprising:
the pretreatment unit (1) of the synthesis gas comprises a gasification unit (A) of fuel in a gasification chamber, a coal gas cooler unit (B) and a dust removal unit (C);
the membrane reactor unit (2) comprises a mixed oxygen permeable conductive membrane and a catalyst on two sides of the membrane. The membrane divides the membrane reactor unit into two parts, one part being membrane reactor unit I (syngas side) and the other part being membrane reactor unit II (water side).
A cooling unit (3);
CO2a compression capture unit (4);
s and H2A filtration unit (5) of O;
a collector unit (6) of S;
providing H to the other side of the membrane reactor2A vaporization chamber (7) for O;
h of the outlet side2The combustion power generation unit (8).
In one embodiment, the membrane material used in the membrane reactor unit (2) is H in consideration of the harsh environment in which the mixed conductor oxygen permeable membrane works in the invention2、H2O, CO and CO2Neutral stable oxygen permeable membranes. The shape of the mixed conductor oxygen permeable membrane can be designed into a sheet membrane or a tubular membrane according to production requirements. As for the method for installing the mixed conductor oxygen permeable membrane in the membrane reactor in a sealing way, the technical personnel can complete the method according to the records in the prior art, the invention preferably uses the sealing method of silver ring sealing or gold ring sealing, the sealing success rate of the two sealing methods is high, and the membrane reactor with good sealing can be operated for a long time in the environment of high-temperature water vapor without leakage caused by the sealing problem.
In particular embodiments, the water-splitting catalyst may be, but is not limited to, Fe, Co, Ni, Cu, Ru, Rh, Pd, or Pt-based catalysts, or mixed-based catalysts thereof. The supporting mode of the catalyst can be, but is not limited to, brushing, dipping or an in-situ reduction precipitation method, and the thickness of the catalyst layer is 5-100 mu m.
The system of the invention is used for catalyzing water vapor in productionUnder the action of the agent, the oxygen ions and hydrogen are generated through pyrolysis, wherein the oxygen ions reach the opposite side through the mixed conductor oxygen permeable membrane to react with the purified synthesis gas; the hydrogen which can not pass through the mixed oxygen permeable conductor membrane can be used for combustion power generation after being collected subsequently. CO formation after reaction of the gas on the synthesis gas side2And H2O, cooling, drying and removing water to obtain high-concentration CO2Collection and capture are carried out.
In combination with the above system, the present invention provides a CO2A novel system and method for pre-combustion capture. In a specific embodiment, the synthesis gas obtained from IGCC is used as raw material, and the operation temperature of the membrane reactor is 600-1000 ℃.
The following specific examples are intended to further illustrate the invention and should not be construed as limiting the invention in any way.
Example 1
75 wt.% Ce0.85Sm0.15O2-δ-25wt.％Sm0.6Sr0.4Cr0.3Fe0.7O3-δ(LL Cai, et.J.Membr.Sci.2016, 520, 607-615.) as a membrane material in a membrane reactor was prepared as a sheet-like supported membrane with a dense layer thickness of-36 μm, as shown in FIG. 2. Coating Ni/Ce on the dense layer (synthesis gas side) of the membrane0.85Sm0.15O1.925(Ni/SDC) catalyst, water side impregnated Ni/SDC catalyst. The membrane was sealed in a membrane reactor with silver rings. Slowly cooling to 900 ℃, and introducing the water side of the membrane at a flow rate of 180mL min-1H of (A) to (B)2O, flow rate for syngas side 100mL min-1Synthesis gas (50% CO, 49.94% H)2，600ppm H2S). The hydrogen separation rate was 14.6mL cm-2min-1And the CO conversion rate is 8.3 percent, and the stability test of 100h is carried out, so that the hydrogen separation performance is not attenuated, and the CO conversion rate is kept constant.
Example 2
Mixing SrFe0.9Ta0.1O3-δ(WQ Jin, et al.J.Mater.chem.A,2015,3, 22564-. Ru/SDC catalyst was coated on both sides of the membrane and the membrane was sealed in a membrane reactor with silver rings. Slowly cooling to 900 ℃, and then filmingThe water side inlet flow rate of (2) is 180mL min-1H of (A) to (B)2O, flow rate for syngas side 100mLmin-1Synthesis gas (50% CO, 49.96% H)2，400ppm H2S). The hydrogen separation rate was 8.2mL cm-2min-1And the CO conversion rate is 6.3%, and the stability test of 100h shows that the hydrogen separation performance is not attenuated and the CO conversion rate is kept constant.
Example 3
75 wt.% Ce0.85Sm0.15O2-δ-25wt.％Sm0.6Sr0.4Al0.3Fe0.7O3-δ(XF Zhu, et al SolidState Ionics 2013,253, 57-63.) the membrane material is prepared into a tubular membrane, and the thickness of the outside dense layer is 40 μm. Ru/SDC catalyst was brushed on the outside of the membrane and impregnated on the inside. The membrane was sealed in a membrane reactor with silver rings. Slowly cooling to 800 deg.C, introducing 180mL min of flow rate into the inner side (water side) of the membrane-1H of (A) to (B)2O, outer (syngas side) flow rate of 100mL min-1Synthesis gas (50% CO, 49.96% H)2，400ppm H2S). The hydrogen separation rate was 11.4mL cm-2min-1And the CO conversion rate is 7.5%, and when the stability test of 100h is carried out, the hydrogen separation performance is not attenuated, and the CO conversion rate is kept constant.
Example 4
Adding Ce0.8Sm0.2O2-δ-Sr2Fe1.5Mo0.5O6-δ(NN Dai, et al J. Power Sources 2013,243, 766-. Coating Pt/Ce on the outer side of the membrane0.85Sm0.15O1.925(Pt/SDC) catalyst, the inside being impregnated with Ru/SDC catalyst. The membrane was sealed in the membrane reactor with silver rings at 961 ℃. After the temperature is reduced to 900 ℃, the flow rate of the inner side (water side) of the membrane is introduced for 180mL min-1H of (A) to (B)2O, outer (syngas side) flow rate of 100mL min-1Synthesis gas (50% CO, 49.94% H)2，600ppm H2S). The hydrogen separation rate was 23.2mL cm-2min-1CO conversion of 13.4%, stability test for 100 hours, hydrogen separabilityNo decay occurred and the CO conversion remained constant.
Example 5
Mixing BaCe0.15Fe0.85O3-δ(XF Zhu, et al. chem. Commun.2004,10, 1130-1131.) A supported membrane was prepared, the thickness of the dense layer was 20 μm, the thickness of the support layer was 0.5mm, and Fe/Ce was coated on the dense layer side of the membrane0.85Sm0.15O1.925(Fe/SDC) catalyst, and the Co/SDC catalyst is impregnated on the side of the carrier layer. The membrane reactor was sealed with a silver ring at 961 ℃. Slowly cooling to 600 ℃, and introducing the dense layer side (water side) of the membrane at the flow rate of 150mL min-1H of (A) to (B)2O, outer (syngas side) flow rate of 100mL min-1Synthesis gas (50% CO, 49.96% H)2，400ppm H2S). The hydrogen separation rate was 3.4mL cm-2min-1And the CO conversion rate is 1.6%, and the stability test of 100h shows that the hydrogen separation performance is not attenuated and the CO conversion rate is kept constant.
Example 6
Adding Ce0.8Tb0.2O2-δ-NiFe2O4(M Balaguer, et al. chem. Mater.2013,25,4986-4993) was prepared as a tubular membrane with an outer dense layer thickness of 20 μ M and an inner support layer thickness of 0.5mm, with Pt/SDC catalyst coated on the outside of the membrane and impregnated on the inside. Sealed in a membrane reactor with a gold ring. Slowly cooling to 1000 deg.C, introducing into the inner side (water side) of the membrane at flow rate of 150mL min-1H of (A) to (B)2O, outer (syngas side) flow rate of 100mL min-1Synthesis gas (50% CO, 49.9% H)2，1000ppm H2S). The hydrogen separation rate was 29.6mL cm-2min-1And the CO conversion rate is 20.2%, and the stability test of 100h shows that the hydrogen separation performance is not attenuated and the CO conversion rate is kept constant.
System embodiment
CO (carbon monoxide)2A system for pre-combustion capture, as in fig. 1, comprising:
the pretreatment unit (1) of the synthesis gas comprises a gasification unit (A) of fuel in a gasification chamber, a coal gas cooler unit (B) and a dust removal unit (C);
a membrane reactor unit (2) comprising the mixed conducting oxygen permeable membrane of example 1 (SDC-SSCF) and catalyst on both sides of the membrane (Ni/SDC). The membrane divides the membrane reactor unit into two parts, one part being membrane reactor unit I (syngas side) and the other part being membrane reactor unit II (water side).
A cooling unit (3);
CO2a compression capture unit (4);
s and H2A filtration unit (5) of O;
a collector unit (6) of S;
providing H to the other side of the membrane reactor2A vaporization chamber (7) for O;
h of the outlet side2The combustion power generation unit (8).
The membrane material membrane used in the membrane reactor unit (2) is a mixed conductor oxygen permeable membrane which conducts electrons and oxygen ions simultaneously. Respectively filled in the mixed conductor oxygen permeable membrane H2The O side catalyst module is a water decomposition catalyst and is used for catalyzing water decomposition reaction to generate hydrogen and oxygen ions; the synthesis gas side catalyst is an oxidation catalyst and is used for catalyzing the reaction of oxygen ions which are permeated through the mixed conductor oxygen permeable membrane and the synthesis gas.
In the examples of the present invention, H is introduced separately, unless otherwise specified2After O and synthesis gas, the raw material gas is decomposed into hydrogen and oxygen ions at high temperature under the action of a water decomposition catalyst. Oxygen ions permeate the mixed oxygen-permeable conductor membrane to react with the purified synthesis gas so as to promote the continuous decomposition of water and the generation of hydrogen, and the mixed oxygen-permeable conductor membrane H2The hydrogen generated by water decomposition on the O side can not pass through the mixed conducting oxygen permeable membrane, and the hydrogen with certain purity is obtained by collecting the hydrogen and is combusted for power generation. CO formation after reaction of the gas on the synthesis gas side2And H2O, cooling, drying and removing water to obtain high-concentration CO2Collection and capture are carried out.
CO is not recovered from the system and the tradition2Recovering CO2The IGCC system of (Selexol case, Pd membrane) was subjected to simulated energy consumption calculation, and the results of the effect on the overall performance were as follows: recovery of CO2(Selexol example) the ratio of the power generation efficiency is notThe recovery rate is reduced by 9.4 percent, the power generation efficiency of the Pd membrane reactor is reduced by 4.6 percent, and the power generation efficiency of the system is 0.9 percent higher.
In the embodiment of the invention:
the gas used is CO/H2/H2The mixed gas of S is used as the raw material of the synthesis gas side, and the embodiment of the invention is only used for verifying the feasibility of the system, so a circulating system is not arranged in the embodiment.
Detection of H by gas chromatography2The purity of hydrogen contained in the gas obtained after the O side reaction; conversion of CO and CO on the syngas side2The recovery rate of (1).
Detection of H with soap bubble flowmeter2Flow rate of gas obtained after O side reaction after cooling and drying. On the premise that the gas after the reaction at the raw material gas side is confirmed to be single-component hydrogen after cooling and drying through gas chromatography, the hydrogen separation rate is calculated through the following formula: r ═ F/S
In the above formula, r is the hydrogen separation rate per unit membrane area, mL cm-2min-1(ii) a F-flow rate of Hydrogen measured by soap bubble flowmeter, mL min-1(ii) a S-effective area of the diaphragm, cm2。
Claims (6)
1. CO for IGCC2A pre-combustion capture system, characterized by a mixed conducting oxygen-permeable membrane reactor for the treatment of syngas, said system comprising:
a syngas supply end;
a steam supply end;
the membrane reactor unit comprises a mixed conductor oxygen permeable membrane; the membrane reactor unit is divided into two parts by the mixed conductor oxygen permeable membrane, one part is a synthesis gas side, and the other part is a water side; one surface of the mixed conductor oxygen permeable membrane positioned at the synthesis gas side carries a hydrogen oxidation catalyst; one surface of the mixed conductor oxygen permeable membrane positioned at the water side carries a water decomposition catalyst;
the gas supply end of the synthesis gas is communicated with the gas inlet end of the synthesis gas side; the water vapor supply end is communicated with the water side air inlet end.
A cooling unit communicated with the gas outlet end of the synthesis gas side for separating gaseous CO2And S and H in solid-liquid state2O；
CO2A compression capture unit for capturing CO discharged from the cooling unit2。
2. The system of claim 1, further comprising:
a filtering unit for collecting S and H discharged from the cooling unit2O, and filtering to separate S and H2O；
Vaporization chamber for collecting the filter unit discharge H2O and H2And introducing the O into the air inlet end of the water side after heating and vaporization.
3. The system of claim 1, further comprising:
and the S collector unit is used for collecting the S discharged by the filtering unit.
4. The system of claim 1, further comprising:
a combustion power generation unit communicated with the air outlet end of the water side for collecting H2And (4) combusting to generate electricity.
5. The system of claim 2, wherein the hydrogen oxidation catalyst and the water splitting catalyst are each independently selected from Fe, Co, Ni, Cu, Ru, Rh, Pd, or Pt-based catalysts.
6. Realization of CO2A method of pre-combustion capture using the system of claim 1, comprising the steps of:
① A gasification furnace (A) is charged with H2O and O2Obtaining crude synthesis gas;
②, introducing the crude synthesis gas into a gas cooling unit (B), and performing heat exchange to control the gas temperature at 700-900 ℃;
③, the cooled gas enters a dust removal unit (C) to remove impurities such as dust, alkali metals and the like;
④ introducing the pretreated synthesis gas into one side (synthesis gas side) of the membrane reactor (2);
⑤ the gas at the outlet of the synthesis gas side enters the cooler (3);
⑥ high concentration CO from cooler (3)2Into CO2A compression trap (4);
⑥ H cooled down from the cooler (3)2O and S, entering a filtering unit (5);
⑦ S obtained from the filtering unit (5) enters the S collector unit (6);
⑧ from the filtration unit (5)2O and additionally provided H2O enters a vaporization chamber (7);
⑨ from the vaporization chamber (7)2O (g) enters the other side (H) of the membrane reactor (2)2Side O);
⑩H2h obtained from the outlet end of the O side2Enters a combustion power generation unit (8).
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| CN201810946800.0A CN110844905A (en) | 2018-08-20 | 2018-08-20 | CO realization by using mixed conductor oxygen-permeable membrane reactor2Novel system and method for pre-combustion capture |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111591957A (en) * | 2020-05-25 | 2020-08-28 | 中国矿业大学(北京) | Coal bed gas combined cycle power generation and CO2Trapping system and method |
| IT202000023470A1 (en) | 2020-10-06 | 2022-04-06 | Agenzia Naz Per Le Nuove Tecnologie Lenergia E Lo Sviluppo Economico Sostenibile Enea | MEMBRANE PROCESS FOR THE PRODUCTION OF HYDROGEN AND OXYGEN BY WATER HYDROLYSIS AND RELATED APPARATUS |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003089117A1 (en) * | 2002-04-18 | 2003-10-30 | Trustees Of Boston University | Hydrogen separation using oxygen ion-electron mixed conducting membranes |
| CN105417494A (en) * | 2016-01-07 | 2016-03-23 | 昆明理工大学 | Device and method for decomposing water through K2NiF4 structure oxygen permeable film material to produce hydrogen |
| CN105692549A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | A system for preparing high-purity hydrogen and a method therefor |
| CN107057767A (en) * | 2017-03-17 | 2017-08-18 | 北京交通大学 | One kind is based on CO before chemical chain making oxygen by air separation and burning2The electricity generation system of trapping |
| JP2018083729A (en) * | 2016-11-22 | 2018-05-31 | 千代田化工建設株式会社 | Hydrogen manufacturing apparatus, hydrogen manufacturing system including the same, and hydrogen manufacturing method |
-
2018
- 2018-08-20 CN CN201810946800.0A patent/CN110844905A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003089117A1 (en) * | 2002-04-18 | 2003-10-30 | Trustees Of Boston University | Hydrogen separation using oxygen ion-electron mixed conducting membranes |
| CN105692549A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | A system for preparing high-purity hydrogen and a method therefor |
| CN105417494A (en) * | 2016-01-07 | 2016-03-23 | 昆明理工大学 | Device and method for decomposing water through K2NiF4 structure oxygen permeable film material to produce hydrogen |
| JP2018083729A (en) * | 2016-11-22 | 2018-05-31 | 千代田化工建設株式会社 | Hydrogen manufacturing apparatus, hydrogen manufacturing system including the same, and hydrogen manufacturing method |
| CN107057767A (en) * | 2017-03-17 | 2017-08-18 | 北京交通大学 | One kind is based on CO before chemical chain making oxygen by air separation and burning2The electricity generation system of trapping |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111591957A (en) * | 2020-05-25 | 2020-08-28 | 中国矿业大学(北京) | Coal bed gas combined cycle power generation and CO2Trapping system and method |
| IT202000023470A1 (en) | 2020-10-06 | 2022-04-06 | Agenzia Naz Per Le Nuove Tecnologie Lenergia E Lo Sviluppo Economico Sostenibile Enea | MEMBRANE PROCESS FOR THE PRODUCTION OF HYDROGEN AND OXYGEN BY WATER HYDROLYSIS AND RELATED APPARATUS |
| WO2022073976A1 (en) | 2020-10-06 | 2022-04-14 | Enea - Agenzia Nazionale Per Le Nuove Tecnologie, L’Energia E Lo Sviluppo Economico Sostenibile | Membrane process for the production of hydrogen and oxygen by hydrolysis of water and related apparatus |
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