CN112744785A - Chemical chain coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ - Google Patents
Chemical chain coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 87
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 79
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 50
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- 238000010168 coupling process Methods 0.000 title claims abstract description 39
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- 150000002431 hydrogen Chemical class 0.000 claims abstract description 10
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- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
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- 239000000969 carrier Substances 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
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- 239000002131 composite material Substances 0.000 claims description 3
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- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
- C01B3/063—Cyclic methods
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- C01—INORGANIC CHEMISTRY
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention provides a chemical chain coupling process for coproducing synthesis gas and hydrogen by utilizing carbon dioxide in situ, which comprises the following steps: 1) reaction of fuel and oxygen carrier to CO2And H2O, passing through a gas-solid separator to obtain gas and solid; 2) reacting the fuel with the solid obtained in the step 1) to generate synthesis gas, and passing the synthesis gas through a gas-solid separator to obtain solid and synthesis gas; 3) carrying out cracking reaction on the gas obtained in the step 1) and the solid obtained in the step 2) to generate synthesis gas, and passing the synthesis gas through a gas-solid separator to obtain the solid and the synthesis gas; 4) reacting the water vapor with the solid obtained in the step 3) to generate hydrogen, and passing the hydrogen through a gas-solid separator to obtain solid and hydrogen; 5) air reacts with the solid obtained in the step 4) to enable the solid to reactAnd (3) obtaining oxidation regeneration, and enabling the solid to enter the step 1) for next recycling after passing through a gas-solid separator. The invention can obtain high-quality synthesis gas and hydrogen, and can realize CO2And converting it into synthesis gas.
Description
Technical Field
The invention relates to the field of synthesis gas and hydrogen production by chemical looping, in particular to a chemical looping coupling process for coproducing synthesis gas and hydrogen by utilizing carbon dioxide in situ.
Background
Along with the increase of global energy demand and the exploitation of large unconventional natural gas reserves such as coal bed gas, shale gas, combustible ice and the like, the utilization of natural gas is more and more emphasized. The conversion of natural gas to syngas and hydrogen is very important in the world because the former is an important feedstock for the synthesis of many chemicals and liquid fuels, while the latter is a clean energy source of high energy density.
Steam reforming of methane (SMR, CH)4+H2O＝CO+3H2) Is the technology for converting methane into synthesis gas or hydrogen relatively mature at present. However, H of the syngas produced2A molar ratio/CO of 3, which is unfavorable for the subsequent Fischer-Tropsch synthesis (ideal H)2the/CO ratio is 2), a subsequent gas conditioning process is required. In order to obtain high purity hydrogen, it is necessary to perform a Water Gas Shift (WGS) reaction and a complicated separation and purification step such as amine washing or Pressure Swing Adsorption (PSA). The SMR reaction itself is highly endothermic, and the conditioning of syngas and the separation and purification of high purity hydrogen exacerbate the energy consumption. The emission of large amounts of carbon dioxide has also accelerated the pace of global warming.
Chemical looping-steam methane reforming (CL-SMR) is an emerging technology for cyclic low energy consumption generation of syngas and high purity hydrogen based on a solid oxygen carrier, typically a transition metal oxide. In the fuel reactor, methane is partially oxidized to synthesis gas by the lattice oxygen of the oxygen carrier (MeOx), and then the reduced oxygen carrier (Me) is oxidized by water vapor to recover the lattice oxygen, while hydrogen is produced by the water vapor cracking reaction. High purity hydrogen can be obtained simply by condensing the water vapor.
In the fuel reactor, the fuel reacts with the surface oxygen of the solid oxygen carrier with the lattice oxygen, so the oxygen species in the oxygen carrier have a large influence on the distribution of the product. Generally, the fuel first reacts with the active surface oxygen to completionOxidation products (CO)2And H2O), then the less reactive lattice oxygen selectively oxidizes the fuel partially to CO and H2. In order to increase the selectivity of the synthesis gas, the amount of carbon dioxide initially formed should be minimized. And air/O2Use of a weaker oxidant (H) than a stronger oxidant2O or CO2) The selectivity of the syngas can be increased by modulating the distribution of oxygen species. However, the oxidation ability of water is weak, and oxygen carriers cannot be completely recovered, and deactivation of oxygen carriers is easily caused in a long-term redox cycle operation.
The oxygen carrier partially oxidized by the water vapor is introduced into the air reactor, so that the oxygen carrier can be completely recovered, the improvement of the circulation stability of the oxygen carrier is facilitated, and the heat release property can be utilized to provide energy for the system. However, due to air/O2Has a relatively strong oxidizing power of air/O2Will inevitably lead to an enrichment of active oxygen species which are liable to lead to complete oxidation of the fuel and to CO2Rather than selective oxidation to produce syngas, thereby reducing the overall selectivity of syngas and increasing global warming.
Many researchers try to modify the oxygen carrier and examine the influence of the properties such as composition, structure and morphology, but it is difficult to avoid CO formed in the early stage of the reaction2. In addition to the reduction of the selectivity of the synthesis gas, the increase of the carbon dioxide content in the initial phase will undoubtedly also lead to carbon dioxide emissions, aggravating the greenhouse effect, due to the excessive oxidation of the air. Therefore, there is a need to develop a new technique for combining CL-SMR with in situ CO2The trapping is combined, and low energy consumption and low carbon footprint are realized.
To date, most research has focused on adsorption enhanced chemical chain reforming (SE-CLR). Adsorption enhanced chemical looping reforming typically uses iron oxide as an oxygen carrier and calcium oxide (CaO) as CO2An adsorbent. In this process, fuel CH4、H2O, oxygen carrier and CO2The sorbent (CaO) enters the fuel reactor together, during which reforming reactions, WGS reactions and CO2The adsorption reaction is carried out simultaneously, and CO can be realized2To be caughtCollecting and obtaining hydrogen-rich synthesis gas, but not obtaining H2Syngas with a/CO ratio of 2. Due to CO2The sorbent is consumed in the fuel reaction, thus requiring high temperature calcination to regenerate CO2An adsorbent. When air is used as oxidant to regenerate oxygen carrier and adsorbent, desorbed CO2Are highly diluted in nitrogen and still require additional equipment or processes to handle and utilize the captured carbon dioxide. In addition, oxygen carriers and CO are used simultaneously2Adsorbents also increase the difficulty of solids handling.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a chemical-looping coupling process for coproducing synthesis gas and hydrogen by utilizing carbon dioxide in situ.
In order to achieve the purpose, the invention adopts the technical scheme that:
in-situ utilization of CO2The chemical chain coupling process for coproducing synthesis gas and hydrogen comprises the following steps:
1) reaction of fuel and oxygen carrier to CO2And H2O, passing through a gas-solid separator to obtain gas and partially reduced solid;
2) reacting the fuel with the partially reduced solid obtained in the step 1) to generate synthesis gas, and passing the synthesis gas through a gas-solid separator to obtain reduced solid and synthesis gas;
3) carrying out a cracking reaction on the gas obtained in the step 1) and the reduced solid obtained in the step 2) to generate synthesis gas, and passing the synthesis gas through a gas-solid separator to obtain solid and synthesis gas;
4) reacting the water vapor with the solid obtained in the step 3) to generate hydrogen, and passing the hydrogen through a gas-solid separator to obtain partially oxidized solid and hydrogen;
5) and (3) reacting air with the solid obtained in the step (4) to oxidize and regenerate the solid, and enabling the solid to enter the step (1) for next recycling after passing through a gas-solid separator.
A further improvement of the invention is that the fuel in step 1) and step 2) is methane.
The further improvement of the invention is that the oxygen carrier in the step 1) is one of the following oxygen carriers:Fe2O3、FeO、Fe、Fe3O4sodium-modified Fe2O3/Al2O3Oxygen carrier, Fe2O3/Al2O3(1.5-Y2O3) Oxygen carrier, nickel-strengthened Fe2O3/Al2O3Oxygen carrier, Fe2O3/Al2O3Oxygen carrier, Ce-Fe-Zr-O/MgO monolithic oxygen carrier, CeO2Modified Fe2O3Oxygen carrier, CeO2Hematite oxygen carrier, NiFe2O4Oxygen carrier, Fe2O3/MgAl2O4An oxygen carrier; la1.6Sr0.4FeCoO6An oxygen carrier; La-Fe-Al oxygen carrier;
Sr(Fe1-xCux)O3-δan oxygen carrier, wherein x is 0, 0.1 or 0.33;
CaTi0.125Mn0.875-xFexTi0.125O3-δan oxygen carrier, wherein x is 0, 0.05, 0.1, 0.15 or 0.2;
BaFe2.8M0.2Al9O19an oxygen carrier, wherein M ═ Fe, Si, Zr, or Ce;
BaFe2MAll9O19an oxygen carrier, wherein M ═ Mn, Ni, or Co;
AFexAl12-xO19oxygen carrier, wherein A ═ La or Ba, 0<x<5；
CeO2And AFenAl12-nO19A composite oxygen carrier, wherein A ═ La or Ba, 0<n≤12；
A1-xBxFe12-xMyO19An oxygen carrier, wherein A ═ La ═ Ba, M ═ Sn, Zr or Ce, 0.2. ltoreq. x.ltoreq.0.6, 0.2. ltoreq. y.ltoreq.1.2.
In a further improvement of the invention, the molar ratio of the solid to the fuel in the step 1) is (1-12): 1, the reaction temperature is 200-1500 ℃.
A further improvement of the invention is that the fuel to solids molar ratio in step 2) is (0.25-1.25): 1, the reaction temperature is 200-1500 ℃.
In a further development of the invention, the CO in step 3) is2Molar ratio to solid (0.11-0.62): 1, the reaction temperature is 200-1500 ℃.
In a further development of the invention, H in step 4) is2The molar ratio of O to solid is (0.1-1.9): 1, the reaction temperature is 200-1500 ℃.
In a further development of the invention, the molar ratio of air to solid in step 5) is (0.75 to 2.25): 1, the reaction temperature is 200-1500 ℃.
The further improvement of the invention is that the pressure of the reaction in the steps 1) to 5) is 1-12 atm.
Compared with the prior art, the invention has the beneficial effects that:
the invention combines CL-SMR with Chemical Looping Combustion (CLC) and CO2-H2Combined with O co-cracking, 5 reactors were included: a fuel combustion reactor (R101), a fuel reforming reactor (R102), a co-cracking reactor (R103), a steam reactor (R104), and an air reactor (R105). In conventional CL-SMR, the CO at the initial stage2Not only reduces the selectivity of the synthesis gas, but also leads to the greenhouse gas CO2And (4) discharging. However, in the coupling process proposed in this application, the CO initially formed in the R101 reactor2And H2O is no longer vented or mixed with syngas, but rather is used as a co-cracking feedstock to generate additional syngas in the R103 reactor. This not only greatly increases the purity of the syngas in the fuel reforming reactor (R102), but also increases the overall yield of syngas. Further, (CO) in R1032+H2O) can remove carbon deposit possibly formed in R102, and avoid polluting high-purity H generated in subsequent R1042. In this chemical chain coupling process, not only can ideal H be produced separately2Syngas and high purity hydrogen suitable for Fischer-Tropsch synthesis with a/CO ratio (2), and also the ability to utilize the greenhouse gas CO2. In addition, synthesis gas regulation, hydrogen purification and carbon dioxide capture and storage are not needed, and cost is greatly saved. Compared with SE-CLR, our coupling processOnly the oxygen carrier is recycled and therefore there are fewer problems with solids handling and more flexibility in the setting of the operating temperature and feed ratio of the reactor.
The coupling process product of the present invention has two strands of H2Synthesis gas with a 2/CO ratio and high purity hydrogen, methane conversion in the R101 and R102 reactors up to 100% and 98%, synthesis gas yields in the R102 and R103 reactors of 97% and 84%, two streams of synthesis gas and H2The purity is respectively as high as 93 percent, 99 percent and 100 percent, and the gas separation cost is greatly reduced. The total energy utilization efficiency of the coupled system added with the heat exchange network is as follows
The efficiency is respectively 90.54% and 72.04%, and CO is utilized in situ2Avoid CO2Trapping and sealing; the method has the advantages of less pollutant discharge, lower requirements on equipment of each process unit, simple production operation and good economic benefit.
The coupling process is applicable to most Fe-based oxygen carriers. The active component of the oxygen carrier is Fe, including Fe in different oxidation states and reduction states2O3、Fe3O4FeO and Fe. The carrier may be Al2O3、CeO2MgO, spinel, perovskite or hexaaluminate, and the like.
Drawings
FIG. 1 is a schematic diagram of a chemical chain coupling process.
FIG. 2 is a schematic flow diagram of a chemical-looping coupling system.
FIG. 3 is a flow diagram of a chemical-looping coupling system including a heat exchange network.
FIG. 4 is an energy balance analysis diagram of a chemical-looping coupling system.
FIG. 5 is Fe2O3/CH4-effect of 1 molar ratio on conversion of product and oxygen carrier. Wherein (a) is the influence on the gas phase component and (b) is the influence on the solid phase component. Wherein, CH4-1 is methane entering the R101 reactor.
FIG. 6 is CH4The influence of the 2/FeO molar ratio on the conversion of the product and of the oxygen carrier. Wherein the content of the first and second substances,(a) the influence on the gas phase component, (b) the influence on the solid phase component, and (c) the influence on the main evaluation index of the gas phase component. Wherein, CH4-2 is methane entering the R102 reactor.
FIG. 7 is CO2Influence of the/Fe molar ratio on the conversion of the product and oxygen carrier. Wherein (a) is an influence on a gas phase component, (b) is an influence on a solid phase component, and (c) is an influence on a main evaluation index of the gas phase component.
FIG. 8 is H2The influence of the O/FeO molar ratio on the conversion of the product and oxygen carriers. Wherein (a) is the influence on the gas phase component and (b) is the influence on the solid phase component.
FIG. 9 is Air/Fe3O4Effect of molar ratio oxygen carrier conversion.
FIG. 10 is a graph of the effect of temperature on product and oxygen carrier conversion in the R101 reactor. Wherein (a) is the influence on the gas phase component and (b) is the influence on the solid phase component.
FIG. 11 is a graph of the effect of temperature on product and oxygen carrier conversion in the R102 reactor. Wherein (a) is an influence on a gas phase component, (b) is an influence on a solid phase component, and (c) is an influence on a main evaluation index of the gas phase component.
FIG. 12 is a graph of the effect of temperature on product and oxygen carrier conversion in the R103 reactor. Wherein (a) is an influence on a gas phase component, (b) is an influence on a solid phase component, and (c) is an influence on a main evaluation index of the gas phase component.
FIG. 13 is a graph of the effect of temperature on product and oxygen carrier conversion in the R104 reactor. Wherein (a) is the influence on the gas phase component and (b) is the influence on the solid phase component.
FIG. 14 is a graph of the effect of pressure on product and oxygen carrier conversion in a reactor. Wherein (a) is the effect on the conversion of product and oxygen carrier in the R101 reactor, (b) is the effect on the conversion of product and oxygen carrier in the R102 reactor, (c) is the effect on the conversion of product and oxygen carrier in the R103 reactor, and (d) is the effect on the conversion of product and oxygen carrier in the R104 reactor.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
As shown in the figure1, the invention comprises a chemical looping combustion reactor, a chemical looping reforming synthesis gas reactor, and CO2And H2The reactor comprises a synthesis gas reactor by O co-cracking, a water cracking hydrogen production reactor and an air regeneration oxygen carrier reactor. The invention relates to two strands of CH4，CH4-1 and CH4-2 is methane entering the R101 and R102 reactors, respectively. The method specifically comprises the following steps:
1) fuel (CH)4-1) and oxygen carrier (Fe)2O3) Is introduced into a combustion reactor (R101). Introduced fuel (CH)4) Is completely oxidized into CO2And H2O, and the oxygen carrier is reduced to a lower valence state (FeO). Gas component CO after separation device (SEP101)2And H2O enters the cracking reactor (R103) to produce additional syngas, rather than being captured and sequestered. Wherein the feed ratio (molar ratio) of the reactor R101 is Fe2O3/CH4-1 is 1-12, the operation temperature is 200-1500 ℃, and the operation pressure is 1-12 atm; preferably, the feed ratio is Fe2O3/CH4-1 is 4, the operating temperature is 900 ℃ and the operating pressure is 1 atm.
R101 reactor: chemical looping combustion
CH4+4Fe2O3→CO2+2H2O+8FeO
2) The solid component FeO from the R101 reactor enters the reforming reactor (R102) and is mixed with fuel (CH)4-2) reacting to form synthesis gas; after the SEP102, the gas component (syngas-1) is collected as product 1. At the same time, the reduced oxygen carrier (FeO) is further reduced to the metallic state (Fe). Wherein the feed ratio CH of the reactor R1024the-2/FeO is 0.25-1.25, the operating temperature is 200-1500 ℃, and the operating pressure is 1-12 atm; preferably, the feed ratio CH4-2/FeO of 4, operating temperature of 900 ℃ and operating pressure of 1 atm.
R102 reactor: chemical looping reforming to produce synthesis gas
CH4+FeO→CO+2H2+Fe
3) Metal (Fe) enters the R103 reactor, with CO in SEP1012And H2O mixture reacts, with or without make-up of feedstock (CO)2And H2O), generating additional synthesis gas by co-cracking; the gas component (syngas-2) after the SEP103 was collected as product 2. Thus, both the R102 and R103 reactors are used to produce syngas, greatly increasing syngas yield and avoiding CO2Capture and sequestration of. Wherein the feed ratio of the reactor R103 is CO2Fe is 0.11-0.62, the operation temperature is 200-1500 ℃, and the operation pressure is 1-12 atm; preferably, the feed ratio is CO2Fe is 0.4, the operating temperature is 850 ℃ and the operating pressure is 1 atm.
R103 reactor: CO 22And H2Co-cracking of O to synthesis gas
CO2+2H2O+3Fe→CO+2H2+3FeO
4) The solid component FeO from the R102 reactor enters the R104 reactor and reacts with the water vapor to generate hydrogen gas, FeO → Fe3O4And oxidizing to generate hydrogen. By separation (SEP104) and condensation, high-purity H is obtained2As product 3. Wherein the feed ratio H of the reactor R1042The O/FeO is 0.1-1.9, the operating temperature is 200-1500 ℃, and the operating pressure is 1-12 atm; preferably, the feed ratio H2The O/FeO was 4, the operating temperature was 500 ℃ and the operating pressure was 1 atm.
R104 reactor: hydrogen production by steam cracking
H2O+3FeO→H2+Fe3O4 
5) Solid component (Fe) due to strong oxidizing power of air3O4) Is completely oxidized to Fe in an air reactor (R105)2O3(ii) a After SEP105-10 separator, Fe2O3Enters the combustion reactor (R101) and starts the next cycle. Wherein the feed ratio of reactor R105 is Air/Fe3O40.75-2.25, the operation temperature is 200-1500 ℃, and the operation pressure is 1-12 atm; preferably, the feed ratio Air/Fe3O4The temperature was 500 ℃ and the pressure was 1 atm.
R105 reactor: oxygen carrier regeneration
O2+4Fe3O4→6Fe2O3 
The following are specific examples.
Example 1
1) Fuel CH4With an oxygen carrier Fe2O3A chemical looping combustion reactor R101 with a temperature of 900 ℃ and a pressure of 1atm was introduced, the flow rate of methane was 1kmol/h, and the feed ratio of oxygen carrier to methane was 4.
2) Fuel CH4With the oxygen carrier FeO from the R101 reactor, was passed into a chemical chain reforming reactor R102 at a temperature of 900 c and a pressure of 1atm, with a feed ratio of methane to oxygen carrier of 1.
3) CO from R101 reactor2And H2Introducing O and Fe as oxygen carrier from R102 reactor into a CO-cracking reactor R103 at 850 deg.C and 1atm, and introducing CO2The feed ratio to oxygen carrier was 0.4.
4) Introducing water vapor and an oxygen carrier FeO from the R103 reactor into a hydrogen production reactor R104 with the temperature of 500 ℃ and the pressure of 1atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 1.1.
5) Air with oxygen carrier Fe from R104 reactor3O4An oxygen carrier regeneration reactor R105 having a temperature of 500 ℃ and a pressure of 1atm was introduced, and the feed ratio of air to oxygen carrier was 1.5.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 2
1) Fuel CH4With sodium-modified Fe2O3/Al2O3Oxygen carrier, into a chemical-looping combustion reactor R101 at 200 ℃ and 12atm, the flow rate of methane is 1kmol/h, and the feeding ratio of the oxygen carrier to the methane is 6.
2) Fuel CH4With the oxygen carrier from the R101 reactor, was passed into a chemical chain reforming reactor R102 at a temperature of 500 c and a pressure of 7atm, with a feed ratio of methane to oxygen carrier of 0.25.
3) CO from R101 reactor2And H2O and oxygen carrier from R102 reactor are introduced into a CO-cracking reactor R103 with the temperature of 200 ℃ and the pressure of 12atm, and CO2The feed ratio to oxygen carrier was 0.11.
4) Introducing water vapor and an oxygen carrier from the R103 reactor into a hydrogen production reactor R104 with the temperature of 700 ℃ and the pressure of 8atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 1.9.
5) Air and oxygen carrier from the R104 reactor were passed into an oxygen carrier regeneration reactor R105 at a temperature of 200 ℃ and a pressure of 12atm at a feed ratio of air to oxygen carrier of 0.75.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 3
1) Fuel CH4With CeO2Modified Fe2O3Oxygen carrier, a chemical-looping combustion reactor R101 with the temperature of 500 ℃ and the pressure of 7atm, the flow rate of methane is 1kmol/h, and the feeding ratio of the oxygen carrier to the methane is 1.
2) Fuel CH4With the oxygen carrier from the R101 reactor, was passed into a chemical chain reforming reactor R102 at 300 ℃ and 12atm pressure, with a methane to oxygen carrier feed ratio of 0.75.
3) CO from R101 reactor2And H2O and oxygen carrier from R102 reactor are introduced into a CO-cracking reactor R103 with the temperature of 800 ℃ and the pressure of 8atm, and CO2The feed ratio to oxygen carrier was 0.3.
4) Introducing water vapor and an oxygen carrier from the R103 reactor into a hydrogen production reactor R104 with the temperature of 200 ℃ and the pressure of 12atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 0.1.
5) Air and oxygen carrier from the R104 reactor were passed into an oxygen carrier regeneration reactor R105 at 400 c and 5atm pressure with an air to oxygen carrier feed ratio of 2.25.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 4
1) Fuel CH4With Fe2O3/Al2O3(1.5-Y2O3) Oxygen carrier, into a chemical-looping combustion reactor R101 at a temperature of 700 ℃ and a pressure of 5atm, a flow rate of methane of 1kmol/h, and a feed ratio of oxygen carrier to methane of 12.
2) Fuel CH4With the oxygen carrier from the R101 reactor, was passed into a chemical chain reforming reactor R102 at 1500 ℃ and a pressure of 10atm, with a feed ratio of methane to oxygen carrier of 1.25.
3) CO from R101 reactor2And H2O and oxygen carrier from R102 reactor are introduced into a CO-cracking reactor R103 with the temperature of 1200 ℃ and the pressure of 4atm, and CO2The feed ratio to oxygen carrier was 0.33.
4) Introducing water vapor and an oxygen carrier from the R103 reactor into a hydrogen production reactor R104 with the temperature of 1500 ℃ and the pressure of 11atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 0.9.
5) Air and oxygen carrier from the R104 reactor were passed into an oxygen carrier regeneration reactor R105 at a temperature of 800 ℃ and a pressure of 6atm at a feed ratio of air to oxygen carrier of 1.0.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 5
1) Fuel CH4With BaFe2.8M0.2Al9O19Oxygen carrier (M ═ Fe, Si, Zr)Or Ce) into a chemical looping combustion reactor R101 at a temperature of 1200 ℃ and a pressure of 10atm, a methane flow of 1kmol/h and a feed ratio of oxygen carrier to methane of 8.
2) Fuel CH4With the oxygen carrier from the R101 reactor, was passed into a chemical chain reforming reactor R102 at 1300 c and 6atm pressure, with a methane to oxygen carrier feed ratio of 0.5.
3) CO from R101 reactor2And H2O and oxygen carrier from the R102 reactor are introduced into a CO-cracking reactor R103 with the temperature of 1500 ℃ and the pressure of 7atm, and CO2The feed ratio to oxygen carrier was 0.5.
4) Introducing water vapor and an oxygen carrier from the R103 reactor into a hydrogen production reactor R104 with the temperature of 900 ℃ and the pressure of 5atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 0.7.
5) Air and oxygen carrier from the R104 reactor were passed into an oxygen carrier regeneration reactor R105 at a temperature of 1000 ℃ and a pressure of 3atm, with a feed ratio of air to oxygen carrier of 1.5.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 6
1) Fuel CH4With CeO2And AFenAl12-nO19Composite oxygen carrier (A ═ La or Ba, 0)<n is less than or equal to 12), a chemical-looping combustion reactor R101 with the temperature of 400 ℃ and the pressure of 4atm is introduced, the flow rate of methane is 1kmol/h, and the feeding ratio of the oxygen carrier to the methane is 3.
2) Fuel CH4With the oxygen carrier from the R101 reactor, was passed into a chemical chain reforming reactor R102 at a temperature of 200 ℃ and a pressure of 2atm, with a feed ratio of methane to oxygen carrier of 0.9.
3) CO from R101 reactor2And H2O and oxygen carrier from R102 reactor are introduced into a CO-cracking reactor R103 with the temperature of 400 ℃ and the pressure of 6atm, and CO2The feed ratio to oxygen carrier was 0.2.
4) Introducing water vapor and an oxygen carrier from the R103 reactor into a hydrogen production reactor R104 with the temperature of 800 ℃ and the pressure of 7atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 0.5.
5) Air and oxygen carrier from the R104 reactor were passed into an oxygen carrier regeneration reactor R105 at 1500 ℃ and a pressure of 10atm at a feed ratio of air to oxygen carrier of 2.0.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 7
1) Fuel CH4And La1.6Sr0.4FeCoO6Oxygen carrier, a chemical-looping combustion reactor R101 with the temperature of 1500 ℃ and the pressure of 8atm, the flow rate of methane is 1kmol/h, and the feeding ratio of the oxygen carrier to the methane is 6.
2) Fuel CH4With the oxygen carrier from the R101 reactor, was passed into a chemical chain reforming reactor R102 at a temperature of 600 c and a pressure of 4atm, with a feed ratio of methane to oxygen carrier of 0.4.
3) CO from R101 reactor2And H2O and oxygen carrier from R102 reactor are introduced into a CO-cracking reactor R103 with the temperature of 600 ℃ and the pressure of 10atm, and CO2The feed ratio to oxygen carrier was 0.55.
4) Introducing water vapor and an oxygen carrier from the R103 reactor into a hydrogen production reactor R104 with the temperature of 1100 ℃ and the pressure of 3atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 1.6.
5) Air and oxygen carrier from the R104 reactor were passed into an oxygen carrier regeneration reactor R105 at 900 c and 7atm pressure with an air to oxygen carrier feed ratio of 1.3.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 8
1) Fuel CH4With Fe2O3/MgAl2O4Oxygen carrier, a chemical-looping combustion reactor R101 with the temperature of 1400 ℃ and the pressure of 3atm, the flow rate of methane is 1kmol/h, and the feeding ratio of the oxygen carrier to the methane is 9.
2) Will burnMaterial CH4With the oxygen carrier from the R101 reactor, was passed into a chemical chain reforming reactor R102 at 1000 c and 8atm pressure, with a methane to oxygen carrier feed ratio of 0.3.
3) CO from R101 reactor2And H2Introducing O and oxygen carrier from R102 reactor into a CO-cracking reactor R103 with temperature of 1300 deg.C and pressure of 2atm, and introducing CO2The feed ratio to oxygen carrier was 0.62.
4) Introducing water vapor and an oxygen carrier from the R103 reactor into a hydrogen production reactor R104 with the temperature of 1400 ℃ and the pressure of 6atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 0.7.
5) Air and oxygen carrier from the R104 reactor were passed into an oxygen carrier regeneration reactor R105 at a temperature of 1200 c and a pressure of 11atm at a feed ratio of air to oxygen carrier of 1.7.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
The above examples may also use the following oxygen carriers:
nickel-strengthened Fe2O3/Al2O3Oxygen carrier, Fe2O3/Al2O3Oxygen carrier, Ce-Fe-Zr-O/MgO monolithic oxygen carrier, CeO2Hematite oxygen carrier, NiFe2O4Oxygen carrier, Sr (Fe)1-xCux)O3-δOxygen carrier (x ═ 0, 0.1, or 0.33), CaTi0.125Mn0.875-xFexTi0.125O3-δOxygen carrier (x ═ 0, 0.05, 0.1, 0.15, or 0.2), La-Fe-Al oxygen carrier, BaFe2MAll9O19Oxygen carrier (M ═ Mn, Ni, and Co), AFexAl12-xO19Oxygen carrier (A ═ La or Ba, 0)<x<5)、A1-xBxFe12- xMyO19(A ═ La, B ═ Ba, M ═ Sn, Zr or Ce, 0.2. ltoreq. x.ltoreq.0.6, 0.2. ltoreq. y.ltoreq.1.2) and the like.
The present invention is applicable to most iron-based oxygen carriers as shown in table 1, but is not limited thereto.
TABLE 1 iron-based oxygen carrier with iron as the active center
The literature is as follows:
[1]Huang WC,Kuo YL,Su PC,et al.Redox performance of Na-modified Fe2O3/Al2O3 with syngas as reducing agent in chemical looping combustion process.Chem Eng J,2018,334:2079-2087.
[2]Kang Y,Tian M,Huang CD,et al.Improving syngas selectivity of Fe2O3/Al2O3 with yttrium modification in chemical looping methane conversion.ACS Catal,2019,9(9):8373-8382.
[3]Kang D,Lim HS,Lee M,et al.Syngas production on a Ni-enhanced Fe2O3/Al2O3 oxygen carrier via chemical looping partial oxidation with dry reforming of methane.Appl Energ,2018,211:174-186.
[4]Zhu M,Song Y H,Chen S Y,et al.Chemical looping dry reforming of methane with hydrogen generation on Fe2O3/Al2O3 oxygen carrier.Chem Eng J,2019,368:812-823.
[5] Ce-Fe-Zr-O/MgO monolithic oxygen carriers were used in Lee Fao, Congress, et al for the chemical chain partial oxidation of methane to syngas [ J ] fuel chemistry report 2015,43(4): 118-.
[6]CeO burnt based on methane chemical chain2Preparation and Performance of modified oxygen Supports [ J]University of Kunming science (Nature science edition), 2015,40(2):12-17.
[7]Miller DD,Siriwardane R.Mechanism of methane chemical looping combustion with hematite promoted with CeO2.Energ Fuel,2013,37:4087-4096.
[8]Ma Z,Zhang S,Lu YG.Phase segregation mechanism of NiFe2O4 oxygen carrier in chemical looping process.Int J Energy Res,2020:1–10.
[9]Ma Z,Zeng DW,Zhang S,et al.Effect of supports on the redox performance of NiFe2O4 in a chemical looping process.Energy Technol,2019,7(9):1900374.
[10]Zafar Q,Mattisson T,Gevert B.Redox investigation of some oxides of transition-state metals Ni,Cu,Fe,and Mn supported on SiO2 and MgAl2O4.Energ Fuel,2006,20(1):34-44.
[11]Ksepko E.Perovskite Sr(Fe1-xCux)O3-δmaterials for chemical looping combustion applications.Int J Hydrogen Energ,2018,43:9622-9634.
[12]Thoréton V,Pishahang M,Mokkelbost T,et al.Beneficial effect of iron substitution on microstructural stability of tailored CaTi0.125Mn0.875- xFexTi0.125O3-δperovskite oxygen carrier material for chemical looping combustion.Energy Technol,2017,5(9):1579-1587.
[13]Li M,Zhao K,Zhao ZL,et al.Enhanced hydrogen-rich syngas generation in chemical looping methane reforming using an interstitial doped La1.6Sr0.4FeCoO6.Int J Hydrogen Energ,2019,44(21):10250-10264.
[14]Zhu YY,Liu RL,Sun XY,et al.Metal modified hexaaluminates for syngas generation and CO2 utilization via chemical looping.Int J Hydrogen Energ,2019,44(21):10218-10231.
[15]Zhu YY,Sun XY,Liu WW,et al.Microstructure and reactivity evolution of La-Fe-Al oxygen carrier for syngas production via chemical looping CH4-CO2 reforming.Int J Hydrogen Energ,2017,42(52):30509-30524.
[16]Zhu Y,Jin N,Liu R,et al.Bimetallic BaFe2MAl9O19(M＝Mn,Ni,and Co)hexaaluminates as oxygen carriers for chemical looping dry reforming of methane.Appl Energ,2020,258:114070.
[17]Zhu YY,Liu WW,Sun XY,et al.La-hexaaluminate for synthesis gas generation by chemical looping partial oxidation of methane using CO2 as sole oxidant.AIChE J,2018,64(2):550-563.
[18] An oxygen carrier for reforming chemically-circulated dry gas, its preparing process and application (P) ZL201510419339.X,2017-10-31 are disclosed.
[19] A carrier of oxygen for generating high-quality synthetic gas, its preparing process and application [ P ]. ZL201611026036.2,2019-11-05.
[20] A Fe-based oxygen carrier with high iron content and dispersion, a preparation method and application thereof [ P ] ZL201711322508.3,2020-12-22.
Example 9
1) Fuel CH4With an oxygen carrier Fe2O3Introducing a chemical-looping combustion reactor R101 with the temperature of 900 ℃, the pressure of 1atm, the flow rate of methane of 1kmol/h and the feeding ratio of an oxygen carrier to methane of 1-12. See (a) and (b) in fig. 5.
2) Fuel CH4With the oxygen carrier FeO from the R101 reactor, is passed into a chemical-looping reforming reactor R102 at a temperature of 900 c and a pressure of 1atm, with a feed ratio of methane to oxygen carrier of 0.25 to 1.25. See (a), (b) and (c) in fig. 6.
3) CO from R101 reactor2And H2Introducing O and Fe as oxygen carrier from R102 reactor into a CO-cracking reactor R103 at 850 deg.C and 1atm, and introducing CO2The feed ratio to the oxygen carrier is from 0.11 to 0.62. See (a), (b) and (c) in FIG. 7.
4) Introducing water vapor and oxygen carrier FeO from the R103 reactor into a hydrogen production reactor R104 with the temperature of 500 ℃ and the pressure of 1atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 0.1-1.9. See (a) and (b) in fig. 8.
5) Air with oxygen carrier Fe from R104 reactor3O4An oxygen carrier regeneration reactor R105 having a temperature of 500 ℃ and a pressure of 1atm was introduced, and the feed ratio of air to oxygen carrier was 0.75 to 2.25. See fig. 9.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 10
1) Fuel CH4With an oxygen carrier Fe2O3Introducing a chemical-looping combustion reactor R101 with the pressure of 1atm, the flow rate of methane is 1kmol/h, the feeding ratio of an oxygen carrier to the methane is 4, and the reaction temperature is 200-1500 ℃. Note: for supporting fig. 10(a, b).
2) Fuel CH4And an oxygen carrier FeO from the R101 reactor, are introduced into a chemical-looping reforming reactor R102 with the pressure of 1atm, the feeding ratio of methane to the oxygen carrier is 1, and the reaction temperature is 200-1500 ℃. See (a), (b) and (c) of FIG. 11.
3) CO from R101 reactor2And H2O and Fe as oxygen carrier from R102 reactor, into a CO-cracking reactor R103 with 1atm pressure, CO2The feed ratio to the oxygen carrier was 0.4 and the reaction temperature was 200 ℃ and 1500 ℃. See (a), (b) and (c) in FIG. 12.
4) Introducing water vapor and an oxygen carrier FeO from the R103 reactor into a hydrogen production reactor R104 with the pressure of 1atm, wherein the feeding ratio of the water vapor to the oxygen carrier is 1.1, and the reaction temperature is 200-1500 ℃. See (a), (b) and (c) in FIG. 13.
5) Air with oxygen carrier Fe from R104 reactor3O4An oxygen carrier regeneration reactor R105 having a pressure of 1atm was introduced, the feeding ratio of air to oxygen carrier was 1.5, and the reaction temperature was 500 ℃.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
Example 11
1) Fuel CH4With an oxygen carrier Fe2O3Introducing into a chemical-looping combustion reactor R101 with the temperature of 900 ℃,the flow rate of methane is 1kmol/h, the feeding ratio of oxygen carrier and methane is 4, and the reaction pressure is 1-12 atm. See (a) of fig. 14.
2) Fuel CH4With the oxygen carrier FeO from the R101 reactor, is passed into a chemical-looping reforming reactor R102 at a temperature of 900 ℃ and with a feed ratio of methane to oxygen carrier of 1 and a reaction pressure of 1 to 12 atm. See fig. 14 (b).
3) CO from R101 reactor2And H2Introducing O and Fe carrier from R102 reactor into a CO-cracking reactor R103 at 850 deg.C, and introducing CO2The feeding ratio with the oxygen carrier was 0.4 and the reaction pressure was 1 to 12atm see (c) in FIG. 14.
4) Introducing water vapor and an oxygen carrier FeO from the R103 reactor into a hydrogen production reactor R104 with the temperature of 500 ℃, wherein the feeding ratio of the water vapor to the oxygen carrier is 1.1, and the reaction pressure is 1-12 atm. See (d) in fig. 14.
5) Air with oxygen carrier Fe from R104 reactor3O4The oxygen carrier regeneration reactor R105 was charged at a temperature of 500 ℃ with a feed ratio of air to oxygen carrier of 1.5 and a reaction pressure of 1 atm.
6) The above steps are repeated in a circulating way to realize the in-situ utilization of CO2Chemical chain coupling process for coproducing synthesis gas and hydrogen.
The invention provides an in-situ utilization method of CO2A chemical-looping coupled process for co-producing synthesis gas and hydrogen is schematically illustrated in fig. 1. It combines CL-SMR with Chemical Looping Combustion (CLC) and CO2-H2Combined with O co-cracking, 5 reactors were included: a fuel combustion reactor R101, a fuel reforming reactor R102, a co-cracking reactor R103, a steam reactor R104, and an air reactor R105. In conventional CL-SMR, the CO at the initial stage2Not only reduces the selectivity of the synthesis gas, but also leads to the greenhouse gas CO2And (4) discharging. However, in the coupling process proposed in this application, the CO initially formed in the R101 reactor2And H2O is no longer vented or mixed with syngas, but rather is used as a co-cracking feedstock to generate additional syngas in the R103 reactor. This not only greatly increases the purity of the synthesis gas, but also increases the overall yield of the synthesis gas. Further, (CO) in R1032+H2O) can remove carbon deposit possibly formed in R102, and avoid polluting high-purity H generated in subsequent R1042. In this chemical chain coupling process, not only can ideal H be produced separately2Syngas and high purity hydrogen suitable for Fischer-Tropsch (F-T) synthesis with a/CO ratio (2), and also the ability to utilize the greenhouse gas CO2. In addition, synthesis gas regulation, hydrogen purification and carbon dioxide capture and storage are not needed, and cost is greatly saved. Compared to SE-CLR, our coupled process circulates only the oxygen carrier, and therefore has fewer problems in solids handling and greater flexibility in the setting of the operating temperature and feed ratio of the reactor.
The present invention is schematically illustrated in FIG. 2, in which two CH streams are present4Are all used for the direct or indirect production of synthesis gas, CH4-1 Combustion with oxygen Carrier in R101 reactor to CO2And H2O, consuming the surface oxygen of the oxygen carrier; CH (CH)4-2 reforming reaction with oxygen carrier depleted of surface oxygen in R102 reactor to high quality synthesis gas; CO produced in R101 reactor2And H2Introducing O into R103 reactor, generating synthesis gas by CO-cracking reaction, and adding supplementary CO according to a certain proportion2And H2O can produce more syngas and, if not supplemented, more high purity hydrogen in the R104 reactor; the solid in the R103 reactor enters the R104 reactor after passing through the gas-solid separator, and is subjected to cracking reaction with water vapor to prepare hydrogen, so that high-purity hydrogen can be obtained only by simple condensed water, and a complex and high-energy-consumption separation process is avoided. In this process, CO will be produced2The in-situ utilization generates more valuable synthesis gas, realizes in-situ conversion and utilization of carbon dioxide, and avoids complex steps of synthesis gas and hydrogen separation and purification. The coupling process can produce high-purity hydrogen and synthesis gas without pollutant and greenhouse gas emission, and realizes full utilization of raw materials and oxygen carriers. In addition, the method also saves the equipment investment and the operation cost of units such as water gas shift reaction, amine washing (MDEA), (PSA) and the like,
the efficiency is improved from 65.2% of the traditional steam methane reforming technical route to 72.04%.
A relevant model is built by adopting Aspen Plus software, reactors all adopt Gibbs reactor modules, waste heat of gas at the outlet of the reactor is used for preheating feed gas and generating water vapor, a heat exchange network is added in the system as shown in figure 3, energy balance analysis is carried out on the heat exchange network as shown in figure 4, energy balance can be achieved, and the energy efficiency of the system is up to 90.54%.
The product flow rate, oxygen carrier conversion, raw material conversion rate, product yield and the like of five reactors at different feeding ratios are respectively explored, and the results are shown as (a) and (b) in figure 5, (a), (b) and (c) in figure 6, (a), (b) and (c) in figure 7, (a) and (b) in figure 8 and figure 9. Fe can be found2O3/CH4At a molar ratio of-1 up to 4, the methane is substantially completely converted to CO2And H2O；CH4When the molar ratio of 2/FeO reaches 1, the yield of the synthesis gas-1 is maximum (97%) and the optimal hydrogen-carbon ratio (2) is reached; CO 22At a/Fe molar ratio of 0.4, the yield of syngas-2 is 83% and the hydrogen to carbon ratio is close to 2; h2When the molar ratio of O/FeO reaches 1.1, the FeO can be completely converted into Fe3O4And 2.67 kmol/hydrogen was generated; Air/Fe3O4When the molar ratio is more than 1.2, the oxygen carrier can be completely recovered.
In optimizing the above Fe2O3/CH4-1、CH4-2/FeO、CO2/Fe、H2O/FeO and Air/Fe3O4The effects of different temperatures and pressures on product flow, oxygen carrier conversion, feedstock conversion and product yield were investigated using the Aspen Plus software under molar ratio conditions, and the results are shown in (a) and (b) in FIG. 10, (a) and (b) in FIG. 11, (a), (b) and (c) in FIG. 12, (a) and (b) in FIG. 13 and (a), (b), (c) and (d) in FIG. 14. It was found that the R101 and R012 reactors performed relatively well at 900 deg.C, whereas the preferred temperature for the R103 reactor was 850 deg.C and the preferred temperature for the R104 reactor was finally 500 deg.C, R for energy savingThe preferred temperature for the 105 reactor is also 500 ℃. Referring again to FIG. 14, it can be seen that increasing the pressure has substantially no effect on the R101 and R104 reactors, whereas increasing the pressure decreases the syngas performance of the R102 and R103 reactors, so the preferred pressure for the final reactor is 1 atm.
Under preferred conditions, the results of the calculations by the Aspen Plus system are shown in Table 2.
Table 2 shows key evaluation indexes of chemical chain coupling system under preferable operation conditions
As can be seen from Table 2, the yields of the two synthesis gases were 97% and 84%, respectively, and the purity of the synthesis gases was 99% and 93%, respectively, with the desired hydrogen to carbon ratios (1.99 and 1.98). The purity of the hydrogen can reach 100%. Energy efficiency of the system and
the efficiency can reach 90.54% and 72.04% respectively. The embodiment can realize in-situ utilization of CO2The synthesis gas and the hydrogen are produced jointly, and the cyclic utilization of the oxygen carrier is realized.
The invention is used for utilizing CO in situ2To co-produce synthesis gas and hydrogen, CH4With an oxygen carrier Fe2O3Entering a chemical-looping combustion reactor, consuming lattice oxygen on the surface of an oxygen carrier and generating CO2And H2O; the partially reduced oxygen carrier FeO enters a chemical chain reforming reactor to prepare high-quality synthesis gas and is reduced into Fe in one step; and self-combustion reactor CO2And H2O and reduced oxygen carrier Fe from the reforming reactor are used for producing synthesis gas in the co-cracking reactor, and the reduced oxygen carrier Fe is oxidized into FeO; oxygen carrier FeO and water vapor from the co-cracking reactor enter a hydrogen production reactor, the oxygen carrier is oxidized, and most of the water vapor is reduced into hydrogen; oxygen carrier (FeO) from the hydrogen production reactor and air from the atmosphere enter the air reactor, the oxygen carrier is oxidized to the maximum valence state, and then the oxygen carrier is sent to chemical chain combustionThe reactor is burned for reaction. The process can not only obtain high-quality synthesis gas and hydrogen, but also realize CO2Zero emission, conversion to synthesis gas, and avoidance of synthesis gas and H which are energy intensive2The separation and purification step (2).
Although preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the present invention.
Claims (9)
1. A chemical chain coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ is characterized by comprising the following steps:
1) reaction of fuel and oxygen carrier to CO2And H2O, passing through a gas-solid separator to obtain gas and partially reduced solid;
2) reacting the fuel with the partially reduced solid obtained in the step 1) to generate synthesis gas, and passing the synthesis gas through a gas-solid separator to obtain reduced solid and synthesis gas;
3) carrying out a cracking reaction on the gas obtained in the step 1) and the reduced solid obtained in the step 2) to generate synthesis gas, and passing the synthesis gas through a gas-solid separator to obtain solid and synthesis gas;
4) reacting the water vapor with the solid obtained in the step 3) to generate hydrogen, and passing the hydrogen through a gas-solid separator to obtain partially oxidized solid and hydrogen;
5) and (3) reacting air with the solid obtained in the step (4) to oxidize and regenerate the solid, and enabling the solid to enter the step (1) for next recycling after passing through a gas-solid separator.
2. The chemical-looping coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ according to claim 1, wherein the fuel in the step 1) and the step 2) is methane.
3. The chemical-looping coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ according to claim 1, wherein the oxygen carrier in the step 1) is one of the following oxygen carriers: fe2O3、FeO、Fe、Fe3O4Sodium-modified Fe2O3/Al2O3Oxygen carrier, Fe2O3/Al2O3(1.5-Y2O3) Oxygen carrier, nickel-strengthened Fe2O3/Al2O3Oxygen carrier, Fe2O3/Al2O3Oxygen carrier, Ce-Fe-Zr-O/MgO monolithic oxygen carrier, CeO2Modified Fe2O3Oxygen carrier, CeO2Hematite oxygen carrier, NiFe2O4Oxygen carrier, Fe2O3/MgAl2O4An oxygen carrier; la1.6Sr0.4FeCoO6An oxygen carrier; La-Fe-Al oxygen carrier;
Sr(Fe1-xCux)O3-δan oxygen carrier, wherein x is 0, 0.1 or 0.33;
CaTi0.125Mn0.875-xFexTi0.125O3-δan oxygen carrier, wherein x is 0, 0.05, 0.1, 0.15 or 0.2;
BaFe2.8M0.2Al9O19an oxygen carrier, wherein M ═ Fe, Si, Zr, or Ce;
BaFe2MAll9O19an oxygen carrier, wherein M ═ Mn, Ni, or Co;
AFexAl12-xO19oxygen carrier, wherein A ═ La or Ba, 0<x<5；
CeO2And AFenAl12-nO19A composite oxygen carrier, wherein A ═ La or Ba, 0<n≤12；
A1-xBxFe12-xMyO19An oxygen carrier, wherein A ═ La ═ Ba, M ═ Sn, Zr or Ce, 0.2. ltoreq. x.ltoreq.0.6, 0.2. ltoreq. y.ltoreq.1.2.
4. The chemical-looping coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ according to claim 1, wherein the molar ratio of the solid to the fuel in the step 1) is (1-12): 1, the reaction temperature is 200-1500 ℃.
5. The chemical-looping coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ according to claim 1, wherein the molar ratio of the fuel to the solid in the step 2) is (0.25-1.25): 1, the reaction temperature is 200-1500 ℃.
6. The chemical-looping coupling process for CO-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ according to claim 1, wherein CO in the step 3)2Molar ratio to solid (0.11-0.62): 1, the reaction temperature is 200-1500 ℃.
7. The chemical-looping coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ according to claim 1, wherein H in the step 4) is2The molar ratio of O to solid is (0.1-1.9): 1, the reaction temperature is 200-1500 ℃.
8. The chemical-looping coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ according to claim 1, wherein the molar ratio of air to solid in the step 5) is (0.75-2.25): 1, the reaction temperature is 200-1500 ℃.
9. The chemical-looping coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ according to claim 1, wherein the reaction pressure in the steps 1) -5) is 1-12 atm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275736A (en) * | 2021-11-30 | 2022-04-05 | 西安交通大学 | Chemical-looping CO (carbon monoxide) method taking red mud as oxygen carrier2Graded regeneration process and system |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050175533A1 (en) * | 2003-12-11 | 2005-08-11 | Thomas Theodore J. | Combustion looping using composite oxygen carriers |
| US20050232859A1 (en) * | 2004-03-23 | 2005-10-20 | Eni S.P.A. | Process for the production of hydrogen and the co-production of carbon dioxide |
| KR20140133077A (en) * | 2013-05-09 | 2014-11-19 | 한국에너지기술연구원 | Combined steam and CO2 reforming method of methane in GTL process |
| CN104591087A (en) * | 2015-02-17 | 2015-05-06 | 重庆大学 | Collaborative process for reforming biomass chemical chains to produce hydrogen and inhibit production of tar |
| CN108117045A (en) * | 2017-12-12 | 2018-06-05 | 西北大学 | A kind of apparatus and method of collecting carbonic anhydride and methane reforming process coupled cogeneration synthesis gas |
| CN108328576A (en) * | 2017-12-26 | 2018-07-27 | 华中科技大学 | A kind of co-generation unit based on chemical chain methane reforming process for making hydrogen |
| US10106407B1 (en) * | 2017-04-26 | 2018-10-23 | U.S. Department Of Energy | Metal ferrite oxygen carriers/catalyst for partial oxidation of methane for production of synthesis gas |
| CN108726480A (en) * | 2018-05-30 | 2018-11-02 | 东南大学 | A kind of device and method preparing the adjustable synthesis gas of C/Hratio using ferriferous oxide and natural gas |
| CN108855109A (en) * | 2018-07-02 | 2018-11-23 | 西北大学 | A kind of chemical chain partial oxidation methane preparing synthetic gas carrier of oxygen and its preparation method and application |
| WO2020210865A1 (en) * | 2019-04-18 | 2020-10-22 | Commonwealth Scientific And Industrial Research Organisation | Chemical looping process for the production of hydrogen |
-
2020
- 2020-12-31 CN CN202011637018.4A patent/CN112744785B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050175533A1 (en) * | 2003-12-11 | 2005-08-11 | Thomas Theodore J. | Combustion looping using composite oxygen carriers |
| US20050232859A1 (en) * | 2004-03-23 | 2005-10-20 | Eni S.P.A. | Process for the production of hydrogen and the co-production of carbon dioxide |
| KR20140133077A (en) * | 2013-05-09 | 2014-11-19 | 한국에너지기술연구원 | Combined steam and CO2 reforming method of methane in GTL process |
| CN104591087A (en) * | 2015-02-17 | 2015-05-06 | 重庆大学 | Collaborative process for reforming biomass chemical chains to produce hydrogen and inhibit production of tar |
| US10106407B1 (en) * | 2017-04-26 | 2018-10-23 | U.S. Department Of Energy | Metal ferrite oxygen carriers/catalyst for partial oxidation of methane for production of synthesis gas |
| CN108117045A (en) * | 2017-12-12 | 2018-06-05 | 西北大学 | A kind of apparatus and method of collecting carbonic anhydride and methane reforming process coupled cogeneration synthesis gas |
| CN108328576A (en) * | 2017-12-26 | 2018-07-27 | 华中科技大学 | A kind of co-generation unit based on chemical chain methane reforming process for making hydrogen |
| CN108726480A (en) * | 2018-05-30 | 2018-11-02 | 东南大学 | A kind of device and method preparing the adjustable synthesis gas of C/Hratio using ferriferous oxide and natural gas |
| CN108855109A (en) * | 2018-07-02 | 2018-11-23 | 西北大学 | A kind of chemical chain partial oxidation methane preparing synthetic gas carrier of oxygen and its preparation method and application |
| WO2020210865A1 (en) * | 2019-04-18 | 2020-10-22 | Commonwealth Scientific And Industrial Research Organisation | Chemical looping process for the production of hydrogen |
Non-Patent Citations (2)
| Title |
|---|
| QIANQIAN SHEN等: "Effect of Regeneration period on the selectivity of synthesis gas of Ba-hexaaluminates in chemical looping partial oxidation of methane", ACS CATALYSIS, no. 9, pages 722 - 731 * |
| 苏小平等: "甲烷化学链重整制合成气的研究进展", 地下水, vol. 39, no. 4, pages 198 - 202 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275736A (en) * | 2021-11-30 | 2022-04-05 | 西安交通大学 | Chemical-looping CO (carbon monoxide) method taking red mud as oxygen carrier2Graded regeneration process and system |
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