CN112744785B - Chemical chain coupling process for co-producing synthesis gas and hydrogen by in-situ utilization of carbon dioxide - Google Patents
Chemical chain coupling process for co-producing synthesis gas and hydrogen by in-situ utilization of carbon dioxide Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 121
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 96
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 96
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 75
- 239000001257 hydrogen Substances 0.000 title claims abstract description 73
- 239000000126 substance Substances 0.000 title claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000010168 coupling process Methods 0.000 title claims abstract description 38
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 245
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 244
- 239000001301 oxygen Substances 0.000 claims abstract description 244
- 239000007787 solid Substances 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000000446 fuel Substances 0.000 claims abstract description 52
- 238000005336 cracking Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 92
- 238000004519 manufacturing process Methods 0.000 claims description 32
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 239000000969 carrier Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910020068 MgAl Inorganic materials 0.000 claims description 3
- 229910007746 Zr—O Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000011019 hematite Substances 0.000 claims description 3
- 229910052595 hematite Inorganic materials 0.000 claims description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 67
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 60
- 230000000694 effects Effects 0.000 description 35
- 238000002485 combustion reaction Methods 0.000 description 22
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- 238000007254 oxidation reaction Methods 0.000 description 7
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- 239000003463 adsorbent Substances 0.000 description 6
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- 230000008878 coupling Effects 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000183024 Populus tremula Species 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
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- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
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- 238000001991 steam methane reforming Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- 101100348341 Caenorhabditis elegans gas-1 gene Proteins 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- 101100447658 Mus musculus Gas1 gene Proteins 0.000 description 1
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- 239000000292 calcium oxide Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
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- 238000000629 steam reforming Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C01B3/08—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
-
- 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
- C01B3/10—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B2203/12—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
-
- 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
Abstract
The application provides a chemical chain coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ, which comprises the following steps: 1) Reaction of fuel and oxygen carrier to form CO 2 And H 2 O, 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 obtaining the solid and the synthesis gas through a gas-solid separator; 3) The gas obtained in the step 1) and the solid obtained in the step 2) are subjected to a cracking reaction to generate synthesis gas, and the synthesis gas and the solid are obtained through a gas-solid separator; 4) The water vapor reacts with the solid obtained in the step 3) to generate hydrogen, and the hydrogen and the solid are obtained through a gas-solid separator; 5) Air reacts with the solid obtained in the step 4) to enable the solid to be oxidized and regenerated, and the solid enters the step 1) for the next recycling after passing through a gas-solid separator. The application can obtain high-quality synthesis gas and hydrogen and realize CO 2 And converts it to synthesis gas.
Description
Technical Field
The application relates to the field of synthesis gas and hydrogen prepared by chemical chains, in particular to a chemical chain coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ.
Background
With the increase of global energy demands 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 increasingly emphasized. The conversion of natural gas to synthesis gas and hydrogen is very important in the world, as the former is an important feedstock for the synthesis of many chemicals and liquid fuels, and the latter is a clean energy source of high energy density.
Steam reforming of methane (SMR, CH) 4 +H 2 O＝CO+3H 2 ) Is a relatively mature technology for converting methane into synthesis gas or hydrogen. However, H of the synthesis gas produced 2 The molar ratio of/CO is 3, which is detrimental to the subsequent Fischer-Tropsch synthesis (ideal H 2 The ratio of/CO is 2), and a subsequent gas conditioning process is required. In order to obtain high purity hydrogen, however, it is also necessary to perform a Water Gas Shift (WGS) reaction and complicated separation and purification steps such as amine washing or Pressure Swing Adsorption (PSA). The SMR reaction itself has strong heat absorption, and the regulation of the synthesis gas and the separation and purification of high-purity hydrogen exacerbate the consumption of energy. The emission of large amounts of carbon dioxide also accelerates the pace of global warming.
Chemical chain-steam methane reforming (CL-SMR) is an emerging technology for the cyclic low energy generation of synthesis gas and high purity hydrogen based on solid oxygen carriers, typically transition metal oxides. In the fuel reactor, methane is partially oxidized to synthesis gas by lattice oxygen (MeOx) of the oxygen carrier, and then the reduced oxygen carrier (Me) is oxidized by water vapor to recover lattice oxygen, while hydrogen is produced by a water vapor cracking reaction. The high purity hydrogen can be obtained by simply condensing the water vapor.
In the fuel reactor, the surface oxygen of the fuel and the solid oxygen carrier reacts with the lattice oxygen, so that the oxygen species in the oxygen carrier have a great influence on the distribution of the product. In general, the fuel is first reacted with reactive surface oxygen to give the complete oxidation product (CO 2 And H 2 O) and then the less reactive lattice oxygen selectively oxidizes the fuel partially to CO and H 2 . In order to increase the selectivity of the synthesis gas, the initially produced carbon dioxide content should be minimized. With air/O 2 A weak oxidant (H) 2 O or CO 2 ) The selectivity of the synthesis gas can be increased by modulating the distribution of oxygen species. However, the oxidation power of water is weak, the oxygen carrier cannot be recovered thoroughly, and the oxygen carrier is easy to deactivate in the long-term oxidation-reduction 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 exothermic property can be utilized to provide energy for the system. However, due to air/O 2 Has relatively high oxidizing power and air/O 2 The oxidation of (a) inevitably leads to an enrichment of reactive oxygen species which tend to lead to complete oxidation of the fuel and CO 2 Instead of selective oxidation, thereby reducing the overall selectivity of the syngas and exacerbating global warming.
Many researchers have tried to modify oxygen carriers and examined the influence of the properties such as composition, structure and morphology, but it is difficult to avoid CO formed at the initial stage of the reaction 2 . In addition to the reduced selectivity of synthesis gas, the increase in carbon dioxide content at the initial stage can undoubtedly lead to carbon dioxide emissions due to excessive oxidation of air, exacerbating the greenhouse effect. Therefore, there is a need to develop a new technology to combine CL-SMR with in situ CO 2 And the trapping is combined, so that low energy consumption and low carbon footprint are realized.
So far, most research has focused on adsorption-enhanced chemical chain reforming (SE-CLR). Adsorption-enhanced chemical chain reforming typically uses iron oxide as the oxygen carrier and calcium oxide (CaO) as CO 2 An adsorbent. In the process, fuel CH 4 、H 2 O, oxygen carrier and CO 2 The adsorbent (CaO) is introduced into the fuel reactor together, during which the reforming reaction, the WGS reaction and the CO 2 Adsorption reactions are carried out simultaneously, and CO can be realized 2 Is trapped and yields hydrogen-rich synthesis gas, but cannot yield H 2 a/CO ratio of 2. Due to CO 2 The adsorbent is consumed in the fuel reaction and therefore requires high temperature calcination to regenerate the CO 2 An adsorbent. When air is used as an oxidant to regenerate the oxygen carrier and the adsorbent, the desorbed CO 2 Is highly diluted in nitrogen, additional equipment or processes are still required to process and utilize the captured carbon dioxide. Furthermore, oxygen carrier and CO are used simultaneously 2 Adsorbents also increase the difficulty of solids handling.
Disclosure of Invention
In order to overcome the problems in the prior art, the application aims to provide a chemical chain coupling process for co-producing synthesis gas and hydrogen by utilizing carbon dioxide in situ.
In order to achieve the above purpose, the application adopts the following technical scheme:
in-situ utilization of CO 2 A chemical chain coupling process for co-producing synthesis gas and hydrogen, comprising the steps of:
1) Reaction of fuel and oxygen carrier to form CO 2 And H 2 O, passing through a gas-solid separator to obtain gas and partially reduced solid;
2) The fuel reacts with the partially reduced solid obtained in the step 1) to generate synthesis gas, and the synthesis gas and the reduced solid are obtained through a gas-solid separator;
3) The gas obtained in the step 1) and the reduced solid obtained in the step 2) are subjected to a cracking reaction to generate synthesis gas, and the synthesis gas and the solid are obtained through a gas-solid separator;
4) The water vapor reacts with the solid obtained in the step 3) to generate hydrogen, and the hydrogen and the solid which are partially oxidized are obtained through a gas-solid separator;
5) Air reacts with the solid obtained in the step 4) to enable the solid to be oxidized and regenerated, and the solid enters the step 1) for the next recycling after passing through a gas-solid separator.
The application is further improved in that the fuel in step 1) and step 2) is methane.
The application is further improved in that the oxygen carrier in step 1) is one of the following oxygen carriers: fe (Fe) 2 O 3 、FeO、Fe、Fe 3 O 4 Sodium modified Fe 2 O 3 /Al 2 O 3 Oxygen carrier, fe 2 O 3 /Al 2 O 3 (1.5-Y 2 O 3 ) Oxygen carrier, nickel-enriched Fe 2 O 3 /Al 2 O 3 Oxygen carrier, fe 2 O 3 /Al 2 O 3 Oxygen carrier, ce-Fe-Zr-O/MgO integrated oxygen carrier, ceO 2 Modified Fe 2 O 3 Oxygen carrier, ceO 2 Hematite oxygen carrierBulk, niFe 2 O 4 Oxygen carrier, fe 2 O 3 /MgAl 2 O 4 An oxygen carrier; la (La) 1.6 Sr 0.4 FeCoO 6 An oxygen carrier; la-Fe-Al oxygen carrier;
Sr(Fe 1-x Cu x )O 3-δ an oxygen carrier, wherein x= 0,0.1 or 0.33;
CaTi 0.125 Mn 0.875-x Fe x Ti 0.125 O 3-δ an oxygen carrier, wherein x= 0,0.05,0.1,0.15 or 0.2;
BaFe 2.8 M 0.2 Al 9 O 19 an oxygen carrier, wherein m=fe, si, zr, or Ce;
BaFe 2 MAl l9 O 19 an oxygen carrier, wherein m=mn, ni or Co;
AFe x Al 12-x O 19 oxygen carrier, wherein a=la or Ba,0<x<5；
CeO 2 And AFe n Al 12-n O 19 A composite oxygen carrier, wherein a=la or Ba,0<n≤12；
A 1-x B x Fe 12-x M y O 19 An oxygen carrier, wherein A=La, B=Ba, M=Sn, zr or Ce, 0.2.ltoreq.x.ltoreq. 0.6,0.2.ltoreq.y.ltoreq.1.2.
The application is further improved in that the mole ratio of the solid to the fuel in the step 1) is (1-12): 1, the reaction temperature is 200-1500 ℃.
The application is further improved in that the molar ratio of fuel to solid in step 2) is (0.25-1.25): 1, the reaction temperature is 200-1500 ℃.
A further development of the application is that in step 3) the CO 2 The molar ratio to the solid is (0.11-0.62): 1, the reaction temperature is 200-1500 ℃.
A further development of the application is that in step 4) H 2 The molar ratio of O to solid is (0.1-1.9): 1, the reaction temperature is 200-1500 ℃.
The application is further improved in that the molar ratio of air to solid in step 5) is (0.75-2.25): 1, the reaction temperature is 200-1500 ℃.
A further improvement of the present application is that the pressure of the reactions in steps 1) to 5) is 1 to 12atm.
Compared with the prior art, the application has the beneficial effects that:
the application combines CL-SMR with Chemical Looping Combustion (CLC) and CO 2 -H 2 O co-cleavage combined, comprised 5 reactors: 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, CO at the initial stage 2 Not only reduces the selectivity of the synthesis gas, but also leads to the greenhouse gas CO 2 Is arranged in the air. However, in the coupling process proposed by the present application, CO is initially formed in the R101 reactor 2 And H 2 O is no longer vented or mixed with the synthesis gas but rather as a co-cracking feedstock produces additional synthesis gas in the R103 reactor. This not only greatly increases the purity of the synthesis gas in the fuel reforming reactor (R102), but also increases the overall yield of synthesis gas. In addition, in R103 (CO 2 +H 2 O) can remove carbon deposit possibly formed in R102 and avoid pollution to high-purity H generated in subsequent R104 2 . In this chemical chain coupling process, not only the desired H can be produced separately 2 Fischer-Tropsch synthesis compatible synthesis gas and high purity hydrogen in a CO ratio of 2, and also the greenhouse gas CO 2 . In addition, synthesis gas conditioning, hydrogen purification and carbon dioxide capture and storage are not needed, so that the cost is greatly saved. Our coupled process circulates only the oxygen carrier compared to SE-CLR, thus having fewer problems in solids handling and greater flexibility in setting the operating temperature and feed ratio of the reactor.
The coupling process product of the application has two H 2 The conversion rate of methane in the R101 and R102 reactors is up to 100% and 98% and the yield of the synthesis gas in the R102 and R103 reactors is 97% and 84%, and the two synthesis gases and H 2 The purity is as high as 93%, 99% and 100%, respectively, and the gas separation cost is greatly reduced.Coupling system added with heat exchange network and its overall energy utilization efficiency andthe efficiency is up to 90.54% and 72.04%, respectively, and CO is utilized in situ 2 Avoiding CO 2 Is trapped and sealed; the method has the advantages of less pollutant emission, lower requirements on various process unit equipment, 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, which comprises Fe in different oxidation states and reduction states 2 O 3 、Fe 3 O 4 FeO and Fe. The carrier may be Al 2 O 3 、CeO 2 MgO, spinel, perovskite or hexaaluminate, etc.
Drawings
FIG. 1 is a schematic diagram of a chemical chain coupling process.
Fig. 2 is a schematic flow chart of a chemical chain coupling system.
FIG. 3 is a flow chart of a chemical looping coupling system including a heat exchange network.
FIG. 4 is a graph of energy balance analysis of a chemical chain coupling system.
FIG. 5 is Fe 2 O 3 /CH 4 Effect of 1 molar ratio on product and oxygen carrier conversion. Wherein (a) is the effect on the gas phase component and (b) is the effect on the solid phase component. Wherein CH is 4 -1 is methane entering the R101 reactor.
FIG. 6 is CH 4 Effect of 2/FeO molar ratio on product and oxygen carrier conversion. Wherein, (a) is the effect on the gas phase component, (b) is the effect on the solid phase component, and (c) is the effect on the main evaluation index of the gas phase component. Wherein CH is 4 -2 is methane entering the R102 reactor.
FIG. 7 is CO 2 Effect of Fe molar ratio on product and oxygen carrier conversion. Wherein, (a) is the effect on the gas phase component, (b) is the effect on the solid phase component, and (c) is the effect on the main evaluation index of the gas phase component.
FIG. 8 is H 2 Effect of O/FeO molar ratio on product and oxygen carrier conversion. Wherein (a)) In order to affect the gas phase component, (b) in order to affect the solid phase component.
FIG. 9 is Air/Fe 3 O 4 Effect of molar ratio oxygen carrier conversion.
FIG. 10 is a graph showing the effect of temperature on the conversion of product and oxygen carrier in the R101 reactor. Wherein (a) is the effect on the gas phase component and (b) is the effect on the solid phase component.
FIG. 11 is a graph showing the effect of temperature on the conversion of product and oxygen carrier in the R102 reactor. Wherein, (a) is the effect on the gas phase component, (b) is the effect on the solid phase component, and (c) is the effect on the main evaluation index of the gas phase component.
FIG. 12 is a graph showing the effect of temperature on the conversion of product and oxygen carrier in the R103 reactor. Wherein, (a) is the effect on the gas phase component, (b) is the effect on the solid phase component, and (c) is the effect on the main evaluation index of the gas phase component.
FIG. 13 is a graph showing the effect of temperature on the conversion of product and oxygen carrier in the R104 reactor. Wherein (a) is the effect on the gas phase component and (b) is the effect on the solid phase component.
FIG. 14 is the effect of pressure on product and oxygen carrier conversion in the reactor. Wherein, (a) is the effect on the conversion of the product and oxygen carrier in the R101 reactor, (b) is the effect on the conversion of the product and oxygen carrier in the R102 reactor, (c) is the effect on the conversion of the product and oxygen carrier in the R103 reactor, and (d) is the effect on the conversion of the product and oxygen carrier in the R104 reactor.
Detailed Description
The present application will be described in detail with reference to the accompanying drawings.
As shown in FIG. 1, the application comprises a chemical looping combustion reactor, a reactor for preparing synthesis gas by chemical looping reforming, and CO 2 And H 2 The reactor for preparing synthesis gas by O co-pyrolysis, the reactor for preparing hydrogen by water pyrolysis and the reactor for regenerating oxygen carrier by air. The application relates to two CH 4 ，CH 4 -1 and CH 4 -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 2 O 3 ) Is introduced into a combustion reactor (R101). Introduced fuel (CH) 4 ) Is completely oxidized into CO 2 And H 2 O, and the oxygen carrier is reduced to a lower valence state (FeO). Gas component CO after separation device (SEP 101) 2 And H 2 The O enters the cracking reactor (R103) to produce additional synthesis gas, rather than being captured and sequestered. Wherein the feed ratio (molar ratio) of the reactor R101 is Fe 2 O 3 /CH 4 -1 is 1-12, the operating temperature is 200-1500 ℃, and the operating pressure is 1-12atm; preferably, the feed ratio Fe 2 O 3 /CH 4 -1 is 4, the operating temperature is 900 ℃, and the operating pressure is 1atm.
R101 reactor: chemical looping combustion
CH 4 +4Fe 2 O 3 →CO 2 +2H 2 O+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 SEP102, the gas component (syngas-1) is collected as product 1. At the same time, the reduced oxygen carrier (FeO) is further reduced to metallic state (Fe). Wherein the feed ratio CH of the reactor R102 4 -2/FeO of 0.25-1.25, operating temperature of 200-1500 ℃, operating pressure of 1-12atm; preferably, the feed ratio CH 4 -2/FeO of 4, operating temperature of 900 ℃, operating pressure of 1atm.
R102 reactor: chemical chain reforming to make synthetic gas
CH 4 +FeO→CO+2H 2 +Fe
3) Metal (Fe) enters the R103 reactor to react with CO in the SEP101 2 And H 2 The O mixture being reacted with or without addition of starting materials (CO 2 And H 2 O), generating additional synthesis gas by co-cracking; the gas component (syngas-2) after SEP103 was collected as product 2. Therefore, the R102 and R103 reactors are used for producing the synthesis gas, thereby greatly improving the yield of the synthesis gas and avoiding CO 2 Is captured and sequestered. Wherein the reaction isThe feed ratio of the R103 reactor was CO 2 Fe is 0.11-0.62, the operating temperature is 200-1500 ℃, and the operating pressure is 1-12atm; preferably, the feed ratio CO 2 Fe is 0.4, the operating temperature is 850 ℃, and the operating pressure is 1atm.
R103 reactor: CO 2 And H 2 Co-cracking of O to produce synthesis gas
CO 2 +2H 2 O+3Fe→CO+2H 2 +3FeO
4) Solid component FeO from the R102 reactor enters the R104 reactor and reacts with water vapor to generate hydrogen, feO- & gtFe 3 O 4 Oxidizing to generate hydrogen. Separating (SEP 104) and condensing to obtain high-purity H 2 As product 3. Wherein the feed ratio H of the reactor R104 2 O/FeO is 0.1-1.9, the operating temperature is 200-1500 ℃, and the operating pressure is 1-12atm; preferably, the feed ratio H 2 O/FeO was 4, the operating temperature was 500℃and the operating pressure was 1atm.
R104 reactor: hydrogen production by steam cracking
H 2 O+3FeO→H 2 +Fe 3 O 4
5) Since air has a strong oxidizing ability, the solid component (Fe 3 O 4 ) Is completely oxidized to Fe in an air reactor (R105) 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the After the SEP105-10 separator, fe 2 O 3 Enters the combustion reactor (R101) to start the next cycle. Wherein, the feeding ratio Air/Fe of the reactor R105 3 O 4 0.75-2.25, operating temperature of 200-1500 ℃ and operating pressure of 1-12atm; preferably, the feed ratio Air/Fe 3 O 4 4, the operating temperature was 500℃and the operating pressure was 1atm.
R105 reactor: oxygen carrier regeneration
O 2 +4Fe 3 O 4 →6Fe 2 O 3
The following are specific examples.
Example 1
1) Fuel CH 4 With oxygen carrier Fe 2 O 3 The mixture was introduced into a chemical looping combustion reactor R101 at a temperature of 900℃and a pressure of 1atm, the flow rate of methane was 1kmol/h, and the feed ratio of oxygen carrier to methane was 4.
2) Fuel CH 4 With the oxygen carrier FeO from the R101 reactor, the feed ratio of methane to oxygen carrier was 1 by passing into the chemical chain reforming reactor R102 at 900 ℃ and 1atm pressure.
3) CO from R101 reactor 2 And H 2 O and oxygen carrier Fe from R102 reactor are introduced into a CO-cracking reactor R103, CO with the temperature of 850 ℃ and the pressure of 1atm 2 The feed ratio to the oxygen carrier was 0.4.
4) The steam and the oxygen carrier FeO from the R103 reactor were introduced into the hydrogen production reactor R104 at a temperature of 500℃and a pressure of 1atm, and the feed ratio of the steam to the oxygen carrier was 1.1.
5) Air was combined with oxygen carrier Fe from R104 reactor 3 O 4 An oxygen carrier regeneration reactor R105 having a temperature of 500℃and a pressure of 1atm was fed with a feed ratio of air to oxygen carrier of 1.5.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 2
1) Fuel CH 4 Modified with sodium Fe 2 O 3 /Al 2 O 3 Oxygen carrier is introduced into a chemical looping combustion reactor R101 with the temperature of 200 ℃ and the pressure of 12atm, the flow rate of methane is 1kmol/h, and the feeding ratio of the oxygen carrier to the methane is 6.
2) Fuel CH 4 With oxygen carrier from R101 reactor, the mixture was fed into a chemical chain reforming reactor R102 at a temperature of 500℃and a pressure of 7atm, and the feed ratio of methane to oxygen carrier was 0.25.
3) CO from R101 reactor 2 And H 2 O and oxygen carrier from R102 reactor are introduced into CO-cracking reactor R103, CO with temperature of 200 ℃ and pressure of 12atm 2 The feed ratio to the oxygen carrier was 0.11.
4) The steam and oxygen carrier from the R103 reactor were fed into a hydrogen production reactor R104 at 700℃and a pressure of 8atm, and the feed ratio of the steam to the oxygen carrier was 1.9.
5) Air and oxygen carrier from the R104 reactor were fed into the oxygen carrier regeneration reactor R105 at a temperature of 200 ℃ and a pressure of 12atm, and the feed ratio of air to oxygen carrier was 0.75.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 3
1) Fuel CH 4 With CeO 2 Modified Fe 2 O 3 Oxygen carrier is introduced into 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 CH 4 With oxygen carrier from R101 reactor, the mixture was fed into a chemical chain reforming reactor R102 at a temperature of 300℃and a pressure of 12atm, and the feed ratio of methane to oxygen carrier was 0.75.
3) CO from R101 reactor 2 And H 2 O and oxygen carrier from R102 reactor are introduced into CO-cracking reactor R103, CO with temperature of 800 ℃ and pressure of 8atm 2 The feed ratio to the oxygen carrier was 0.3.
4) Steam and oxygen carrier from the R103 reactor were fed into a hydrogen production reactor R104 at a temperature of 200℃and a pressure of 12atm, and the feed ratio of steam to oxygen carrier was 0.1.
5) Air and oxygen carrier from the R104 reactor were fed into the oxygen carrier regeneration reactor R105 at a temperature of 400 ℃ and a pressure of 5atm, and the feed ratio of air to oxygen carrier was 2.25.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 4
1) Fuel CH 4 With Fe 2 O 3 /Al 2 O 3 (1.5-Y 2 O 3 ) Oxygen carrier is introduced into a chemical looping combustion reactor R101 with the temperature of 700 ℃ and the pressure of 5atm, the flow rate of methane is 1kmol/h, and the feeding ratio of the oxygen carrier to the methane is 12.
2) Fuel CH 4 With oxygen carrier from R101 reactor, the mixture was fed into a chemical chain reforming reactor R102 at a temperature of 1500℃and a pressure of 10atm, and the feed ratio of methane to oxygen carrier was 1.25.
3) CO from R101 reactor 2 And H 2 O and oxygen carrier from R102 reactor are introduced into CO-cracking reactor R103, CO with temperature of 1200 ℃ and pressure of 4atm 2 The feed ratio to the oxygen carrier was 0.33.
4) The steam and oxygen carrier from the R103 reactor were fed into a hydrogen production reactor R104 at a temperature of 1500℃and a pressure of 11atm, and the feed ratio of the steam to the oxygen carrier was 0.9.
5) Air and oxygen carrier from the R104 reactor were introduced into the oxygen carrier regeneration reactor R105 at a temperature of 800 ℃ and a pressure of 6atm, and the feed ratio of air to oxygen carrier was 1.0.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 5
1) Fuel CH 4 With BaFe 2.8 M 0.2 Al 9 O 19 Oxygen carrier (m=fe, si, zr, or Ce) was fed into a chemical-looping combustion reactor R101 at 1200 ℃ and at a pressure of 10atm, the flow rate of methane was 1kmol/h, and the feed ratio of oxygen carrier to methane was 8.
2) Fuel CH 4 With oxygen carrier from the R101 reactor, the mixture was fed into a chemical chain reforming reactor R102 at 1300℃and a pressure of 6atm, and the feed ratio of methane to oxygen carrier was 0.5.
3) CO from R101 reactor 2 And H 2 O and oxygen carrier from R102 reactor are introduced into a CO-cracking reactor R103, CO with the temperature of 1500 ℃ and the pressure of 7atm 2 The feed ratio to the oxygen carrier was 0.5.
4) Steam and oxygen carrier from the R103 reactor were fed into a hydrogen production reactor R104 at 900℃and 5atm, and the feed ratio of steam to oxygen carrier was 0.7.
5) Air and oxygen carrier from the R104 reactor were introduced into the oxygen carrier regeneration reactor R105 at a temperature of 1000 ℃ and a pressure of 3atm, and the feed ratio of air to oxygen carrier was 1.5.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 6
1) Fuel CH 4 With CeO 2 And AFe n Al 12-n O 19 Composite oxygen carrier (a=la or Ba, 0)<n is less than or equal to 12), the mixture is introduced into a chemical looping combustion reactor R101 with the temperature of 400 ℃ and the pressure of 4atm, the flow rate of methane is 1kmol/h, and the feeding ratio of oxygen carrier to methane is 3.
2) Fuel CH 4 With oxygen carrier from R101 reactor, the mixture was fed into a chemical chain reforming reactor R102 at 200℃and 2atm, and the feed ratio of methane to oxygen carrier was 0.9.
3) CO from R101 reactor 2 And H 2 O and oxygen carrier from R102 reactor are introduced into CO-cracking reactor R103, CO with temperature of 400 ℃ and pressure of 6atm 2 The feed ratio to the oxygen carrier was 0.2.
4) Steam and oxygen carrier from the R103 reactor were fed into a hydrogen production reactor R104 at 800℃and 7atm, and the feed ratio of steam to oxygen carrier was 0.5.
5) Air and oxygen carrier from the R104 reactor were introduced into the oxygen carrier regeneration reactor R105 at a temperature of 1500 ℃ and a pressure of 10atm, and the feed ratio of air to oxygen carrier was 2.0.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 7
1) Fuel CH 4 With La 1.6 Sr 0.4 FeCoO 6 Oxygen carrier, introducing temperature of 1500 ℃ and pressureThe flow rate of methane was 1kmol/h and the feed ratio of oxygen carrier to methane was 6 for a chemical looping combustion reactor R101 of 8 atm.
2) Fuel CH 4 With oxygen carrier from R101 reactor, the feed ratio of methane to oxygen carrier was 0.4 by passing into chemical chain reforming reactor R102 at 600℃and 4 atm.
3) CO from R101 reactor 2 And H 2 O and oxygen carrier from R102 reactor are introduced into CO-cracking reactor R103, CO with temperature of 600 ℃ and pressure of 10atm 2 The feed ratio to the oxygen carrier was 0.55.
4) The steam and oxygen carrier from the R103 reactor were fed into a hydrogen production reactor R104 at 1100℃and 3atm, and the feed ratio of steam to oxygen carrier was 1.6.
5) Air and oxygen carrier from the R104 reactor were introduced into the oxygen carrier regeneration reactor R105 at a temperature of 900 ℃ and a pressure of 7atm, and the feed ratio of air to oxygen carrier was 1.3.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 8
1) Fuel CH 4 With Fe 2 O 3 /MgAl 2 O 4 Oxygen carrier is introduced into 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) Fuel CH 4 With oxygen carrier from R101 reactor, the mixture was fed into a chemical chain reforming reactor R102 at 1000℃and a pressure of 8atm, and the feed ratio of methane to oxygen carrier was 0.3.
3) CO from R101 reactor 2 And H 2 O and oxygen carrier from R102 reactor are introduced into CO-cracking reactor R103, CO with temperature of 1300 ℃ and pressure of 2atm 2 The feed ratio to the oxygen carrier was 0.62.
4) The steam and oxygen carrier from the R103 reactor were fed into a hydrogen production reactor R104 having a temperature of 1400℃and a pressure of 6atm, and the feed ratio of the steam to the oxygen carrier was 0.7.
5) Air and oxygen carrier from the R104 reactor were introduced into the oxygen carrier regeneration reactor R105 at a temperature of 1200 c and a pressure of 11atm, and the feed ratio of air to oxygen carrier was 1.7.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
The above embodiments may also use the following oxygen carriers:
nickel-reinforced Fe 2 O 3 /Al 2 O 3 Oxygen carrier, fe 2 O 3 /Al 2 O 3 Oxygen carrier, ce-Fe-Zr-O/MgO integrated oxygen carrier, ceO 2 Hematite oxygen carrier, niFe 2 O 4 Oxygen carrier, sr (Fe) 1-x Cu x )O 3-δ Oxygen carrier (x= 0,0.1 or 0.33), caTi 0.125 Mn 0.875-x Fe x Ti 0.125 O 3-δ Oxygen carrier (x= 0,0.05,0.1,0.15, or 0.2), la-Fe-Al oxygen carrier, baFe 2 MAl l9 O 19 Oxygen carrier (m=mn, ni, and Co), AFe x Al 12-x O 19 Oxygen carrier (a=la or Ba, 0)<x<5)、A 1-x B x Fe 12- x M y O 19 (A=La, B=Ba, M=Sn, zr or Ce, 0.2.ltoreq.x.ltoreq. 0.6,0.2.ltoreq.y.ltoreq.1.2).
The present application 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 active center
The literature is as follows:
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[4]Zhu M,Song Y H,Chen S Y,et al.Chemical looping dry reforming of methane with hydrogen generation on Fe 2 O 3 /Al 2 O 3 oxygen carrier.Chem Eng J,2019,368:812-823.
[5] the Ce-Fe-Zr-O/MgO integrated oxygen carrier is used for preparing synthetic gas [ J ]. Fuel chemistry report, 2015,43 (4): 118-125 by chemical chain partial oxidation of methane in crane, li Fashe, zhou Xing.
[6]Gu Zhenhua, duan Yuejuan, wei Yonggang et al CeO based on methane chemical looping combustion 2 Preparation and Property grinding of modified oxygen Carrier [ J ]]University of Kunming university (Nature science edition), 2015,40 (2): 12-17.
[7]Miller DD,Siriwardane R.Mechanism of methane chemical looping combustion with hematite promoted with CeO 2 .Energ Fuel,2013,37:4087-4096.
[8]Ma Z,Zhang S,Lu YG.Phase segregation mechanism of NiFe 2 O 4 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 NiFe 2 O 4 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 SiO 2 and MgAl 2 O 4 .Energ Fuel,2006,20(1):34-44.
[11]Ksepko E.Perovskite Sr(Fe 1-x Cu x )O 3-δ materials 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 CaTi 0.125 Mn 0.875- x Fe x T i0.125 O 3-δ perovskite 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 La 1.6 Sr 0.4 FeCoO 6 .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 CO 2 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 CH 4 -CO 2 reforming.Int J Hydrogen Energ,2017,42(52):30509-30524.
[16]Zhu Y,Jin N,Liu R,et al.Bimetallic BaFe 2 MAl 9 O 19 (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 CO 2 as sole oxidant.AIChE J,2018,64(2):550-563.
[18] Zhu Yanyan, ma Xiaoxun, liu Weiwei, liu Ying, liu Zemin an oxygen carrier for chemical looping dry gas reforming, a method for its preparation and its use [ P ]. ZL2015110419339. X,2017-10-31.
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[20] Zhu Yanyan, liu Ruilin, shen Qianqian, nana, sun Xueyan, li Shuang. An iron-based oxygen carrier with high iron content and high dispersion, and its preparation method and application [ P ]. ZL201711322508.3,2020-12-22.
Example 9
1) Fuel CH 4 With oxygen carrier Fe 2 O 3 The mixture is introduced into a chemical looping combustion reactor R101 with the temperature of 900 ℃ and the pressure of 1atm, the flow rate of methane is 1kmol/h, and the feeding ratio of oxygen carrier to methane is 1-12. See fig. 5 (a) and (b).
2) Fuel CH 4 And the oxygen carrier FeO from the R101 reactor is introduced into a chemical chain reforming reactor R102 with the temperature of 900 ℃ and the pressure of 1atm, and the feeding ratio of methane to the oxygen carrier is 0.25-1.25. See fig. 6 (a), (b) and (c).
3) CO from R101 reactor 2 And H 2 O and oxygen carrier Fe from R102 reactor are introduced into a CO-cracking reactor R103, CO with the temperature of 850 ℃ and the pressure of 1atm 2 The feed ratio to the oxygen carrier is 0.11-0.62. See fig. 7 (a), (b) and (c).
4) The steam and the oxygen carrier FeO from the R103 reactor are introduced into a hydrogen production reactor R104 with the temperature of 500 ℃ and the pressure of 1atm, and the feeding ratio of the steam and the oxygen carrier is 0.1-1.9. See fig. 8 (a) and (b).
5) Air was combined with oxygen carrier Fe from R104 reactor 3 O 4 The oxygen carrier regeneration reactor R105 was charged at 500℃and a pressure of 1atm, and the feed ratio of air to oxygen carrier was 0.75 to 2.25. See fig. 9.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 10
1) Fuel CH 4 With oxygen carrier Fe 2 O 3 Introducing into a chemical looping combustion reactor R101 with the pressure of 1atm, the flow rate of methane being 1kmol/h, the feed ratio of oxygen carrier to methane being 4, and reactingThe temperature is 200-1500 ℃. And (3) injection: for supporting fig. 10 (a, b).
2) Fuel CH 4 With the oxygen carrier FeO from the R101 reactor, the mixture is introduced into a chemical chain 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 fig. 11 (a), (b) and (c).
3) CO from R101 reactor 2 And H 2 O and oxygen carrier Fe from R102 reactor are introduced into a CO-cracking reactor R103, CO with pressure of 1atm 2 The feed ratio with the oxygen carrier is 0.4, and the reaction temperature is 200-1500 ℃. See fig. 12 (a), (b) and (c).
4) The steam and the oxygen carrier FeO from the R103 reactor are introduced into a hydrogen production reactor R104 with the pressure of 1atm, the feeding ratio of the steam and the oxygen carrier is 1.1, and the reaction temperature is 200-1500 ℃. See fig. 13 (a), (b) and (c).
5) Air was combined with oxygen carrier Fe from R104 reactor 3 O 4 An oxygen carrier regeneration reactor R105 having a pressure of 1atm was charged, the feed ratio of air to oxygen carrier was 1.5, and the reaction temperature was 500 ℃.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
Example 11
1) Fuel CH 4 With oxygen carrier Fe 2 O 3 Introducing into a chemical-looping combustion reactor R101 with the temperature of 900 ℃, wherein the flow rate of methane is 1kmol/h, the feed ratio of oxygen carrier to methane is 4, and the reaction pressure is 1-12atm. See fig. 14 (a).
2) Fuel CH 4 With the oxygen carrier FeO from the R101 reactor, the mixture is introduced into a chemical chain reforming reactor R102 with the temperature of 900 ℃, the feeding ratio of methane to the oxygen carrier is 1, and the reaction pressure is 1-12atm. See fig. 14 (b).
3) CO from R101 reactor 2 And H 2 O and oxygen carrier Fe from the R102 reactor are introduced into a CO-cracking reactor R103 and CO with the temperature of 850 DEG C 2 The feed ratio to the oxygen carrier was 0.4, and the reaction pressure was 1 to 12atm, see FIG. 14 (c).
4) The steam and the oxygen carrier FeO from the R103 reactor are introduced into a hydrogen production reactor R104 with the temperature of 500 ℃, the feeding ratio of the steam and the oxygen carrier is 1.1, and the reaction pressure is 1atm to 12atm. See fig. 14 (d).
5) Air was combined with oxygen carrier Fe from R104 reactor 3 O 4 An oxygen carrier regeneration reactor R105 having a temperature of 500℃was fed, the feed ratio of air to oxygen carrier was 1.5, and the reaction pressure was 1atm.
6) So as to circularly reciprocate and realize the in-situ utilization of CO 2 Chemical chain coupling process for co-production of synthesis gas and hydrogen.
The application provides an in-situ utilization method of CO 2 A chemical chain coupling process for co-producing synthesis gas and hydrogen, schematically shown in figure 1. It combines CL-SMR with Chemical Looping Combustion (CLC) and CO 2 -H 2 O co-cleavage combined, comprised 5 reactors: 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, CO at the initial stage 2 Not only reduces the selectivity of the synthesis gas, but also leads to the greenhouse gas CO 2 Is arranged in the air. However, in the coupling process proposed by the present application, CO is initially formed in the R101 reactor 2 And H 2 O is no longer vented or mixed with the synthesis gas but rather as a co-cracking feedstock produces additional synthesis gas in the R103 reactor. This not only greatly improves the purity of the synthesis gas, but also improves the overall yield of the synthesis gas. In addition, in R103 (CO 2 +H 2 O) can remove carbon deposit possibly formed in R102 and avoid pollution to high-purity H generated in subsequent R104 2 . In this chemical chain coupling process, not only the desired H can be produced separately 2 Synthetic gas suitable for Fischer-Tropsch (F-T) synthesis in a CO ratio (2) and high purity hydrogen, and also the greenhouse gas CO 2 . In addition, synthesis gas conditioning, hydrogen purification and carbon dioxide capture and storage are not needed, so that the cost is greatly saved. Our coupled process circulates only the oxygen carrier compared to SE-CLR, thus causing fewer problems in solids handling and setting at reactor operating temperature and feed ratioThe placement has higher flexibility.
The brief flow of the present application is shown in FIG. 2, where two CH's are 4 Are all used for directly or indirectly producing synthesis gas, CH 4 -1 and oxygen carrier are combusted in an R101 reactor to produce CO 2 And H 2 O, consuming surface oxygen of the oxygen carrier; CH (CH) 4 2 reforming reaction is carried out between the R102 reactor and the oxygen carrier which consumes the surface oxygen to convert the surface oxygen into high-quality synthesis gas; CO produced in R101 reactor 2 And H 2 Introducing O into an R103 reactor to generate synthesis gas through a CO-cracking reaction, and adding additional CO according to a certain proportion 2 And H 2 O can produce more synthesis gas and if not replenished, more high purity hydrogen can be produced in the R104 reactor; the solid of the R103 reactor enters the R104 reactor after passing through the gas-solid separator, and is subjected to a cracking reaction with steam to prepare hydrogen, and the hydrogen with high purity can be obtained by simply condensing water, so that a complex and high-energy-consumption separation process is avoided. In this process, CO is generated 2 In situ utilization to produce more valuable synthesis gas, in situ conversion and utilization of carbon dioxide is achieved, and complex synthesis gas and hydrogen separation and purification steps are avoided. The coupling process can produce high-purity hydrogen and synthesis gas without pollutant and greenhouse gas emission, and can fully utilize 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,efficiency is improved from 65.2% to 72.04% of the traditional steam methane reforming technology route.
Related models are built by adopting Aspen Plus software, the reactor adopts Gibbs reactor modules, waste heat of gas at the outlet of the reactor is used for preheating raw material gas and generating steam, a heat exchange network is added to the system as shown in figure 3, and energy balance analysis is carried out on the system as shown in figure 4, so that energy balance can be achieved, and the energy efficiency of the system is as high as 90.54%.
The application respectively explores the product flow rates of five reactors under different feed ratiosThe results of the oxygen carrier conversion, the raw material conversion, the product yield, and the like are shown in fig. 5 (a) and (b), fig. 6 (a), (b), and (c), fig. 7 (a), (b), and (c), fig. 8 (a) and (b), and fig. 9. Fe can be found 2 O 3 /CH 4 At a molar ratio of-1 up to 4, the methane is substantially completely converted to CO 2 And H 2 O；CH 4 When the 2/FeO molar ratio reaches 1, the yield of synthesis gas-1 is maximum (97%) and the optimal hydrogen-carbon ratio (-2) is reached; CO 2 At a molar ratio of/Fe of 0.4, the yield of synthesis gas-2 is 83% and the hydrogen-to-carbon ratio is close to 2; h 2 When the O/FeO molar ratio reaches 1.1, feO can be completely converted into Fe 3 O 4 And generates 2.67 kmol/hydrogen; air/Fe 3 O 4 When the molar ratio is greater than 1.2, the oxygen carrier can be completely recovered.
Optimizing the Fe 2 O 3 /CH 4 -1、CH 4 -2/FeO、CO 2 /Fe、H 2 O/FeO and Air/Fe 3 O 4 The effect of different temperatures and pressures on product flow, oxygen carrier conversion, raw material conversion and product yield was investigated using Aspen Plus software at molar ratios 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 perform better at 900 ℃, whereas the preferred temperature for the R103 reactor was 850 ℃, and finally the preferred temperature for the R104 reactor was 500 ℃, and the preferred temperature for the R105 reactor was 500 ℃ for energy savings. It can be seen from fig. 14 that increasing the pressure has substantially no effect on the R101 and R104 reactors, while increasing the pressure reduces the synthesis gas performance of the R102 and R103 reactors, so the preferred pressure for the final reactor is 1atm.
Under preferred conditions, the results of the calculation by Aspen Plus system are shown in table 2.
Table 2 shows key evaluation indexes of chemical chain coupling system under preferred operation conditions
As can be seen from Table 2, the yields of the two synthesis gases are 97% and 84%, respectively, the purity of the synthesis gases can reach 99% and 93%, respectively, and the ideal hydrogen-to-carbon ratios (1.99 and 1.98) are achieved. The purity of the hydrogen can reach 100 percent. Energy efficiency and of the systemThe efficiency can reach 90.54% and 72.04% respectively. This embodiment enables in situ utilization of CO 2 And co-producing synthesis gas and hydrogen, and realizing the recycling of oxygen carriers.
The application is used for utilizing CO in situ 2 To co-produce synthesis gas and hydrogen, CH 4 With oxygen carrier Fe 2 O 3 Into a chemical looping combustion reactor, lattice oxygen on the surface of an oxygen carrier is consumed and CO is generated 2 And H 2 O; the partially reduced oxygen carrier FeO enters a chemical chain reforming reactor to prepare high-quality synthesis gas and is reduced into Fe by one step; while self-combustion reactor CO 2 And H 2 O and the reduced oxygen carrier Fe from the reforming reactor are used in a co-cracking reactor to produce synthesis gas, while the reduced oxygen carrier Fe is oxidized to FeO; the oxygen carrier FeO and water vapor from the co-cracking reactor enter a hydrogen production reactor, the oxygen carrier is oxidized, and the water vapor is reduced to hydrogen in a large part; oxygen carrier (FeO) from the hydrogen production reactor and air from the atmosphere enter the air reactor, and the oxygen carrier is oxidized to the highest valence state and then sent to the chemical looping combustion reactor for reaction. The process not only can obtain high-quality synthesis gas and hydrogen, but also can realize CO 2 Zero emission and conversion into synthesis gas, and simultaneously avoids synthesis gas and H with higher energy consumption 2 Is a step of separation and purification.
Although the preferred embodiments of the present application have been described above with reference to the accompanying drawings, the present application is not limited to the above-described embodiments, which are merely illustrative, not restrictive, and many more modifications may be made thereto by those of ordinary skill in the art without departing from the spirit of the application and the scope of the appended claims, which are within the scope of the present application.
Claims (7)
1. A chemical looping coupling process for co-producing synthesis gas and hydrogen in situ using carbon dioxide, comprising the steps of:
1) Reaction of fuel and oxygen carrier to form CO 2 And H 2 O, passing through a gas-solid separator to obtain gas and partially reduced solid;
2) The fuel reacts with the partially reduced solid obtained in the step 1) to generate synthesis gas, and the synthesis gas and the reduced solid are obtained through a gas-solid separator;
3) The gas obtained in the step 1) and the reduced solid obtained in the step 2) are subjected to a cracking reaction to generate synthesis gas, and the synthesis gas and the solid are obtained through a gas-solid separator;
4) The water vapor reacts with the solid obtained in the step 3) to generate hydrogen, and the hydrogen and the solid which are partially oxidized are obtained through a gas-solid separator;
5) Air reacts with the solid obtained in the step 4) to enable the solid to be oxidized and regenerated, and the solid enters the step 1) for the next recycling after passing through a gas-solid separator;
the fuel in the step 1) and the step 2) is methane;
the oxygen carrier is one of the following oxygen carriers: fe (Fe) 2 O 3 、FeO、Fe、Fe 3 O 4 Sodium modified Fe 2 O 3 /Al 2 O 3 Oxygen carrier, fe 2 O 3 /Al 2 O 3 (1.5-Y 2 O 3 ) Oxygen carrier, nickel-enriched Fe 2 O 3 /Al 2 O 3 Oxygen carrier, fe 2 O 3 /Al 2 O 3 Oxygen carrier, ce-Fe-Zr-O/MgO integrated oxygen carrier, ceO 2 Modified Fe 2 O 3 Oxygen carrier, ceO 2 Hematite oxygen carrier, niFe 2 O 4 Oxygen carrier, fe 2 O 3 /MgAl 2 O 4 An oxygen carrier; la (La) 1.6 Sr 0.4 FeCoO 6 An oxygen carrier; la-Fe-Al oxygen carrier;
Sr(Fe 1-x Cu x )O 3-δ an oxygen carrier, wherein x= 0,0.1 or 0.33;
CaTi 0.125 Mn 0.875-x Fe x Ti 0.125 O 3-δ an oxygen carrier, wherein x= 0,0.05,0.1,0.15 or 0.2;
BaFe 2.8 M 0.2 Al 9 O 19 an oxygen carrier, wherein m=fe, si, zr, or Ce;
BaFe 2 MAl 9 O 19 an oxygen carrier, wherein m=mn, ni or Co;
AFe x Al 12-x O 19 oxygen carrier, wherein a=la or Ba,0<x<5；
CeO 2 And AFe n Al 12-n O 19 A composite oxygen carrier, wherein a=la or Ba,0<n≤12；
A 1-x B x Fe 12-x M y O 19 An oxygen carrier, wherein A=La, B=Ba, M=Sn, zr or Ce, 0.2.ltoreq.x.ltoreq. 0.6,0.2.ltoreq.y.ltoreq.1.2.
2. A chemical looping coupling process for co-production of synthesis gas and hydrogen using carbon dioxide in situ according to claim 1, wherein the molar ratio of solids to fuel in step 1) is (1-12): 1, the reaction temperature is 200-1500 o C。
3. A chemical looping coupling process for co-production of synthesis gas and hydrogen using carbon dioxide in situ according to claim 1, wherein the molar ratio of fuel to solids in step 2) is (0.25-1.25): 1, the reaction temperature is 200-1500 o C。
4. A chemical looping coupling process for CO-production of synthesis gas and hydrogen using carbon dioxide in situ according to claim 1, wherein said CO in step 3) 2 The molar ratio to the solid is (0.11-0.62): 1, the reaction temperature is 200-1500 o C。
5. According to claimA chemical looping coupling process for co-production of synthesis gas and hydrogen in situ using carbon dioxide as described in claim 1, wherein H in said step 4) 2 The molar ratio of O to solid is (0.1-1.9): 1, the reaction temperature is 200-1500 o C。
6. A chemical looping coupling process for co-production of synthesis gas and hydrogen using carbon dioxide in situ according to claim 1, wherein the molar ratio of air to solids in step 5) is (0.75-2.25): 1, the reaction temperature is 200-1500 o C。
7. A chemical looping coupling process for co-production of synthesis gas and hydrogen using carbon dioxide in situ according to claim 1, wherein the pressure of the reactions in steps 1) -5) is 1-12atm.
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