CN114955999A - Biological glycerol chemical chain reforming hydrogen production CO 2 In-situ trapping and utilizing process and device thereof - Google Patents
Biological glycerol chemical chain reforming hydrogen production CO 2 In-situ trapping and utilizing process and device thereof Download PDFInfo
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- CN114955999A CN114955999A CN202210740349.3A CN202210740349A CN114955999A CN 114955999 A CN114955999 A CN 114955999A CN 202210740349 A CN202210740349 A CN 202210740349A CN 114955999 A CN114955999 A CN 114955999A
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 238000002407 reforming Methods 0.000 title claims abstract description 130
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 115
- 239000001257 hydrogen Substances 0.000 title claims abstract description 111
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 56
- 239000000126 substance Substances 0.000 title claims abstract description 55
- 230000008569 process Effects 0.000 title claims abstract description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 288
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 174
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 174
- 239000001301 oxygen Substances 0.000 claims abstract description 174
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 156
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 144
- 239000003463 adsorbent Substances 0.000 claims abstract description 136
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 98
- 239000000292 calcium oxide Substances 0.000 claims abstract description 94
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 94
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000007789 gas Substances 0.000 claims abstract description 74
- 239000000446 fuel Substances 0.000 claims abstract description 60
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 49
- 230000008929 regeneration Effects 0.000 claims abstract description 40
- 238000011069 regeneration method Methods 0.000 claims abstract description 40
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000012159 carrier gas Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 229910000943 NiAl Inorganic materials 0.000 claims description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000013589 supplement Substances 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000005431 greenhouse gas Substances 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000002594 sorbent Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003225 biodiesel Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012358 sourcing Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000003313 weakening effect Effects 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
- C01B3/38—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 using catalysts
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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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than 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
- 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
- C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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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
- C01B2203/1217—Alcohols
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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
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Abstract
The invention provides a biological glycerol chemical chain reforming hydrogen production CO 2 A process and a device for in-situ capture and utilization. Firstly putting biological glycerol, water, calcium oxide adsorbent and nickel-based oxygen carrier into a fuel reactor for adsorption-enhanced chemical-looping reforming hydrogen production to obtain high-purity hydrogen, reducing the oxygen carrier, and adsorbing CO in situ by the adsorbent 2 (ii) a Decomposition of calcium carbonate in adsorbent regeneration/methane dry reforming reactor releases CO 2 Regeneration of the adsorbent, CO 2 Preparing synthetic gas under the catalysis of the introduced methane and the reduction-state oxygen carrier; regenerating oxygen carrier in air reactor and then using it and regenerated adsorbent cyclically. The invention carries out in-situ dry reforming while decomposing and regenerating the adsorption-enhanced chemical-looping reforming hydrogen production adsorbent, and also solves the problems of separation of the oxygen carrier and the adsorbent and carbon deposition of the chemical-looping reforming hydrogen production and the methane dry reformingThe heat released by the combustion of the air reactor can supplement the heat absorbed by a system, reduce the energy consumption, have simple flow, and are efficient, low-cost and renewable energy sources for converting hydrogen, preparing synthesis gas, reducing emission and utilizing CO 2 And a new process of methane greenhouse gas.
Description
Technical Field
The invention belongs to the field of hydrogen energy, and particularly relates to a biological glycerol chemical chain reforming hydrogen production CO 2 A process and a device for in-situ capture and utilization.
Background
The biodiesel is a novel fuel which is renewable, biodegradable, environment-friendly, nontoxic and low in sulfur content, has performance similar to that of fossil diesel, and is a clean renewable energy source capable of replacing the fossil fuel. In the actual production process of the biodiesel, about 0.1 ton of by-product biological glycerol is produced when 1 ton of biodiesel is produced. Along with the continuous expansion of the production scale of the biodiesel, the scale of the byproduct biological glycerol is increased, so that the development and utilization of the byproduct biological glycerol must be improved while the biological diesel is developed and produced, the biological glycerol is converted into hydrogen by catalytic reforming, the technology is a conventional technology, and CO is discharged in the process 2 How to invent a new hydrogen production mode with carbon capture technology and how to utilize captured CO 2 The comprehensive utilization rate and the economical efficiency of the whole process can be improved, and huge social benefits and environmental benefits are generated.
A great deal of research has been carried out on the chemical-looping reforming hydrogen production technology at home and abroad, and the hydrogen production technology comprises a fuel reactor and an air reactor, wherein the main raw materials are respectively hydrocarbon fuel and water vapor. In the fuel reactor, the oxygen carrier in the oxidized state chemically reacts with the fuel, the oxygen carrier is reduced, and the reduced oxygen carrier then catalyzes the fuel to reform the fuel with steam to produce hydrogen and CO 2 (ii) a The reduced oxygen carrier enters the air reactor to perform oxidation reaction with air, the oxygen carrier is re-oxidized, the heat released by the air reactor can be supplied to the fuel reactor to absorb heat, and the system can realize self-heating. If calcium oxide adsorbent is added into the fuel reactor, the fuel is oxidized by oxygen carrier and CO generated by steam reforming 2 Is trapped in situ by the adsorbent according toThe Lisatlet principle, the reaction moves towards the direction of generating hydrogen, the conversion rate of raw materials is improved, and simultaneously, the CO is trapped in situ 2 High-purity hydrogen can be generated in one step; adsorb and capture CO 2 To CaCO 3 Separating the adsorbent from the oxygen carrier, oxidizing the oxygen carrier with air, heating the adsorbent to regenerate the adsorbent and release CO 2 The process is also complicated. Patent CN202210198327.9 discloses a hydrogen production device by reforming chemical chain methane, which improves the problems of oxygen carrier breakage and reactor abrasion in the traditional fluidized bed reactor by the design of induction heating temperature control mode, heat transfer/mass transfer sequential control and the like in the heating process of the integral honeycomb oxygen carrier, and does not relate to the discharge of hydrogen production by reforming chemical chain and CO utilization 2 And (5) problems are solved. The patent CN201911199104.9 discloses a method for preparing Ce-Mn-Co-O oxygen carrier and application thereof in chemical chain reforming hydrogen production of blast furnace gas, wherein CeO is prepared by utilizing cobalt nitrate, manganese nitrate and cerium nitrate 2 -MnCo 2 O 4 The oxygen carrier is used for preparing hydrogen by chemical looping reforming of blast furnace gas, the blast furnace gas is converted at the temperature of 800-900 ℃ to obtain a loss oxygen carrier and carbon dioxide, and then steam is introduced into the loss oxygen carrier to carry out steam reforming to generate H 2 And CO 2 Purifying the tail gas to obtain pure H 2 Not involving CO 2 Trapping and utilization problems. Patent CN202111452462.3 discloses a method and system for preparing hydrogen-rich synthesis gas by chemical chain reforming of carbon-based solid fuel, wherein the carbon-based solid fuel is pyrolyzed in a pyrolysis reactor to generate volatile matter and coke, the volatile matter enters a reforming reactor, and hydrogen-rich gas and CO are generated under the catalytic action of an oxygen carrier 2 The oxygen carrier reacts with air in the air reactor to supplement lattice oxygen, the oxygen carrier carries heat to the reforming reactor to provide lattice oxygen and heat and play a catalytic role, and CO is not involved 2 And (4) trapping and utilizing. Patent CN201911296263.0 discloses a chemical looping reforming hydrogen production device for recycling reaction byproducts, which can recycle and reuse the reaction byproducts to improve the utilization rate of fuel in the chemical looping reforming hydrogen production process, but does not relate to CO in the chemical looping reforming hydrogen production process 2 Is collected byAnd utilization. Patent CN201310188839.8 discloses a process for preparing hydrogen by continuous catalytic adsorption enhanced chemical-looping reforming of a moving bed, wherein a nickel-based oxygen carrier is adopted to prepare hydrogen by adsorption enhanced chemical-looping reforming in a double-moving-bed reactor, and the problem is that an adsorbent CaCO 3 The components are decomposed and regenerated to release CO 2 It still needs to be collected and stored although CO is solved 2 In situ capture, but not involving a large amount of post-capture CO 2 The problem of utilization.
Hydrogen energy is one of the national major strategic demands, cheap hydrogen production is an important challenge for hydrogen energy development, and chemical-looping reforming hydrogen production is a new hydrogen production mode and is a new way for producing CO 2 And collecting and utilizing. CO adsorption by calcium oxide adsorbent 2 Is a well established technology, methane and CO 2 Under the action of catalyst, dry reforming to prepare synthetic gas is also a very mature technology at home and abroad, the key point is the research and development of dry reforming catalyst, in order to prevent the catalyst from sintering, the dry reforming temperature is usually selected below 850 ℃, and CO is not involved 2 The source of the raw material. CN202111231386.3 discloses a catalytic method for dry reforming of methane, which utilizes low-temperature plasma to introduce mixed raw material gas of methane, carbon dioxide and inert gas into a reactor filled with a catalyst to prepare synthesis gas of hydrogen and carbon monoxide, thereby realizing methane and CO under the conditions of low temperature and normal pressure 2 High efficiency, directional syngas conversion without CO involvement 2 The source of the raw material. CN202111674507.1 discloses a hydrogen production system based on methane dry reforming, which utilizes methane and valve gas to burn in the combustion area of a thermochemical reactor to provide heat source for the methane dry reforming reaction, and redundant CO 2 The carbon sealing is carried out through pressurization, so that the preparation of hydrogen by methane dry reforming negative carbon emission is effectively realized, and compared with the conventional hydrogen preparation method, the method has better hydrogen preparation efficiency and carbon reduction effect, and does not relate to CO 2 The source of the raw material.
It can be seen that CO is ubiquitous in the chemical looping reforming hydrogen production process of the prior art 2 Trapping and utilization problems, adsorbent and oxygen carrier separation problems, and catalyst carbon deposition problems. The process for preparing synthetic gas by dry reforming of methane in the prior art utilizes methane and CO 2 Under the action of catalyst, the synthesis gas is prepared by dry reforming, which not only has the problem of carbon deposition of the catalyst, but also does not consider CO 2 Sourcing and trapping.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a biological glycerol chemical chain reforming hydrogen production CO 2 A process and a device for in-situ capture and utilization.
The specific technical scheme of the invention is as follows:
the invention provides a biological glycerol chemical chain reforming hydrogen production CO 2 The in-situ trapping and utilizing process is characterized by comprising the following steps of: step S1, putting biological glycerol, water, calcium oxide adsorbent and nickel-based oxygen carrier into a fuel reactor, introducing first carrier gas into the fuel reactor, performing adsorption enhanced chemical looping reforming hydrogen production at a first preset temperature to obtain high-purity hydrogen, reducing the nickel-based oxygen carrier to obtain reduced nickel-based oxygen carrier, and generating CO 2 Calcium carbonate is obtained through in-situ adsorption of a calcium oxide adsorbent; step S2, transferring the calcium carbonate and the reduced nickel-based oxygen carrier into an adsorbent regeneration/methane dry reforming reactor, introducing a mixed gas of a second carrier gas and methane into the adsorbent regeneration/methane dry reforming reactor, and decomposing the calcium carbonate to release CO at a second preset temperature 2 Conversion of calcium carbonate to regenerated calcium oxide sorbent, CO 2 Carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of a reduced nickel-based oxygen carrier to obtain synthesis gas; step S3, transferring the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent into an air reactor, introducing a third carrier gas into the air reactor, oxidizing the reduced nickel-based oxygen carrier at a third preset temperature, burning carbon deposited in the reduced nickel-based oxygen carrier at the third preset temperature to obtain a regenerated nickel-based oxygen carrier, and transferring the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent into a fuel reactor to perform adsorption-enhanced chemical-looping reforming hydrogen production cycle.
The biological glycerol chemical chain reforming hydrogen production CO provided by the invention 2 The process of in-situ capture and utilization,also has the technical characteristics that the molar ratio of the water to the biological glycerol in the step S1 is 1: 1-1.2, the nickel-based oxygen carrier comprises NiO and NiAl 2 O 4 The particle size of the nickel-based oxygen carrier is 0.40-0.90mm, the mass concentration of CaO in the calcium oxide adsorbent is more than 98%, the particle size of the calcium oxide adsorbent is 0.40-0.90mm, and the mass ratio of the calcium oxide adsorbent to the nickel-based oxygen carrier is 1: 1-1.2, the first carrier gas is nitrogen, and the first preset temperature is 600-650 ℃.
The biological glycerol chemical chain reforming hydrogen production CO provided by the invention 2 The in-situ trapping and utilizing process is also characterized in that the mass concentration of NiO is 10-20%, and NiAl is 2 O 4 The mass concentration of (A) is 80-90%.
The biological glycerol chemical chain reforming hydrogen production CO provided by the invention 2 The in-situ trapping and utilizing process also has the technical characteristics that the second carrier gas in the step S2 is nitrogen, the volume concentration of methane in the mixed gas is 20-40%, and the second preset temperature is 850-.
The biological glycerol chemical chain reforming hydrogen production CO provided by the invention 2 The in-situ trapping and utilizing process further has the technical characteristics that the third carrier gas is air in the step S3, and the third preset temperature is 600-700 ℃.
The invention also provides a biological glycerol chemical chain reforming hydrogen production CO 2 The in-situ capture and utilization process device is characterized in that the process device is used for the chemical chain reforming of the biological glycerol to produce hydrogen CO 2 And (3) in-situ trapping and utilizing.
The biological glycerol chemical chain reforming hydrogen production CO provided by the invention 2 The in-situ trapping and utilizing process device also has the technical characteristics that the device consists of a fuel reactor, an adsorbent regeneration/methane dry reforming reactor, an air reactor and a riser, wherein the fuel reactor, the adsorbent regeneration/methane dry reforming reactor and the air reactor are connected through the riser.
The biological glycerol chemical chain reforming hydrogen production CO provided by the invention 2 The in-situ trapping and utilizing process device also has the technical characteristics that the fuelThe reactor is provided with a calcium oxide adsorbent, a nickel-based oxygen carrier and nitrogen mixing inlet, a biological glycerol and water mixing inlet, a hydrogen outlet, a slag discharge port, a calcium carbonate and reduction-state nickel-based oxygen carrier mixing outlet, a regenerated nickel-based oxygen carrier and a regenerated calcium oxide adsorbent circulating inlet.
The biological glycerol chemical chain reforming hydrogen production CO provided by the invention 2 The in-situ trapping and utilizing process device is also characterized in that the adsorbent regeneration/methane dry reforming reactor is provided with a calcium carbonate and reduced nickel-based oxygen carrier mixed inlet, a mixed gas inlet, a synthetic gas outlet, a reduced nickel-based oxygen carrier and a regenerated calcium oxide adsorbent mixed outlet.
The biological glycerol chemical chain reforming hydrogen production CO provided by the invention 2 The process device for in-situ capture and utilization also has the technical characteristics that the air reactor is provided with a mixed inlet of a reduced nickel-based oxygen carrier and a regenerated calcium oxide adsorbent, an air inlet, a gas outlet, a mixed outlet of the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent and a slag discharge hole.
Action and Effect of the invention
According to the invention, biological glycerol, water, calcium oxide adsorbent and nickel-based oxygen carrier are firstly put into a fuel reactor for adsorption enhanced chemical-looping reforming hydrogen production to obtain high-purity hydrogen, the nickel-based oxygen carrier is reduced, and CO generated by in-situ adsorption of the calcium oxide adsorbent is reduced 2 Obtaining calcium carbonate; the calcium carbonate and reduced nickel-based oxygen carrier are transferred to an adsorbent regeneration/methane dry reforming reactor where the calcium carbonate decomposes to release CO 2 To become regenerated calcium oxide sorbent, CO 2 Carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of a reduced nickel-based oxygen carrier to obtain synthesis gas; the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent are transferred to an air reactor, the reduced nickel-based oxygen carrier is oxidized and burnt to regenerate carbon, and the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent are transferred to a fuel reactor to perform adsorption-enhanced chemical-looping reforming hydrogen production cycle.
The invention better utilizes Lexhlet's principle to produce hydrogen by chemical chain reforming and simultaneously carry out CO product 2 The in-situ adsorption is carried out, and the conditions of the reversible reaction of water-vapor transformation involved in the process of hydrogen production by reforming are changed
Continuously reducing CO in hydrogen production system 2 The concentration and the chemical equilibrium of the hydrogen production system are destroyed and move towards the direction of weakening the change, thereby improving the conversion rate and the selectivity of the hydrogen production raw material; secondly, in the decomposition and regeneration stage of the adsorbent, methane is introduced to react with CO generated by the decomposition of the adsorbent 2 Performing in-situ dry reforming reaction by using CO 2 And methane to generate synthesis gas and continuously reduce CO 2 Concentration, which is also beneficial to the decomposition and regeneration of the adsorbent; and finally, oxidizing the reduced-state oxygen carrier into an oxidized-state oxygen carrier in the air reactor, and simultaneously removing the carbon deposition of the oxygen carrier, wherein the separation of the adsorbent and the oxygen carrier is not needed in the whole process.
Therefore, compared with the prior art, the method takes the biological glycerol as the raw material to carry out partial oxidation, steam reforming, steam-water shift, CO conversion 2 The adsorption is highly coupled in the fuel reactor, the decomposition of the adsorbent and the dry reforming of methane are simultaneously carried out under the same condition in the adsorbent regeneration/dry reforming of methane reactor, and the CO is realized 2 The utilization of (1). The method does not need to consider the separation problem of the oxygen carrier and the adsorbent and the carbon deposition problem of hydrogen production by chemical chain reforming and methane dry reforming, the heat release of the air reactor can supplement the heat absorption of the system, the energy consumption is reduced, the process is simple, and the method is efficient, low-cost and renewable energy conversion for hydrogen production, synthesis gas preparation and CO emission reduction and utilization 2 And a new process of methane greenhouse gas.
Drawings
FIG. 1 is a diagram of a process apparatus according to an embodiment of the present invention.
Detailed Description
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.
The reagents used in the following examples are commercially available and the experimental procedures and experimental conditions not specified are those conventional in the art.
FIG. 1 is a diagram of a process apparatus according to an embodiment of the present invention. The same process equipment is adopted in the following embodiments, and the biological glycerol chemical chain reforming hydrogen production CO 2 The in-situ trapping and utilizing process device 1 comprises a fuel reactor 2, an adsorbent regeneration/dry methane reforming reactor 3, an air reactor 4 and risers 10, 15 and 21, wherein the fuel reactor 2 and the adsorbent regeneration/dry methane reforming reactor 3 are connected through the riser 10, the adsorbent regeneration/dry methane reforming reactor 3 and the air reactor 4 are connected through the riser 15, and the air reactor 4 and the fuel reactor 2 are connected through the riser 21. Wherein, the fuel reactor 2 is provided with a calcium oxide adsorbent, a nickel-based oxygen carrier and nitrogen mixing inlet 5, a biological glycerol and water mixing inlet 6, a hydrogen outlet 7, a slag discharge port 8, a calcium carbonate and reduced nickel-based oxygen carrier mixing outlet 9, and a regenerated nickel-based oxygen carrier and regenerated calcium oxide adsorbent circulating inlet 22. The adsorbent regeneration/methane dry reforming reactor 3 is provided with a calcium carbonate and reduced nickel-based oxygen carrier mixed inlet 11, a mixed gas inlet 12, a synthetic gas outlet 13, a reduced nickel-based oxygen carrier and regenerated calcium oxide adsorbent mixed outlet 14. The air reactor 4 is provided with a reduced nickel-based oxygen carrier and regenerated calcium oxide adsorbent mixing inlet 16, an air inlet 17, a gas outlet 18, a regenerated nickel-based oxygen carrier and regenerated calcium oxide adsorbent mixing outlet 19 and a slag discharge port 20.
The nickel-based oxygen carriers used in the following examples are the same and are all nickel-based oxygen carriers produced by Johnson Matthey Catalysts (zhuangyifung catalyst) in england, with product numbers: 60/15T, the composition comprises 10-20 wt% of NiO and 80-90 wt% of NiAl 2 O 4 The particle size of the nickel-based oxygen carrier is 0.40-0.90 mm. The calcium oxide adsorbents used in the following examples are the same and are all produced by Shantou Kangsu chemical industry Co., LtdThe execution criteria are: Q/STXH114-2007, wherein the mass concentration of CaO is more than 98%, and the balance is impurities, and the impurities comprise CaCO 3 、MgO、CaCl 2 The particle size of the calcium oxide adsorbent is 0.40-0.90 mm.
The following examples are given to illustrate specific embodiments of the present invention.
< example 1>
The embodiment provides CO for hydrogen production by chemical chain reforming of biological glycerol 2 The in-situ trapping and utilizing process comprises the following steps:
step S1, putting biological glycerol, water, calcium oxide adsorbent and nickel-based oxygen carrier into a fuel reactor, introducing first carrier gas into the fuel reactor, performing adsorption enhanced chemical looping reforming hydrogen production at a first preset temperature to obtain high-purity hydrogen, reducing the nickel-based oxygen carrier to obtain reduced nickel-based oxygen carrier, and generating CO 2 Calcium carbonate is obtained through in-situ adsorption of a calcium oxide adsorbent, and the specific process comprises the following steps:
and spraying a mixture of the calcium oxide adsorbent and the nickel-based oxygen carrier into the fuel reactor 2 from a calcium oxide adsorbent, nickel-based oxygen carrier and nitrogen mixed inlet 5, and feeding a mixture of the biological glycerol and water into the fuel reactor 2 from a biological glycerol and water mixed inlet 6, wherein the mass ratio of the calcium oxide adsorbent to the nickel-based oxygen carrier is 1:1, and the molar ratio of the biological glycerol to the water is 1:1. Nitrogen (i.e. the primary carrier gas) is introduced through inlet 5 at a flow rate of: 0.5X 10 -3 m 3 min -1 (STP). Performing adsorption enhanced chemical looping reforming for hydrogen production at 600 deg.C (i.e. first preset temperature) to obtain high-purity hydrogen, reducing nickel-based oxygen carrier to obtain reduced nickel-based oxygen carrier, and generating CO 2 Calcium carbonate is obtained through in-situ adsorption of a calcium oxide adsorbent, the time for performing adsorption enhanced chemical looping reforming hydrogen production in the fuel reactor 2 is 20min, and the total chemical reaction occurring in the fuel reactor 2 can be expressed as:
C 3 H 8 O 3 +H 2 O+5NiO+3CaO→5H 2 +3CaCO 3 +5Ni；
step S2, transferring the calcium carbonate and the reduced nickel-based oxygen carrierIntroducing mixed gas of a second carrier gas and methane into the adsorbent regeneration/methane dry reforming reactor, and decomposing calcium carbonate to release CO at a second preset temperature 2 Conversion of calcium carbonate to regenerated calcium oxide sorbent, CO 2 And carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of a reduction-state nickel-based oxygen carrier to obtain synthesis gas, wherein the specific process comprises the following steps:
calcium carbonate and reduced nickel-based oxygen carrier are discharged from a mixed outlet 9 of the calcium carbonate and reduced nickel-based oxygen carrier out of the fuel reactor 2, and then transferred from a mixed inlet 11 of the calcium carbonate and reduced nickel-based oxygen carrier to the adsorbent regeneration/methane dry reforming reactor 3 by a riser 10, and mixed gas of nitrogen (i.e. secondary carrier gas) and methane is introduced from a mixed gas inlet 12, wherein the volume concentration of the methane in the mixed gas is 30%, and the flow rate of the mixed gas is as follows: 0.5X 10 -3 m 3 min -1 (STP). At 850 deg.C (i.e. the second preset temperature), the calcium carbonate decomposes to release CO 2 Conversion of calcium carbonate to regenerated calcium oxide sorbent, CO 2 And carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of a reduction-state nickel-based oxygen carrier to obtain synthesis gas, wherein the time for preparing the synthesis gas in the adsorbent regeneration/methane dry reforming reactor 3 is 20min, and the total chemical reaction in the adsorbent regeneration/methane dry reforming reactor 3 can be represented as:
CaCO 3 +CH 4 →2CO+2H 2 +CaO；
step S3, transferring the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent into an air reactor, introducing a third carrier gas into the air reactor, oxidizing the reduced nickel-based oxygen carrier at a third preset temperature, and burning carbon deposited in the reduced nickel-based oxygen carrier at the third preset temperature to obtain a regenerated nickel-based oxygen carrier, and transferring the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent into a fuel reactor to perform adsorption-enhanced chemical-looping reforming hydrogen production cycle, wherein the specific process comprises the following steps:
reduced nickel-based oxygen carriers and regeneratedThe calcium oxide adsorbent is discharged from the mixing outlet 14 of the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent, and is discharged from the adsorbent regeneration/methane dry reforming reactor 3, and is transferred to the air reactor 4 from the mixing inlet 16 of the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent by the riser 15, air (namely, third carrier gas) is introduced from the air inlet 17, and the flow rate of the air is as follows: 0.5X 10 -3 m 3 min -1 (STP). Oxidizing the reduced nickel-based oxygen carrier at 650 ℃ (namely, a third preset temperature), and simultaneously burning carbon deposited in the reduced nickel-based oxygen carrier at 650 ℃ to obtain a regenerated nickel-based oxygen carrier, wherein after the air reactor 4 is used for oxidizing and burning carbon for 20min, the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent are discharged out of the air reactor 4 from a mixed outlet 19 of the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent, and are transferred to the fuel reactor 2 from a circulating inlet 22 of the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent by a riser 21 to perform a cycle of adsorption-enhanced chemical-looping reforming hydrogen production, and the chemical reaction occurring in the air reactor 4 is as follows:
2Ni+O 2 →2NiO
C+O 2 →CO 2 。
the system runs for 60min, the mixed gas at the hydrogen outlet 7 of the fuel reactor 2 is collected, and a TS101-GC analysis instrument is adopted to measure H in the mixed gas 2 Has an average volume concentration of 16.1%, CH 4 Has an average volume concentration of 1.0%, CO 2 Has an average volume concentration of 0.09% and an average volume concentration of CO of 0.5%, minus N 2 And steam, the purity of the product hydrogen was calculated to be 91.0%. Collecting the synthesis gas at the synthesis gas outlet 13 of the adsorbent regeneration/methane dry reforming reactor 3, and determining the average volume concentration of CO in the synthesis gas to be 14.5% by adopting a TS101-GC analysis instrument and H 2 Is 12.5%, calculating to obtain CO and H in the synthesis gas 2 The molar ratio was 1.16: 1.
< example 2>
The embodiment provides a method for preparing CO by chemical chain reforming of biological glycerol 2 The in-situ trapping and utilizing process comprises the following steps:
step S1, putting biological glycerol, water, calcium oxide adsorbent and nickel-based oxygen carrier into a fuel reactor, introducing first carrier gas into the fuel reactor, performing adsorption enhanced chemical looping reforming hydrogen production at a first preset temperature to obtain high-purity hydrogen, reducing the nickel-based oxygen carrier to obtain reduced nickel-based oxygen carrier, and generating CO 2 Calcium carbonate is obtained through in-situ adsorption of a calcium oxide adsorbent, and the specific process comprises the following steps:
and spraying a mixture of the calcium oxide adsorbent and the nickel-based oxygen carrier into the fuel reactor 2 from a mixed inlet 5 of the calcium oxide adsorbent, the nickel-based oxygen carrier and nitrogen, and feeding a mixture of the biological glycerol and water into the fuel reactor 2 from a mixed inlet 6 of the biological glycerol and water, wherein the mass ratio of the calcium oxide adsorbent to the nickel-based oxygen carrier is 1:1.1, and the molar ratio of the biological glycerol to the water is 1: 1.1. Nitrogen (i.e. the primary carrier gas) is introduced through inlet 5 at a flow rate of: 0.5X 10 -3 m 3 min -1 (STP). Performing adsorption enhanced chemical looping reforming for hydrogen production at 650 ℃ (i.e. the first preset temperature) to obtain high-purity hydrogen, reducing nickel-based oxygen carrier to obtain reduced nickel-based oxygen carrier, and generating CO 2 Calcium carbonate is obtained through in-situ adsorption of a calcium oxide adsorbent, the time for carrying out adsorption enhanced chemical chain reforming hydrogen production in the fuel reactor 2 is 23min, and the total chemical reaction in the fuel reactor 2 can be represented as:
C 3 H 8 O 3 +H 2 O+5NiO+3CaO→5H 2 +3CaCO 3 +5Ni；
step S2, transferring the calcium carbonate and the reduced nickel-based oxygen carrier into an adsorbent regeneration/methane dry reforming reactor, introducing mixed gas of a second carrier gas and methane into the adsorbent regeneration/methane dry reforming reactor, and decomposing the calcium carbonate to release CO at a second preset temperature 2 Conversion of calcium carbonate to regenerated calcium oxide sorbent, CO 2 And carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of a reduction-state nickel-based oxygen carrier to obtain synthesis gas, wherein the specific process comprises the following steps:
calcium carbonate and reduced nickel-based oxygen carriers from calcium carbonate and reduced formThe nickel-based oxygen carrier mixed outlet 9 is discharged out of the fuel reactor 2, and then is transferred to the adsorbent regeneration/methane dry reforming reactor 3 from a calcium carbonate and reduced nickel-based oxygen carrier mixed inlet 11 by a riser 10, and a mixed gas of nitrogen (i.e. a second carrier gas) and methane is introduced from a mixed gas inlet 12, wherein the volume concentration of methane in the mixed gas is 30%, and the flow rate of the mixed gas is as follows: 0.5X 10 -3 m 3 min -1 (STP). At 900 deg.C (i.e. the second preset temperature), the calcium carbonate decomposes to release CO 2 Conversion of calcium carbonate to regenerated calcium oxide sorbent, CO 2 And carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of a reduction-state nickel-based oxygen carrier to obtain synthesis gas, wherein the time for preparing the synthesis gas in the adsorbent regeneration/methane dry reforming reactor 3 is 23min, and the total chemical reaction in the adsorbent regeneration/methane dry reforming reactor 3 can be represented as follows:
CaCO 3 +CH 4 →2CO+2H 2 +CaO；
step S3, transferring the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent into an air reactor, introducing a third carrier gas into the air reactor, oxidizing the reduced nickel-based oxygen carrier at a third preset temperature, and burning carbon deposited in the reduced nickel-based oxygen carrier at the third preset temperature to obtain a regenerated nickel-based oxygen carrier, and transferring the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent into a fuel reactor to perform adsorption-enhanced chemical-looping reforming hydrogen production cycle, wherein the specific process comprises the following steps:
the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent are discharged from a mixed outlet 14 of the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent out of the adsorbent regeneration/methane dry reforming reactor 3, and are transferred to the air reactor 4 from a mixed inlet 16 of the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent by a riser 15, air (namely third carrier gas) is introduced from an air inlet 17, and the flow rate of the air is as follows: 0.5X 10 -3 m 3 min -1 (STP). At 650 deg.C (i.e. the third preset temperature), the nickel-based oxygen carrier in the reduction state is oxidized, and at the same time, the nickel-based oxygen carrier in the reduction state is oxidized at 650 deg.CCarbon burning is carried out on carbon deposition in the oxygen carrier to obtain a regenerated nickel-based oxygen carrier, after carbon burning is carried out for 23min in the air reactor 4 by oxidation, the regenerated nickel-based oxygen carrier and a regenerated calcium oxide adsorbent are discharged out of the air reactor 4 from a regenerated nickel-based oxygen carrier and regenerated calcium oxide adsorbent mixed outlet 19, and are transferred into the fuel reactor 2 from a regenerated nickel-based oxygen carrier and regenerated calcium oxide adsorbent circulating inlet 22 by a riser 21 to carry out adsorption-enhanced chemical-chain reforming hydrogen production cycle, wherein the chemical reaction in the air reactor 4 is as follows:
2Ni+O 2 →2NiO
C+O 2 →CO 2 。
the system runs for 69min, the mixed gas of the hydrogen outlet 7 of the fuel reactor 2 is collected, and the TS101-GC analysis instrument is adopted to measure H in the mixed gas 2 Has an average volume concentration of 20.1%, CH 4 Has an average volume concentration of 0.8%, CO 2 Has an average volume concentration of 0.03% and an average volume concentration of CO of 0.11%, minus N 2 And steam, the purity of the product hydrogen was calculated to be 95.5%. Collecting the synthesis gas at the synthesis gas outlet 13 of the adsorbent regeneration/methane dry reforming reactor 3, and determining the average volume concentration of CO in the synthesis gas to be 15.0% by adopting a TS101-GC analysis instrument, wherein H is H 2 Has an average volume concentration of 14.5%, and calculates to obtain CO and H in the synthesis gas 2 The molar ratio was 1.03: 1.
< example 3>
The embodiment provides CO for hydrogen production by chemical chain reforming of biological glycerol 2 The in-situ trapping and utilizing process comprises the following steps:
step S1, putting biological glycerol, water, calcium oxide adsorbent and nickel-based oxygen carrier into a fuel reactor, introducing first carrier gas into the fuel reactor, performing adsorption enhanced chemical looping reforming hydrogen production at a first preset temperature to obtain high-purity hydrogen, reducing the nickel-based oxygen carrier to obtain reduced nickel-based oxygen carrier, and generating CO 2 Calcium carbonate is obtained through in-situ adsorption of a calcium oxide adsorbent, and the specific process comprises the following steps:
mixing calcium oxide adsorbent and nickel-based oxygen carrierAnd a mixed inlet 5 for the calcium oxide adsorbent, the nickel-based oxygen carrier and the nitrogen is sprayed into the fuel reactor 2, and a mixture of the biological glycerol and the water is fed into the fuel reactor 2 from a mixed inlet 6 for the biological glycerol and the water, wherein the mass ratio of the calcium oxide adsorbent to the nickel-based oxygen carrier is 1:1.2, and the molar ratio of the biological glycerol to the water is 1:1. Nitrogen (i.e. the primary carrier gas) is introduced through inlet 5 at a flow rate of: 0.5X 10 -3 m 3 min -1 (STP). Performing adsorption enhanced chemical looping reforming for hydrogen production at 650 ℃ (i.e. the first preset temperature) to obtain high-purity hydrogen, reducing nickel-based oxygen carrier to obtain reduced nickel-based oxygen carrier, and generating CO 2 Calcium carbonate is obtained through in-situ adsorption of a calcium oxide adsorbent, the time for carrying out adsorption enhanced chemical chain reforming hydrogen production in the fuel reactor 2 is 25min, and the total chemical reaction in the fuel reactor 2 can be expressed as:
C 3 H 8 O 3 +H 2 O+5NiO+3CaO→5H 2 +3CaCO 3 +5Ni；
step S2, transferring the calcium carbonate and the reduced nickel-based oxygen carrier into an adsorbent regeneration/methane dry reforming reactor, introducing mixed gas of a second carrier gas and methane into the adsorbent regeneration/methane dry reforming reactor, and decomposing the calcium carbonate to release CO at a second preset temperature 2 Conversion of calcium carbonate to regenerated calcium oxide sorbent, CO 2 And carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of a reduction-state nickel-based oxygen carrier to obtain synthesis gas, wherein the specific process comprises the following steps:
calcium carbonate and reduced nickel-based oxygen carrier are discharged from a mixed outlet 9 of the calcium carbonate and reduced nickel-based oxygen carrier out of the fuel reactor 2, and then transferred from a mixed inlet 11 of the calcium carbonate and reduced nickel-based oxygen carrier to the adsorbent regeneration/methane dry reforming reactor 3 by a riser 10, and mixed gas of nitrogen (i.e. secondary carrier gas) and methane is introduced from a mixed gas inlet 12, wherein the volume concentration of the methane in the mixed gas is 30%, and the flow rate of the mixed gas is as follows: 0.5X 10 -3 m 3 min -1 (STP). At 900 deg.C (i.e. the second preset temperature), the calcium carbonate decomposes to release CO 2 After conversion of calcium carbonate to regenerationCalcium oxide adsorbent of, CO 2 And carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of a reduction-state nickel-based oxygen carrier to obtain synthesis gas, wherein the time for preparing the synthesis gas in the adsorbent regeneration/methane dry reforming reactor 3 is 25min, and the total chemical reaction in the adsorbent regeneration/methane dry reforming reactor 3 can be represented as:
CaCO 3 +CH 4 →2CO+2H 2 +CaO；
step S3, transferring the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent into an air reactor, introducing a third carrier gas into the air reactor, oxidizing the reduced nickel-based oxygen carrier at a third preset temperature, and burning carbon deposited in the reduced nickel-based oxygen carrier at the third preset temperature to obtain a regenerated nickel-based oxygen carrier, and transferring the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent into a fuel reactor to perform adsorption-enhanced chemical-looping reforming hydrogen production cycle, wherein the specific process comprises the following steps:
the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent are discharged from a mixed outlet 14 of the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent out of the adsorbent regeneration/methane dry reforming reactor 3, and are transferred to the air reactor 4 from a mixed inlet 16 of the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent by a riser 15, air (namely third carrier gas) is introduced from an air inlet 17, and the flow rate of the air is as follows: 0.5X 10 -3 m 3 min -1 (STP). Oxidizing the reduced nickel-based oxygen carrier at 650 ℃ (namely, the third preset temperature), and simultaneously burning carbon deposited in the reduced nickel-based oxygen carrier at 650 ℃ to obtain a regenerated nickel-based oxygen carrier, wherein after the air reactor 4 is used for oxidizing and burning carbon for 25min, the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent are discharged out of the air reactor 4 from a mixed outlet 19 of the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent, and are transferred to the fuel reactor 2 from a circulating inlet 22 of the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent by a riser 21 to perform a cycle of adsorption-enhanced chemical-looping reforming hydrogen production, and the chemical reaction occurring in the air reactor 4 is as follows:
2Ni+O 2 →2NiO
C+O 2 →CO 2 。
the system runs for 75min, the mixed gas at the hydrogen outlet 7 of the fuel reactor 2 is collected, and a TS101-GC analysis instrument is adopted to measure H in the mixed gas 2 Has an average volume concentration of 19.1%, CH 4 Has an average volume concentration of 1.0%, CO 2 Has an average volume concentration of 0.02% and an average volume concentration of CO of 0.8%, minus N 2 And steam, the purity of the product hydrogen was calculated to be 91.3%. Collecting the synthesis gas at the synthesis gas outlet 13 of the adsorbent regeneration/methane dry reforming reactor 3, and determining the average volume concentration of CO in the synthesis gas to be 16.5% and H by adopting a TS101-GC (gas chromatography) analyzer 2 Is 15.0%, calculating to obtain CO and H in the synthesis gas 2 The molar ratio was 1.07: 1.
The foregoing is a detailed description of embodiments that will enable those skilled in the art to make and use the invention. The technical solutions of the present invention, which can be improved or modified only by analysis, analogy or limited enumeration, should be within the scope of protection determined by the claims.
Claims (10)
1. Biological glycerol chemical chain reforming hydrogen production CO 2 The in-situ trapping and utilizing process is characterized by comprising the following steps of:
step S1, putting biological glycerol, water, calcium oxide adsorbent and nickel-based oxygen carrier into a fuel reactor, introducing first carrier gas into the fuel reactor, performing adsorption enhanced chemical looping reforming hydrogen production at a first preset temperature to obtain high-purity hydrogen, reducing the nickel-based oxygen carrier to obtain a reduced nickel-based oxygen carrier, and generating CO 2 Calcium carbonate is obtained through in-situ adsorption of the calcium oxide adsorbent;
step S2, transferring the calcium carbonate and the reduced nickel-based oxygen carrier into an adsorbent regeneration/methane dry reforming reactor, and introducing the calcium carbonate and the reduced nickel-based oxygen carrier into the adsorbent regeneration/methane dry reforming reactorA mixed gas of a second carrier gas and methane, at a second preset temperature, the calcium carbonate is decomposed to release CO 2 Said calcium carbonate is converted to regenerated calcium oxide adsorbent, said CO 2 Carrying out in-situ decomposition and dry reforming with introduced methane under the catalytic action of the reduced nickel-based oxygen carrier to obtain synthesis gas;
step S3, transferring the reduced nickel-based oxygen carrier and the regenerated calcium oxide adsorbent to an air reactor, introducing a third carrier gas into the air reactor, oxidizing the reduced nickel-based oxygen carrier at a third preset temperature, burning carbon deposited in the reduced nickel-based oxygen carrier at the third preset temperature to obtain a regenerated nickel-based oxygen carrier, and transferring the regenerated nickel-based oxygen carrier and the regenerated calcium oxide adsorbent to the fuel reactor to perform an adsorption-enhanced chemical-looping reforming hydrogen production cycle.
2. The chemical looping reforming hydrogen production CO of biological glycerol according to claim 1 2 The in-situ trapping and utilizing process is characterized in that,
wherein the molar ratio of the water to the biological glycerol in step S1 is 1: 1-1.2,
the nickel-based oxygen carrier comprises NiO and NiAl 2 O 4 The particle size of the nickel-based oxygen carrier is 0.40-0.90mm,
the mass concentration of CaO in the calcium oxide adsorbent is more than 98 percent, the particle size of the calcium oxide adsorbent is 0.40-0.90mm,
the mass ratio of the calcium oxide adsorbent to the nickel-based oxygen carrier is 1: 1-1.2,
the first carrier gas is nitrogen gas,
the first preset temperature is 600-650 ℃.
3. The chemical looping reforming hydrogen production CO of biological glycerol according to claim 2 2 The in-situ trapping and utilizing process is characterized in that,
wherein the mass concentration of the NiO is 10-20%,
the NiAl 2 O 4 The mass concentration of (A) is 80-90%.
4. The chemical looping reforming of biological glycerol to produce hydrogen CO as claimed in claim 1 2 The in-situ trapping and utilizing process is characterized in that,
wherein the second carrier gas is nitrogen in step S2,
the volume concentration of the methane in the mixed gas is 20-40%,
the second preset temperature is 850-.
5. The chemical looping reforming hydrogen production CO of biological glycerol according to claim 1 2 The in-situ trapping and utilizing process is characterized in that,
wherein the third carrier gas is air in step S3,
the third preset temperature is 600-700 ℃.
6. Biological glycerol chemical chain reforming hydrogen production CO 2 Process plant for the in situ capture and utilization of hydrogen CO by chemical looping reforming of biological glycerol according to any of claims 1 to 5 2 And (3) in-situ trapping and utilizing.
7. The chemical looping reforming hydrogen production CO of biological glycerol according to claim 6 2 The in-situ trapping and utilizing process device is characterized by consisting of the fuel reactor, the adsorbent regeneration/methane dry reforming reactor, the air reactor and a riser,
wherein the fuel reactor, the adsorbent regeneration/dry methane reforming reactor, and the air reactor are connected by the riser.
8. The chemical looping reforming hydrogen production CO of biological glycerol according to claim 7 2 The in-situ trapping and utilizing process device is characterized in that,
the fuel reactor is provided with a calcium oxide adsorbent, a nickel-based oxygen carrier and nitrogen mixing inlet, a biological glycerol and water mixing inlet, a hydrogen outlet, a slag discharge port, a calcium carbonate and reduced nickel-based oxygen carrier mixing outlet, a regenerated nickel-based oxygen carrier and a regenerated calcium oxide adsorbent circulating inlet.
9. The chemical looping reforming hydrogen production CO of biological glycerol according to claim 7 2 The in-situ trapping and utilizing process device is characterized in that,
the adsorbent regeneration/methane dry reforming reactor is provided with a calcium carbonate and reduced nickel-based oxygen carrier mixing inlet, a mixed gas inlet, a synthetic gas outlet, a reduced nickel-based oxygen carrier and a regenerated calcium oxide adsorbent mixing outlet.
10. The chemical looping reforming hydrogen production CO of biological glycerol according to claim 7 2 The in-situ trapping and utilizing process device is characterized in that,
the air reactor is provided with a reducing nickel-based oxygen carrier and regenerated calcium oxide adsorbent mixing inlet, an air inlet, a gas outlet, a regenerated nickel-based oxygen carrier and regenerated calcium oxide adsorbent mixing outlet and a slag discharge port.
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