CN114716294B - Method for preparing olefin and co-producing high-purity hydrogen by using natural gas hydrate chemical chain - Google Patents
Method for preparing olefin and co-producing high-purity hydrogen by using natural gas hydrate chemical chain Download PDFInfo
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- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000000126 substance Substances 0.000 title claims abstract description 46
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000001257 hydrogen Substances 0.000 title claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 40
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000001301 oxygen Substances 0.000 claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 49
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 5
- 238000011069 regeneration method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000001338 self-assembly Methods 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 4
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- 239000007788 liquid Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
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- 238000004088 simulation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- -1 Natural gas hydrates Chemical class 0.000 description 1
- 229910018098 Ni-Si Inorganic materials 0.000 description 1
- 229910018529 Ni—Si Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
- C01B3/40—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 characterised by the catalyst
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
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- 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
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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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a method for preparing olefin and co-producing high-purity hydrogen by using a natural gas hydrate chemical chain. The method converts gas and liquid two-phase substances of the natural gas hydrate into olefin platform compounds and high-purity hydrogen in a clean and efficient way through the steps of oxygen carrier preparation, chemical chain alkene preparation, chemical chain hydrogen preparation, oxygen carrier regeneration and the like, solves the problem of efficient resource utilization after the exploitation of the traditional natural gas hydrate, has the advantages of simple process, low cost, cleanness, environmental protection and high added value of products, and has wide application prospect.
Description
Technical Field
The invention relates to the fields of clean conversion of fuel, functional materials and environmental protection, in particular to a method for preparing olefin and co-producing high-purity hydrogen by using a natural gas hydrate chemical chain.
Background
Natural gas hydrate is mainly produced in submarine sediments and land permanent frozen soil zones, and is a novel potential energy source. The global resource reserves reach 2.1 multiplied by 10 16m3, and the method has huge development potential. Natural gas hydrates have been studied for many years, and have undergone the stages of combustible ice discovery, laboratory synthesis, pipeline blockage prevention and control, resource investigation and the like, and some countries have entered the resource trial production stage and progressed to happiness. The sea area hydrate test exploitation engineering is successfully implemented in the south sea god fox area three times in 2017 and 2020 in China, so that a great breakthrough in the test exploitation field is obtained, and the commercial exploitation utilization is expected to be realized before and after 2030 after a series of technical, economic and environmental problems are solved. The technology for efficiently utilizing the natural gas hydrate is greatly developed, is hopeful to improve the existing energy structure which is mainly conducted by non-clean energy such as coal, petroleum and the like, and has important significance for protecting ecological environment and promoting a double-carbon strategy.
At present, the main focus of research and study on natural gas hydrate in various countries in the world is mainly on research such as finding production places, determining production and explaining the cause, further calculating resource quantity and the like. The Chinese patent CN202111353480.6 discloses an active excitation type accurate evaluation method for vertical content distribution of a submarine hydrate reservoir, which is characterized in that the device is screwed into submarine drilling, and components and contents of natural gas hydrate excited into the reservoir are analyzed and recorded through an optical ranging unit and a resistivity unit, so that statistics and evaluation of occurrence and contents of natural gas hydrate in any reservoir are completed. The Chinese patent CN202010223932.8 discloses a natural gas hydrate methane decomposition leakage and cold spring ecological simulation system and method, which realize simulation researches on the formation evolution of natural gas hydrate, gas migration and conversion, reservoir sedimentation, development of cold spring system, formation evolution of cold spring ecological system and the like related to the natural gas hydrate decomposition leakage. The Chinese patent CN202110416250.3 discloses a method for exploiting natural gas hydrate by utilizing warm-pressing and step-by-step depressurization, which is characterized in that the heat loss is reduced by step-by-step depressurization, and the exploitation efficiency is improved. Chinese patent CN201820407317.0 discloses a natural gas hydrate conveying device, which can realize safe and efficient transportation of weather hydrate, and avoid the problem of pipeline blockage in the conventional transportation.
The patent relates to the processes of detecting, evaluating, exploiting, storing and transporting the natural gas hydrate, but does not relate to the process of subsequent clean recycling of the natural gas hydrate. Chinese patent No. CN201810228343.1 discloses a method for natural gas peak shaving and water quality purification using hydrates, which combines the advantages of hydrate slurry with good fluidity and hydrate with good gas storage capacity to realize the storage of surplus natural gas in solid form. However, this approach is essentially directed to the physical utilization of the natural gas hydrate formation and release process. In order to realize efficient and high-valued clean conversion of natural gas hydrate, the invention provides a method for preparing olefin and high-purity hydrogen from natural gas hydrate.
Disclosure of Invention
The invention aims to provide a method for preparing olefin and co-producing high-purity hydrogen by using a natural gas hydrate chemical chain.
The technical scheme adopted by the invention is as follows:
A method for preparing olefin and co-producing high-purity hydrogen by using a natural gas hydrate chemical chain comprises the following steps:
(1) The natural gas hydrate is released by grading and decompressing to obtain a gas phase product and a liquid phase product;
(2) Preparing olefin by chemical chain reforming of gas phase product, oxygen carrier and auxiliary agent in a reactor, wherein the temperature of a reaction zone is 600-1000 ℃ and the reaction time is 3-25 min;
(3) The liquid phase product reacts with the oxygen carrier after the reaction for preparing the olefin to prepare the hydrogen, the temperature of a reaction zone is 600-1000 ℃, and the reaction time is 10-30 min;
(4) The oxygen carrier after the hydrogen production reaction is regenerated by air, and lattice oxygen in the oxygen carrier is recovered.
In the step (1), the step-by-step decompression is carried out under the pressure of 8-2 MPa, and the temperature range is-180-normal temperature.
In the step (2), the oxygen carrier is at least one selected from iron-based, manganese-based, copper-based, cobalt-based, zinc-based and nickel-based, and the oxygen carrier can also contain Al 2O3 or SiO 2 as a carrier. The preparation method of the oxygen carrier comprises the following steps: preparing a precursor by adopting chemical coprecipitation, chemical wet impregnation, chemical self-assembly method or sol-gel method, then carrying out high-temperature reaction for 3-5 h at 800-1000 ℃, and then crushing and screening to obtain the product with the particle size range of 40-80 meshes.
In the step (2), the auxiliary agent is at least one selected from Na +、K+、Ca2+.
In the step (2), the method also comprises the step of introducing a small amount of water vapor to inhibit carbon deposition on the surface of the oxygen carrier.
In the step (2), the natural gas hydrate gas-phase product is subjected to bond breaking, dissociation and partial oxidation reaction dehydration with oxygen in an oxygen carrier lattice to obtain an olefin product. The secondary reaction of carbon deposition on the surface of the oxygen carrier and olefin can be inhibited by the high-efficiency oxygen carrier auxiliary agent and the dynamic regulation and control method of the reaction process, and the yield and selectivity of the low-carbon olefin are improved.
In the step (3), the liquid phase product of the natural gas hydrate reacts with the reduced oxygen carrier to generate high-purity hydrogen, and meanwhile, a small amount of Na + contained in the liquid phase product can be used as an oxygen carrier auxiliary agent to improve the product selectivity of preparing olefin by chemical chains in subsequent circulation.
In the step (4), the reaction temperature of the oxygen carrier regeneration is 800-1000 ℃ and the reaction time is 30-90 min. The reaction heat obtained in the regeneration process provides heat for the process of preparing olefin and hydrogen by chemical chains through oxygen carrier circulation, and the heat balance is realized by burning part of gas phase products obtained in the step (1) in the part of the system with insufficient overall heat.
The invention has the following beneficial effects:
1. The technology for preparing the olefin and co-producing the high-purity hydrogen through the chemical chain of the natural gas hydrate solves the problem of high-efficiency recycling utilization after the exploitation of the traditional natural gas hydrate, can clean and efficiently convert the natural gas hydrate into the olefin platform compound and the high-purity hydrogen directly, and has the advantages of simple process, low cost, cleanness, environmental protection and high added value of products.
2. The invention utilizes the gas-liquid two-phase products in the natural gas hydrate, and a small amount of salt in the liquid phase product can also be used for improving the selectivity of olefin, has the advantage of high comprehensive utilization efficiency of resources, can be used as chemical synthesis raw materials, has high purity of the obtained hydrogen product, does not need complex separation process, and can be directly used for fuel cells.
Drawings
FIG. 1 is a flow chart for co-producing high purity hydrogen from natural gas hydrate chemical looping.
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof.
The methods for preparing the composite oxygen carrier in the examples below are all conventional in the art.
Example 1
The embodiment discloses a method for preparing olefin co-production high-purity hydrogen by using a natural gas hydrate chemical chain, which comprises the following steps:
(1) The natural gas hydrate is released into a gas phase product and a liquid phase product through three-stage grading decompression (the temperature range is-180 ℃ to normal temperature) of 8MPa, 4MPa and 2MPa, so that the heat loss is reduced, and the gas-liquid separation is realized.
(2) The Fe/Cu/Zn-based composite oxygen carrier (with the atomic ratio of 0.6/0.3/0.1) precursor is constructed by adopting a chemical precipitation method, and then the precursor is calcined for 4 hours at 900 ℃, and then crushed and screened to prepare the oxygen carrier particles with the particle size range of 40-60 meshes.
(3) The gas phase product of the natural gas hydrate reacts with Fe/Cu/Zn-based composite oxygen carrier and the electronic auxiliary agent NaCl in a reactor to prepare olefin by chemical chain, the reaction temperature is 600 ℃, the reaction time is 20 minutes, and a small amount of steam is introduced during the reaction to inhibit carbon deposition on the surface of the oxygen carrier.
(4) And carrying out a chemical chain hydrogen production process on the natural gas hydrate liquid-phase product and an oxygen carrier after the reaction for preparing olefin to obtain high-purity hydrogen, wherein the reaction temperature is 750 ℃ and the reaction time is 25 minutes. Meanwhile, a small amount of Na + contained in the liquid-phase product can be used as an oxygen carrier auxiliary agent, so that the product selectivity of the olefin prepared by chemical chains in subsequent circulation is improved.
(5) The oxygen carrier after the hydrogen production reaction recovers lattice oxygen in the oxygen carrier through air regeneration, the reaction temperature is 900 ℃, the reaction time is 60 minutes, and the generated heat is circularly transported to the process of preparing olefin by chemical chains and producing hydrogen by chemical chains through the oxygen carrier. And (3) in the part with insufficient overall heat of the system, the natural gas hydrate gas-phase product in the part (1) is combusted by the burner to realize heat balance.
The flow of co-production of high purity hydrogen from natural gas hydrate chemical chain is shown in figure 1.
The results show that the relative composition of gas phase products in the process of preparing olefins by chemical chains is 7.69% of CH 4 31.66％,C2 ＝–C4 ＝38.62％,C2–C4 hydrocarbon, 6.75% of C 5+ product, 15.28% of H 2/CO/CO2 and other gases. The methane conversion rate exceeds 68.02%, and the low-carbon olefin selectivity exceeds 38.62%. The hydrogen yield in the chemical-looping hydrogen production process is 1.21L/g, and the H 2 concentration is 98.5%.
Example 2
Since the method for preparing olefin and co-producing high purity hydrogen from natural gas hydrate chemical chains is the same as that of example 1, the details are not repeated here, and only the implementation conditions are listed in table 1, and the implementation results are shown in table 1.
Table 1 example of co-production of high purity hydrogen from natural gas hydrate chemical looping
In the embodiment, a Cu/Co/Mn composite oxygen carrier precursor is constructed by adopting a sol-gel method, and then the precursor is calcined at 900 ℃ for 4 hours, and then crushed and sieved to prepare oxygen carrier particles with the particle size range of 40-60 meshes.
Example 3
Since the method for co-producing high purity hydrogen from natural gas hydrate chemical looping olefins is the same as in example 1, the details are not repeated here, and only the implementation conditions are listed in table 2, and the implementation results are shown in table 2.
Table 2 example of the preparation of olefins from natural gas hydrate chemical chains with co-production of high purity hydrogen
In the embodiment, a chemical self-assembly method is adopted to construct a Fe/Cu/Ni-Si composite oxygen carrier precursor, and after calcining for 4 hours at 950 ℃, the precursor is crushed and sieved to prepare oxygen carrier particles with the particle size range of 40-60 meshes.
Example 4
Since the method for co-producing high purity hydrogen from natural gas hydrate chemical looping olefins is the same as in example 1, the details are not repeated here, and only the implementation conditions are listed in table 3, and the implementation results are shown in table 3.
Table 3 example of the preparation of olefins from natural gas hydrate chemical chains with co-production of high purity hydrogen
In the embodiment, a chemical self-assembly method is adopted to construct a Fe/Cu/Al/Mn composite oxygen carrier precursor, and after calcining for 4 hours at 900 ℃, the precursor is crushed and sieved to prepare oxygen carrier particles with the particle size range of 40-60 meshes.
Example 5
Since the method for co-producing high purity hydrogen from natural gas hydrate chemical looping olefins is the same as in example 1, the details are not repeated here, and only the implementation conditions are listed in table 4, and the implementation results are shown in table 4.
Table 4 example of the preparation of olefins from natural gas hydrate chemical chains with co-production of high purity hydrogen
In the embodiment, a sol-gel method is adopted to construct a Fe/Cu/Co/Al composite oxygen carrier precursor, and after calcining for 4 hours at 950 ℃, the precursor is crushed and sieved to prepare oxygen carrier particles with the particle size range of 40-60 meshes.
Comparative example 1
Since the method for co-producing high purity hydrogen from natural gas hydrate chemical looping olefin is the same as in example 1, the description thereof will not be repeated here. In contrast, the specific implementation results of this example without adding any olefin preparation aid are shown in Table 5.
Table 5 example of the preparation of olefins from natural gas hydrate chemical chains with co-production of high purity hydrogen
In this comparative example, a chemical precipitation method was used to construct a Fe/Cu/Zn/Mn composite oxygen carrier precursor, which was calcined at 900℃for 4 hours, and then pulverized and sieved to prepare oxygen carrier particles having a particle size range of 40 to 60 mesh.
The results of comparative example 1 show that the yield of olefin C 2 ＝–C4 ＝ is reduced and the yield of other gases (miscellaneous gases) such as H 2/CO/CO2 is improved without adding any reaction electron auxiliary agent in the process of preparing olefin by chemical chain. The results show that the addition of the reaction electron auxiliary agent is beneficial to the improvement of the yield of the olefin in the process of preparing the olefin by chemical chain.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (3)
1. The method for preparing the olefin and co-producing the high-purity hydrogen by using the chemical chain of the natural gas hydrate is characterized by comprising the following steps of:
(1) The natural gas hydrate is released by grading and decompressing to obtain a gas phase product and a liquid phase product; the step-by-step decompression is carried out under 8-2 MPa, and the temperature range is-180-normal temperature;
(2) Preparing olefin by chemical chain reforming of the gas-phase product, an oxygen carrier and an auxiliary agent in a reactor, wherein the temperature of a reaction zone is 600-1000 ℃ and the reaction time is 3-25 min; the oxygen carrier is selected from at least one of iron base, manganese base, copper base, cobalt base, zinc base and nickel base, and also contains Al 2O3 or SiO 2 as a carrier; the preparation method of the oxygen carrier comprises the following steps: preparing a precursor by adopting chemical coprecipitation, chemical wet impregnation, chemical self-assembly method or sol-gel method, reacting for 3-5 hours at 800-1000 ℃, crushing and screening to obtain the precursor with the particle size range of 40-80 meshes; the auxiliary agent is at least one selected from Na +、K+、Ca2+;
(3) The liquid phase product reacts with an oxygen carrier after the reaction for preparing the olefin to prepare hydrogen, the temperature of a reaction zone is 600-1000 ℃, and the reaction time is 10-30min;
(4) The oxygen carrier after the hydrogen production reaction is regenerated by air, and lattice oxygen in the oxygen carrier is recovered.
2. The method for preparing olefin and co-producing high purity hydrogen by using natural gas hydrate chemical looping according to claim 1, wherein,
In the step (2), the method also comprises the step of introducing a small amount of water vapor to inhibit carbon deposition on the surface of the oxygen carrier.
3. The method for preparing olefin and co-producing high purity hydrogen by using natural gas hydrate chemical looping according to claim 1, wherein,
In the step (4), the reaction temperature of oxygen carrier regeneration is 800-1000 ℃ and the reaction time is 30-90 min.
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