CN114716294A - Method for preparing olefin and co-producing high-purity hydrogen by natural gas hydrate chemical chain - Google Patents
Method for preparing olefin and co-producing high-purity hydrogen by natural gas hydrate chemical chain Download PDFInfo
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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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- 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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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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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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Abstract
The invention discloses a method for preparing olefin and co-producing high-purity hydrogen by a natural gas hydrate chemical chain. The method cleanly and efficiently converts the gas-liquid two-phase substances of the natural gas hydrate into the olefin platform compound and the high-purity hydrogen through the steps of oxygen carrier preparation, chemical chain alkene preparation, chemical chain hydrogen production, oxygen carrier regeneration and the like, solves the problem of efficient resource utilization after the traditional natural gas hydrate is mined, and has the advantages of simple process, low cost, cleanness, environmental protection, high product added value and wide application prospect.
Description
Technical Field
The invention relates to the fields of clean fuel conversion, functional materials and environmental protection, in particular to a method for preparing olefin and co-producing high-purity hydrogen by a natural gas hydrate chemical chain.
Background
The natural gas hydrate is mainly produced in seabed sediments and land permafrost zones, and is a novel potential energy source. The global resource reserve reaches 2.1 multiplied by 1016m3And has great development potential. People have studied natural gas hydrate for years, and the natural gas hydrate generally passes through stages of combustible ice discovery, laboratory synthesis, pipeline blockage prevention, resource investigation and the like, and some countries enter a resource pilot production stage and are favored to develop. In 2017 and 2020, China successfully implements sea hydrate trial production engineering in south China sea Shenhu areas three times in sequence, so that a major breakthrough in the trial production field is obtained, and after a series of technical, economic and environmental problems are overcome, the commercial exploitation and utilization are expected to be realized before and after 2030 years. The technology for efficiently utilizing the natural gas hydrate is developed greatly, the existing energy structure which is dominated by non-clean energy such as coal, petroleum and the like is expected to be improved, and the method has important significance for protecting the ecological environment and promoting the strategy of 'double carbon'.
At present, the research and study of natural gas hydrates in various countries in the world mainly focuses on the research of finding the producing area, determining the producing state and explaining the cause, further calculating the resource amount and the like. The invention patent CN202111353480.6 discloses an active excitation type precise evaluation method for vertical content distribution of a seabed hydrate reservoir, which is characterized in that the device is screwed into a seabed well, and the components and the content of the excited natural gas hydrate are analyzed and recorded through an optical distance measuring unit and a resistivity unit, so that the statistics and evaluation of the occurrence and the content of the natural gas hydrate of any reservoir are completed. The Chinese patent CN202010223932.8 discloses a system and a method for simulating methane leakage decomposition of natural gas hydrate and cold spring ecology, which realizes simulation researches on formation evolution of natural gas hydrate, gas migration transformation, reservoir sedimentation and development of cold spring system, formation evolution of cold spring ecosystem and the like related to natural gas hydrate decomposition and leakage. The Chinese patent CN202110416250.3 discloses a method for exploiting natural gas hydrate by utilizing temperature and pressure in cooperation with step-by-step depressurization, which is characterized in that the heat loss is reduced by the step-by-step depressurization, and the exploitation efficiency is improved. Chinese patent CN201820407317.0 discloses a natural gas hydrate conveyor, can realize transporting weather hydrate safely, high-efficiently, has avoided the problem of pipeline jam in traditional transportation.
The patent relates to the processes of detection, evaluation, exploitation, storage and transportation and the like of the natural gas hydrate, but does not relate to the subsequent clean resource utilization process of the natural gas hydrate. Chinese patent CN201810228343.1 discloses a method for natural gas peak regulation and water purification by using hydrate, 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 method is essentially directed to the physical utilization of the natural gas hydrate formation and release process. The invention provides a method for preparing olefin and high-purity hydrogen from natural gas hydrate in order to realize efficient and high-valued clean conversion of the 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 a natural gas hydrate chemical chain comprises the following steps:
(1) the natural gas hydrate is released by stage decompression to obtain a gas phase product and a liquid phase product;
(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;
(3) reacting the liquid-phase product with an oxygen carrier after olefin preparation reaction to prepare hydrogen, wherein the temperature of a reaction zone is 600-1000 ℃, and the reaction time is 10-30 min;
(4) the oxygen carrier after hydrogen production reaction is regenerated by air to recover lattice oxygen in the oxygen carrier.
In the step (1), the step-by-step pressure reduction is carried out at 8-2 MPa, and the temperature range is-180-normal temperature.
In the step (2), the oxygen carrier is selected from at least one of iron-based, manganese-based, copper-based, cobalt-based, zinc-based and nickel-based, and the oxygen carrier can also contain Al2O3Or SiO2As a support. The preparation method of the oxygen carrier comprises the following steps: the precursor is prepared by adopting a chemical coprecipitation method, a chemical wet impregnation method, a chemical self-assembly method or a sol-gel method, and is obtained by crushing and screening after reacting at the high temperature of 800-1000 ℃ for 3-5 h, wherein the particle size range is 40-80 meshes.
In the step (2), the auxiliary agent is selected from Na+、K+、Ca2+At least one of (a).
And (2) 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 and dissociation on the surface of an oxygen carrier, and is subjected to partial oxidation reaction with oxygen of an oxygen carrier lattice for dehydration to obtain an olefin product. The high-efficiency oxygen carrier additive and the reaction process dynamic regulation method can inhibit carbon deposition on the surface of the oxygen carrier and secondary reaction of olefin, and improve the yield and selectivity of low-carbon olefin.
In the step (3), the natural gas hydrate liquid phase product reacts with the reduced oxygen carrier to generate high-purity hydrogen, and 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 chemical chain preparation olefin in subsequent circulation.
In the step (4), the reaction temperature for regenerating the oxygen carrier is 800-1000 ℃, and the reaction time is 30-90 min. The reaction heat obtained in the regeneration process provides heat for the chemical chain olefin production and hydrogen production process through oxygen carrier circulation, the part with insufficient heat of the whole system is obtained, and the heat balance is realized through burning part of gas-phase products obtained in the step (1).
The invention has the following beneficial effects:
1. the technology for preparing olefin and co-producing high-purity hydrogen by using the natural gas hydrate chemical chain solves the problem of efficient resource utilization after the traditional natural gas hydrate is mined, can cleanly 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 product added value.
2. The method simultaneously utilizes gas-liquid two-phase products in the natural gas hydrate, and a small amount of salt in the liquid-phase product can be used for improving the selectivity of the olefin, so that the method has the advantage of high comprehensive utilization efficiency of resources, the obtained olefin product can be used as a chemical synthesis raw material, the obtained hydrogen product has high purity, a complex separation process is not needed, and the method can be directly used for fuel cells.
Drawings
FIG. 1 is a flow diagram of the co-production of high purity hydrogen from olefin production by natural gas hydrate chemical looping.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
The methods for preparing the composite oxygen carriers in the following examples are all conventional in the art.
Example 1
The embodiment discloses a method for preparing olefin and co-producing high-purity hydrogen by 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 graded decompression (the temperature range is minus 180 ℃ to normal temperature) of 8MPa, 4MPa and 2MPa, so that the heat loss is reduced, and the gas-liquid separation is realized.
(2) A precursor of the Fe/Cu/Zn-based composite oxygen carrier (with the atomic ratio of 0.6/0.3/0.1) is constructed by adopting a chemical precipitation method, and is calcined at 900 ℃ for 4 hours, and then is crushed and screened to prepare oxygen carrier particles with the particle size range of 40-60 meshes.
(3) The gas phase product of the natural gas hydrate, the Fe/Cu/Zn-based composite oxygen carrier and the reaction electronic assistant NaCl are subjected to chemical chain olefin preparation reaction in a reactor, the reaction temperature is 600 ℃, the reaction time is 20 minutes, and a small amount of water vapor is introduced during the reaction to inhibit carbon deposition on the surface of the oxygen carrier.
(4) The liquid phase product of the natural gas hydrate and the oxygen carrier after the reaction of preparing the olefin are used for carrying out the chemical chain hydrogen production process to obtain high-purity hydrogen, the reaction temperature is 750 ℃, and the reaction time is 25 minutes. While 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 chemical chain preparation olefin in subsequent circulation.
(5) The oxygen carrier after hydrogen production reaction is regenerated by air, lattice oxygen in the oxygen carrier is recovered, the reaction temperature is 900 ℃, the reaction time is 60 minutes, and the generated heat is circularly transported to the processes of preparing olefin by a chemical chain and producing hydrogen by the chemical chain through the oxygen carrier. And (3) burning the partial gas hydrate gas phase product in the step (1) by a burner to realize heat balance in the part with insufficient heat of the whole system.
The flow of the chemical chain olefin production and high-purity hydrogen production by natural gas hydrate is shown in figure 1.
The results show that the gas phase product of the chemical chain olefin production process has a relative composition CH4 31.66％，C2 ＝–C4 ＝38.62％，C2–C4Hydrocarbons 7.69%, C5+Product 6.75%, H2/CO/CO2And other gases 15.28%. The methane conversion rate exceeds 68.02%, and the low-carbon olefin selectivity exceeds 38.62%. The hydrogen yield in the chemical chain hydrogen production process is 1.21L/g, H2The concentration was 98.5%.
Example 2
Since the method for preparing olefin and co-producing high-purity hydrogen by using the natural gas hydrate chemical chain is the same as that in example 1, the detailed description is omitted, only the implementation conditions are listed in table 1, and the implementation results are shown in table 1.
TABLE 1 example of chemical looping of natural gas hydrates to olefins and co-produce high purity hydrogen
In the embodiment, a Cu/Co/Mn composite oxygen carrier precursor is constructed by a sol-gel method, and is calcined at 900 ℃ for 4 hours, and then is 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 by olefin production through natural gas hydrate chemical looping is the same as that in example 1, the detailed description is omitted, only the implementation conditions are listed in table 2, and the implementation results are shown in table 2.
Table 2 example of chemical looping of natural gas hydrates to produce olefins and co-produce 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 the precursor is calcined at 950 ℃ for 4 hours, and then 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 by olefin production through natural gas hydrate chemical looping is the same as that in example 1, the detailed description is omitted, only the implementation conditions are listed in table 3, and the implementation results are shown in table 3.
Table 3 example of chemical looping of natural gas hydrates to produce olefins and co-produce 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 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 5
Since the method for co-producing high-purity hydrogen by olefin production through natural gas hydrate chemical looping is the same as that in example 1, the detailed description is omitted, only the implementation conditions are listed in table 4, and the implementation results are shown in table 4.
Table 4 example of chemical looping of natural gas hydrates to produce olefins and co-produce high purity hydrogen
In the embodiment, a Fe/Cu/Co/Al composite oxygen carrier precursor is constructed by a sol-gel method, and is calcined at 950 ℃ for 4 hours, and then 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 by olefin production through natural gas hydrate chemical looping is the same as that in example 1, the details are not repeated herein. For comparison, no olefin preparation aid was added in this example, and the specific implementation results are shown in table 5.
Table 5 example of chemical looping of natural gas hydrates to produce olefins and co-produce high purity hydrogen
In the comparative example, a Fe/Cu/Zn/Mn composite oxygen carrier precursor is constructed by a chemical precipitation method, calcined at 900 ℃ for 4 hours, and crushed and sieved to prepare oxygen carrier particles with the particle size range of 40-60 meshes.
The results of comparative example 1 show that in the process of preparing olefin by chemical chain, no reaction electron assistant is added, and olefin C2 ＝–C4 ＝Reduced yield, H2/CO/CO2And the yield of other gases (miscellaneous gases) is improved. The above results show that in the process of preparing olefin by chemical chain, the addition of reaction electron auxiliary agent is beneficial to improving the yield of olefin.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the 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 these modifications and adaptations should be considered within the scope of the invention.
Claims (8)
1. A method for preparing olefin and co-producing high-purity hydrogen by a natural gas hydrate chemical chain is characterized by comprising the following steps:
(1) the natural gas hydrate is released by stage decompression to obtain a gas phase product and a liquid phase product;
(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;
(3) reacting the liquid-phase product with an oxygen carrier after olefin preparation reaction to prepare hydrogen, wherein the temperature of a reaction zone is 600-1000 ℃, and the reaction time is 10-30 min;
(4) the oxygen carrier after hydrogen production reaction is regenerated by air to recover lattice oxygen in the oxygen carrier.
2. The method for preparing olefin and co-producing high-purity hydrogen by using the natural gas hydrate chemical chain as claimed in claim 1, wherein in the step (1), the step-by-step pressure reduction is carried out at 8-2 MPa, and the temperature range is-180 ℃ to normal temperature.
3. The method for preparing olefin and co-producing high-purity hydrogen by using natural gas hydrate chemical chain as claimed in claim 1, wherein in the step (2), the oxygen carrier is selected from at least one of iron-based, manganese-based, copper-based, cobalt-based, zinc-based and nickel-based.
4. The method of claim 3, wherein the oxygen carrier further comprises Al2O3Or SiO2As a support.
5. The method for preparing olefin and co-producing high-purity hydrogen by using the natural gas hydrate chemical chain as claimed in claim 4, wherein the preparation method of the oxygen carrier is as follows: the precursor is prepared by adopting a chemical coprecipitation method, a chemical wet impregnation method, a chemical self-assembly method or a sol-gel method, and is obtained by crushing and screening after reacting at the high temperature of 800-1000 ℃ for 3-5 h, wherein the particle size range is 40-80 meshes.
6. The method for preparing olefin and co-producing high-purity hydrogen by using natural gas hydrate chemical chain as claimed in claim 1, wherein in the step (2), the auxiliary agent is selected from Na+、K+、Ca2+At least one of (1).
7. The method for preparing olefin and coproducing high-purity hydrogen by using the natural gas hydrate chemical chain as claimed in claim 1, wherein the step (2) further comprises the step of introducing a small amount of water vapor to inhibit carbon deposition on the surface of the oxygen carrier.
8. The method for preparing olefin and co-producing high purity hydrogen by natural gas hydrate chemical looping according to claim 1,
in the step (4), the reaction temperature for regenerating the oxygen carrier is 800-1000 ℃, and the reaction time is 30-90 min.
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