CN114736095A - Method for preparing hydrogen and olefin by catalytic oxidation of natural gas - Google Patents
Method for preparing hydrogen and olefin by catalytic oxidation of natural gas Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003345 natural gas Substances 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 7
- 238000002407 reforming Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- -1 C3+ Chemical compound 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- C01B3/36—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 oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
-
- 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
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
-
- 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
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for preparing hydrogen and olefin by catalytic oxidation of natural gas. The method comprises the following steps: gasifying LNG after cascade heat exchange to obtain methane; mixing methane and oxygen, and then carrying out a methane oxidation coupling reaction; the produced product gas is passed through a first high temperatureCarrying out catalytic cracking reaction to prepare olefin after heat exchange; carrying out CO conversion reaction on product gas generated in the reaction of preparing olefin by catalytic cracking after second high-temperature heat exchange; the produced product gas is subjected to medium-temperature heat exchange and then sequentially subjected to CO2Washing with amine and drying; carrying out cascade heat exchange on the treated product gas to obtain mixed gas; and (3) performing membrane separation on the mixed gas, mixing the obtained methane and the LNG to be used as a raw material gas, and purifying the obtained hydrogen through pressure swing adsorption. The method couples the oxidative coupling process and the LNG cold energy utilization process, can realize the energy conversion from methane to hydrogen, can fully utilize carbon in the methane to generate high value-added industrial olefin products, and completes methane, olefin and CO through LNG cryogenic heat exchange2And H2The separation of (2) is an important way for high value-added utilization of methane.
Description
Technical Field
The invention relates to a method for preparing hydrogen and olefin by catalytic oxidation of natural gas, belonging to the technical field of hydrogen preparation from natural gas.
Background
The development of hydrogen energy application technology, especially the maturity of hydrogen fuel cell technology, provides great thrust for the arrival of hydrogen energy society. Currently, there are four main sources of hydrogen: natural substance (such as natural gas)Hydrogen production by gas, hydrogen production by water electrolysis, industrial byproduct hydrogen production and photocatalytic hydrogen production. The natural gas hydrogen production is clean in source, and low in price is the main source of the hydrogen at present. The common natural gas hydrogen production methods include natural gas reforming hydrogen production, natural gas partial oxidation hydrogen production, natural gas cracking hydrogen production and the like. Among them, hydrogen production by reforming is the most mature route, by steam or CO2Converting natural gas into synthetic gas under the action of catalyst, further raising hydrogen concentration by means of subsequent conversion reaction, oxidizing CO, finally utilizing membrane separation and pressure-swing adsorption technology to make purification to form high-purity hydrogen and CO2And emptying to cause carbon resource waste and carbon emission. The natural gas catalytic oxidation coupling technology can directly perform catalytic coupling on natural gas to generate high value-added products such as olefin, hydrogen and the like, but the catalytic oxidation has high requirements on raw material gas, a large number of products and a complex separation process, so that the economic benefit of the path is not obvious enough.
Chinese patent application (CN 111450779A) discloses a reaction device for preparing olefin by methane oxidative coupling and a process thereof, and the technology is characterized in that an oxidative coupling reactor is designed, and through arrangement of a uniform distribution plate, a reaction layer baffle plate and the like in the reactor, heat transfer of the temperature in the reaction process is enhanced, the problem of hot spots existing in the reaction is reduced, and the risk of catalyst sintering is reduced. Chinese patent application (CN 110386853A) discloses a coupling process for preparing ethylene by methane oxidative coupling and preparing synthetic gas by methane dry reforming, which is characterized in that CO is separated from a one-step oxidative coupling product by cooling2The product is sent back to the dry reforming reactor, and the dry reforming reactor and the oxidative coupling reactor are coupled together to realize the high-efficiency utilization of energy, but the technical reactor has a complex structure and low industrial applicability, and after the product is quenched to separate ethylene, the gas needs to be heated and sent back to the reforming reactor, so that the energy efficiency is not high. It is seen that there is a need for a process that can produce high purity hydrogen and olefins using oxidative coupling technology and LNG cold energy cascade technology.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen and olefin by catalytic oxidation of natural gas, which couples an oxidative coupling process and an LNG cold energy utilization process,not only can realize the energy conversion from methane to hydrogen, but also can fully utilize carbon in methane to generate high value-added industrial olefin products, and methane, olefin and CO are finished through LNG cryogenic heat exchange2And H2The separation method has the advantages of short process flow, high energy efficiency and low carbon emission, and is an important way for high value-added utilization of methane.
The method for preparing hydrogen and olefin by catalytic oxidation of natural gas comprises the following steps:
s1, gasifying the LNG after cascade heat exchange to obtain methane;
s2, mixing the methane and oxygen to perform a methane oxidation coupling reaction;
s3, carrying out catalytic cracking reaction on the product gas generated by the methane oxidative coupling reaction to prepare olefin after first high-temperature heat exchange;
the product gas comprises methane, ethane, ethylene, C3+, CO2、CO、H2、H2O and the like;
s4, carrying out CO conversion reaction on the product gas generated by the reaction of preparing olefin by catalytic cracking after second high-temperature heat exchange;
s5, sequentially carrying out CO conversion on the product gas generated by the CO conversion reaction after medium-temperature heat exchange2Amine washing and drying to remove CO separately2And moisture;
s6, performing the cascade heat exchange on the product gas treated in the step S5 to obtain a C3+ component, a C2 component, methane and H2The mixed gas of (3); and performing membrane separation on the mixed gas, mixing the obtained methane with the LNG to be used as a raw material gas, and purifying the obtained hydrogen through pressure swing adsorption.
In the method, the step heat exchange is three-stage low-temperature heat exchange;
in step S6, the temperature of the product gas after primary low-temperature heat exchange is-40 to-50 ℃, the temperature of the product gas after secondary low-temperature heat exchange is-80 to-90 ℃, the C3+ component is obtained at the same time, and the temperature of the product gas after tertiary low-temperature heat exchange is-100 to-120 ℃, and the C2 component is obtained at the same time.
In the method, the temperature of the LNG subjected to the three-stage low-temperature heat exchange is-130 ℃ to-100 ℃, and the liquid state is rich in C2/C3 components for medium hydrocarbon separation treatment.
In the method, the temperature of the methane after the secondary low-temperature heat exchange is-90 ℃ to-100 ℃, and the temperature of the methane after the primary low-temperature heat exchange is-45 ℃ to-55 ℃.
In the method, the methane subjected to the step heat exchange is mixed with the oxygen to serve as a raw material gas after the medium-temperature heat exchange, the second high-temperature heat exchange and the first high-temperature heat exchange are sequentially carried out on the methane;
after the medium-temperature heat exchange, the temperature is raised to 240-270 ℃, after the second high-temperature heat exchange, the temperature is raised to 330-540 ℃, and after the first high-temperature heat exchange, the temperature is raised to 710-850 ℃.
In the above method, in step S2, the feed volume ratio of methane to oxygen is 2 to 4, and the pressure is 3 to 5 MPa.
In the above method, in step S2, the temperature of the alkoxylation coupling reaction may be 700 to 900 ℃.
In the above method, in step S3, the temperature of the catalytic cracking olefin production reaction may be 600 to 800 ℃, and the pressure may be 3 to 5 MPa.
In the above method, in step S4, the CO shift reaction includes a CO high temperature shift reaction and a CO low temperature shift reaction that are sequentially performed;
the temperature of the CO high-temperature shift reaction is 300-500 ℃, the pressure is 2-4 MPa, the temperature of the CO low-temperature shift reaction is 180-250 ℃, and the pressure is 2-4 MPa.
The method of the invention has the following beneficial effects:
1. the method can convert the natural gas into clean energy hydrogen energy and can partially convert the natural gas into olefin products with high industrial added values, thereby realizing high-value utilization of the natural gas and having good economical efficiency.
2. The LNG cold energy can be fully utilized, the energy efficiency of the system is improved, the LNG cold energy is utilized in a cascade manner, the cascade separation of the product gas is realized, and the comprehensive energy efficiency is high.
3. The invention has good environmental benefit, and can reduce carbon emission in the natural gas utilization process and reduce environmental influence.
4. The catalyst has low performance requirement, the LNG has low impurity content, and particularly the content of substances which have toxic effects on the catalyst is extremely low, so that the catalyst has long service life, the catalytic reaction is more stable, and the contents of sulfur oxides and nitrogen oxides in the product are extremely low.
5. By using cold energy in a cascade mode, C2 and C3 alkanes in LNG can be separated, and the industrial added values of C2 and C3 are further improved.
Drawings
FIG. 1 is a flow diagram of a process for the catalytic oxidation of natural gas to produce hydrogen and olefins in accordance with the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The method couples the oxidative coupling process and the LNG cold energy utilization process, can realize the energy conversion from methane to hydrogen, can fully utilize carbon in the methane to generate high value-added industrial olefin products, and completes methane, olefin and CO through LNG cryogenic heat exchange2And H2The separation method has the advantages of short process flow, high energy efficiency and low carbon emission, and is an important way for high value-added utilization of methane.
The process of the method for preparing hydrogen and olefin by catalytic oxidation of natural gas comprises the following steps: LNG from an LNG receiving station is heated and gasified through a three-step low-temperature heat exchanger, the gasified methane is heated through medium-temperature heat exchange and high-temperature heat exchange to be used as a raw material gas, the raw material gas is mixed with oxygen from outside and enters an oxidation coupling reactor to carry out internal oxidation coupling reaction, and the natural gas and the oxygen are subjected to the oxidation coupling reaction to generate C2, C3+ and CO2、H2O、H2CO, and simultaneously the product gas contains CH which is not completely reacted4The product gas is subjected to first high-temperature heat exchange and then subjected to catalytic cracking to prepare olefin, the olefin is further cracked into olefin and hydrogen, after second high-temperature heat exchange, the CO high-temperature shift reaction and the CO low-temperature shift reaction are sequentially performed, and CO is further converted under the action of steamIs CO2Simultaneously generating H2The product gas is subjected to medium-temperature heat exchange and cooling and sequentially passes through CO2Amine scrubbing unit CO removal2The water is removed through a dryer, and then the water is subjected to primary low-temperature heat exchange, secondary low-temperature heat exchange and tertiary low-temperature heat exchange in sequence, wherein a C3+ component is obtained through the secondary low-temperature heat exchange, a C2 component is obtained through the tertiary low-temperature heat exchange, preferably, a mixer of the obtained methane and hydrogen is subjected to membrane separation, the separated hydrogen can be stored and transported at low temperature and high pressure after being purified through pressure swing adsorption, and the separated methane is mixed with LNG after being pressurized to serve as raw material gas.
As shown in fig. 1, is a flow chart of the method of the present invention:
after LNG is gasified, the methane is subjected to high-temperature heat exchange, then mixed with oxygen in a mixer and then enters an oxidative coupling reactor for oxidative coupling reaction, wherein the methane and O2The feed volume ratio of (A) is 4, the pressure is 5MPa, the reaction temperature is 880 ℃, and the outlet gas contains methane, ethane, ethylene, C3+ and CO2、CO、H2、H2O and other components are subjected to first high-temperature heat exchange, then the temperature is reduced to about 850 ℃, and then the catalytic cracking reaction is carried out to prepare olefin, the reaction temperature is 700 ℃, the pressure is 4.5MPa, and the olefin content and the H are further improved2The content of the CO is reduced to be 1-3%, and the H content is improved by performing second high-temperature heat exchange on the reacted gas to 350-550 ℃, then performing first CO conversion reaction at the temperature of 300-400 ℃ and the pressure of 4MPa2The content is reduced to 180-280 ℃ and then the second CO transformation reaction is carried out, the pressure is 3.8MPa, the CO content is further reduced, and the H content is improved2And (4) content. Then the temperature is reduced to 40 ℃ after medium temperature heat exchange, and the mixed solution is sequentially treated by CO2Amine scrubbing to remove CO2The water is removed by drying to ensure that no dry ice or ice is produced on entry to the low temperature stage. The product gas is subjected to primary low-temperature heat exchange, the temperature is reduced to about minus 40 ℃, secondary low-temperature heat exchange is carried out, the temperature is reduced to minus 80 to minus 90 ℃, C3+ medium hydrocarbon components are produced, the temperature is reduced to minus 100 to minus 120 ℃ after the heat exchange with LNG is carried out through tertiary low-temperature heat exchange, C2 products are further produced as byproducts, the concentration of residual methane and hydrogen is more than 95%, hydrogen and methane mixed gas is produced after membrane separation, demethanization is carried out through pressure swing adsorption, high-purity hydrogen is produced, and membrane separation is carried outThe methane gas enters the LNG inlet pipeline after being pressurized.
LNG is heated to about minus 130 ℃ after three-stage low-temperature heat exchange, methane is gasified, C2+ rich liquid is separated and then is independently subjected to medium hydrocarbon separation treatment, gasified methane is heated to about minus 100 ℃ after two-stage low-temperature heat exchange, the temperature is heated to about minus 60 ℃ after first-stage low-temperature heat exchange, the temperature is heated to about 10 ℃ after air heating, the temperature is heated to about 120 ℃ through medium temperature heat exchange, the temperature is heated to 400 ℃ through second high-temperature heat exchange, the temperature is heated to 600-700 ℃ through first high-temperature heat exchange, and the mixture is mixed with oxygen to serve as a raw material gas to enter an oxidative coupling reactor for oxidative coupling reaction.
Claims (10)
1. A method for preparing hydrogen and olefin by catalytic oxidation of natural gas comprises the following steps:
s1, gasifying the LNG after cascade heat exchange to obtain methane;
s2, mixing the methane and oxygen, and then carrying out a methane oxidation coupling reaction;
s3, carrying out catalytic cracking reaction on the product gas generated by the methane oxidative coupling reaction to prepare olefin after first high-temperature heat exchange;
s4, carrying out CO conversion reaction on the product gas generated by the reaction of preparing olefin by catalytic cracking after second high-temperature heat exchange;
s5, sequentially carrying out CO conversion on the product gas generated by the CO conversion reaction after medium-temperature heat exchange2Amine washing and drying to remove CO respectively2And moisture;
s6, performing the cascade heat exchange on the product gas treated in the step S5 to obtain a C3+ component, a C2 component, methane and H2The mixed gas of (2); and performing membrane separation on the mixed gas, mixing the obtained methane with the LNG to be used as a raw material gas, and purifying the obtained hydrogen through pressure swing adsorption.
2. The method of claim 1, wherein: the step heat exchange is three-stage low-temperature heat exchange.
3. The method of claim 2, wherein: in step S6, the temperature of the product gas after the first-stage low-temperature heat exchange is-40 to-50 ℃, the temperature of the product gas after the second-stage low-temperature heat exchange is-80 to-90 ℃, the C3+ component is obtained at the same time, and the temperature of the product gas after the third-stage low-temperature heat exchange is-100 to-120 ℃, and the C2 component is obtained at the same time.
4. The method of claim 3, wherein: the temperature of the LNG subjected to the three-stage low-temperature heat exchange is-130 to-100 ℃, and the liquid state is rich in C2/C3 components for medium hydrocarbon separation treatment.
5. The method of claim 3, wherein: the temperature of the methane after the secondary low-temperature heat exchange is-90 ℃ to-100 ℃, and the temperature of the methane after the primary low-temperature heat exchange is-45 ℃ to-55 ℃.
6. The method according to any one of claims 1-5, wherein: the methane subjected to the step heat exchange is mixed with the oxygen to serve as a raw material gas after the medium-temperature heat exchange, the second high-temperature heat exchange and the first high-temperature heat exchange are sequentially carried out on the methane;
after the medium-temperature heat exchange, the temperature is raised to 240-270 ℃, after the second high-temperature heat exchange, the temperature is raised to 330-540 ℃, and after the first high-temperature heat exchange, the temperature is raised to 710-850 ℃.
7. The method according to any one of claims 1-6, wherein: in step S2, the feeding volume ratio of methane to oxygen is 2-4, and the pressure is 3-5 MPa.
8. The method according to any one of claims 1-7, wherein: in step S2, the temperature of the alkoxylation coupling reaction is 700-900 ℃.
9. The method according to any one of claims 1-8, wherein: in step S3, the temperature of the catalytic cracking olefin production reaction is 600-800 ℃, and the pressure is 3-5 MPa.
10. The method according to any one of claims 1-9, wherein: in step S4, the CO shift reaction includes a CO high temperature shift reaction and a CO low temperature shift reaction that are performed in sequence;
the temperature of the CO high-temperature shift reaction is 300-.
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