CN117735480A - Hydrocarbon conversion method and device - Google Patents
Hydrocarbon conversion method and device Download PDFInfo
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- CN117735480A CN117735480A CN202311853462.3A CN202311853462A CN117735480A CN 117735480 A CN117735480 A CN 117735480A CN 202311853462 A CN202311853462 A CN 202311853462A CN 117735480 A CN117735480 A CN 117735480A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 35
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 35
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 111
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000003245 coal Substances 0.000 claims abstract description 20
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 19
- 230000023556 desulfurization Effects 0.000 claims abstract description 18
- 238000011084 recovery Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 238000000629 steam reforming Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000005431 greenhouse gas Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- -1 methane and the like Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940062043 nitrogen 50 % Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Abstract
The invention discloses a hydrocarbon conversion method and device, and belongs to the technical field of coalbed methane. The invention solves the problem that the gas layer in the prior art can not fully exert the resource value thereof, and comprises the following steps: step S1: the raw material gas is subjected to a one-stage conversion deoxidization process to obtain raw material gas A; step S2: boosting the obtained raw material gas A to obtain raw material gas B; step S3: desulfurizing the raw material gas B to obtain a desulfurized gas C; step S4: conveying the desulfurization gas C into a furnace tube of a secondary reformer to perform hydrocarbon steam reforming reaction to obtain reformed gas D; step S5: conveying the converted gas D into a three-stage conversion furnace to carry out deep conversion reaction of methane to obtain converted gas E; step S6: and (5) carrying out heat recovery on the converted gas E to obtain the synthesis gas. Aiming at the characteristic of high oxygen content and high nitrogen content of the coal bed gas, the invention provides a hydrocarbon three-stage conversion technology, and solves the problems of safe utilization of oxygen content in the coal bed gas and environmental pollution caused by emission of greenhouse gases.
Description
Technical Field
The invention belongs to the technical field of coalbed methane, and particularly relates to a hydrocarbon conversion method and device.
Background
Coal bed gas, also called coal bed gas, is a mixed gas composed of methane, nitrogen, oxygen, carbon dioxide and the like which are escaped from coal and surrounding rock. Typical compositions of coalbed methane are methane-38%, nitrogen-50%, oxygen-12%, and small amounts of carbon dioxide and sulfides. The explosion limit of the coal bed gas is about 14% -40%, and because the coal bed gas is close to the explosion lower limit, explosion accidents frequently occur in the coal mining process, the safe utilization of the coal bed gas is a difficult point all the time, and the greenhouse effect caused by the in-situ emission of the low-concentration coal bed gas also has a negative influence on the climate.
Although the coalbed methane belongs to available energy, the coalbed methane is limited by technical means due to regional limitation, air source dispersion and poor safety, for example, the patent with the patent number of CN 1789111A discloses a process method for producing hydrogen by self-heating conversion of oxygen in a medium methane content coal gas layer, but the oxygen content of the coalbed methane before deoxidation is generally not more than 1% in a desulfurization device, otherwise, the desulfurization device cannot operate due to severe overtemperature, and the method is not suitable for treating 1-15% oxygen concentration gas. Patent No. CN 101613627B discloses an oxygen-containing coal bed gas catalytic deoxidation process, which solves the problem that O is used in the process of liquefying and storing coal bed gas 2 The potential safety hazard caused by the existence of the catalyst can be applied to the catalytic deoxidation of oxygen-containing coal bed gas and other oxygen-containing gas, but the catalyst adopts a noble metal catalyst and has high cost. Therefore, coal bed gas is sent to end users for combustion through a pipe network at present, or methane is concentrated through a physical method, so that the resource value of the coal bed gas is not fully exerted.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hydrocarbon conversion method and a device.
The technical scheme adopted by the invention is as follows:
a hydrocarbon conversion process comprising the steps of:
step S1: one-stage conversion: the raw material gas is subjected to combustion reaction of oxygen and hydrogen or methane in a primary reformer, and oxygen in the raw material gas is removed to obtain raw material gas A;
step S2: boosting the raw material gas A obtained in the step S1 after cooling to obtain raw material gas B;
step S3: desulfurizing the raw material gas B obtained in the step S2 to obtain a desulfurized gas C;
step S4: two-stage conversion: conveying the desulfurization gas C obtained in the step S3 into a furnace tube of a two-stage reformer to carry out hydrocarbon steam reforming reaction to obtain reformed gas D;
step S5: three-stage conversion: conveying the converted gas D obtained in the step S4 into a three-stage converter for deep conversion reaction of methane to obtain converted gas E;
step S6: and (5) carrying out heat recovery on the converted gas E obtained in the step (S5) to obtain the synthesis gas.
Preferably, when the raw material gas is conveyed into a primary reformer for carrying out the combustion reaction of oxygen and hydrogen or methane, the reaction pressure is between normal pressure and 1.0MpaG, the temperature is between 600 and 1300 ℃, and the primary reformer is a non-catalytic partial oxidation furnace without filling catalyst.
Preferably, the pressure boosting device used in step S2 is a reciprocating compressor or a centrifugal compressor, and the pressure after boosting is 1.0-4.0MPaG.
After the technical scheme is adopted, the boosting device is a reciprocating compressor or a centrifugal compressor, and the purpose of boosting is to reduce the equipment size, reduce the investment and the occupied area and facilitate transportation.
Preferably, the desulfurization device used in step S2 removes the total sulfur in the gas to 0.2ppm or less.
Preferably, in the step S4, the secondary reformer is a heat exchange reformer and/or a van reformer, the temperature of the reformed gas D is 600-900 ℃, and the secondary reformer adopts a fuel combustion heat supply and/or non-fuel combustion heat supply mode.
Preferably, the three-stage reformer in step S5 is a partial oxidation furnace with a catalyst, and the temperature of the reformed gas E is 800-1000 ℃.
Preferably, the feed gas in step S1 is a gaseous hydrocarbon, and the gaseous hydrocarbon includes hydrocarbon-containing gases such as natural gas, coke oven gas, and coal bed gas.
A hydrocarbon conversion device comprises a primary reformer, a supercharging device, a desulfurizing device, a secondary reformer, a tertiary reformer, a heat recovery device and a synthetic gas storage device which are connected in sequence.
Preferably, the primary reformer is not filled with a reaction catalyst, a long through port for introducing high-temperature gas is arranged on the primary reformer, and a plurality of raw gas inlets for introducing raw gas are also arranged on the primary reformer; the secondary reformer is a van-type reformer or a heat exchange type reformer, and a reaction catalyst is arranged in a reformer tube of the secondary reformer; the three-section reformer is a partial oxidation furnace filled with a catalyst, the partial oxidation furnace is a self-heating reactor, a high-temperature mixer is arranged in the three-section reformer, and the high-temperature mixer is connected with an oxygen-containing gas input pipeline.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. according to the invention, the oxygen in the coal bed gas is treated by adding a first-stage conversion process, so that the safety of secondary transportation and conversion of the coal bed gas is greatly improved, the carbon emission is reduced, the greenhouse effect is reduced, and the problem of mine mouth emission pollution is solved.
2. The primary conversion process adopts a non-catalytic partial oxidation process, does not need additional oxygen, can be used for preparing steam in a non-matched or less-matched mode, and can be used for carrying out on-site conversion treatment on the coal bed gas.
3. The two-stage conversion process of the present invention may employ a conventional pressurized steam conversion process or a heat exchange type conversion process or a parallel or serial conversion process in which the pressurized steam conversion process and the heat exchange type conversion process are combined.
4. The hydrocarbon conversion method has the advantages of simple structure and convenient manufacture and maintenance, can realize the joint production of hydrogen, methanol, ammonia, acetic acid and the like, and realizes the recycling of resources, thereby greatly reducing various consumption indexes.
5. The three-stage conversion process adopts an autothermal catalytic partial oxidation process, and pure oxygen or air or oxygen-enriched/nitrogen-enriched air is added to deeply convert alkanes such as methane and the like, so that the utilization rate of raw materials is improved.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic view of a device connection mechanism according to the present invention;
wherein, 1-primary reformer, 2-supercharging device, 3-desulfurization device, 4-secondary reformer, 5-tertiary reformer, 6-heat recovery unit, 7-synthetic gas storage device.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, which are generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present application, as provided in the accompanying drawings, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to be within the scope of the present application.
In the description of the embodiments of the present application, it should be noted that, directions or positional relationships indicated by terms such as "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are directions or positional relationships based on those shown in the drawings, or those that are conventionally put in use of the inventive product, are merely for convenience of description and simplicity of description, and are not indicative or implying that the apparatus or element to be referred to must have a specific direction, be configured and operated in a specific direction, and thus should not be construed as limiting the present application. Furthermore, the terms "first," "second," "third," and the like are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
As shown in fig. 1 and 2, a hydrocarbon conversion process is performed by a hydrocarbon conversion apparatus including a primary reformer 1, a supercharging apparatus 2, a desulfurization apparatus 3, a secondary reformer 4, a tertiary reformer 5, a heat recovery apparatus 6, and a synthesis gas storage apparatus 7, which are connected in this order. The air outlet end of the primary reformer 1 is communicated with the air inlet of the supercharging device 2, the air inlet end of the desulfurization device 3 is communicated with the air outlet of the supercharging device 2, the air inlet end of the secondary reformer 4 is communicated with the air outlet of the desulfurization device 3, the air inlet end of the tertiary reformer 5 is communicated with the air outlet of the secondary reformer 4, the air inlet end of the heat recovery device 6 is communicated with the air outlet of the tertiary reformer 5, and the air outlet end of the heat recovery device 6 is communicated with the synthetic gas storage device.
In this embodiment, the heat recovery device 6 is a heat exchanger or a separator, and can recover the waste heat of the gas and cool down the gas.
In this embodiment, the primary reformer 1 is not filled with a reaction catalyst, a long port for introducing high-temperature gas is provided on the primary reformer 1, and a plurality of raw gas inlets for introducing raw gas are provided on the primary reformer 1; the secondary reformer 4 is a van-type reformer and/or a heat exchange type reformer, and a reaction catalyst is filled in a reformer tube of the secondary reformer 4; the three-stage reformer 5 is a partial oxidation furnace filled with a catalyst, the partial oxidation furnace is a self-heating reactor, a high-temperature mixer is arranged in the three-stage reformer 5, and the high-temperature mixer is connected with an oxygen-containing gas input pipeline.
In this embodiment, the booster is a reciprocating compressor, and the boosted pressure is 3MPaG.
In this example, the desulfurization unit 3 uses a dry desulfurization method, specifically, a desulfurization catalyst to remove the total sulfur in the gas to 0.2ppm or less.
The hydrocarbon conversion process comprises the steps of:
step S1: one-stage conversion: delivering the coalbed methane into a primary reformer 1, introducing high-temperature gas, performing combustion reaction of oxygen and hydrogen or methane, wherein the reaction pressure is normal pressure, the temperature is 800 ℃, no additional oxygen is needed, no steam is needed, and the oxygen in the coalbed methane is removed to obtain feed gas A;
step S2: the raw material gas A obtained in the step S1 cooled to 40 ℃ is conveyed into a pressurizing device 2 for pressurizing, and raw material gas B is obtained;
step S3: conveying the raw material gas B obtained in the step S2 into a desulfurization device for desulfurization to obtain a desulfurization gas C;
step S4: two-stage conversion: conveying the desulfurization gas C obtained in the step S3 to a catalyst bed layer of a conversion pipe of the secondary converter 4 to carry out hydrocarbon steam conversion reaction to obtain converted gas D, wherein the temperature is 650 ℃, and the hydrocarbon conversion rate reaches about 30% -80%;
step S5: three-stage conversion: conveying the converted gas D obtained in the step S4 into a three-stage converter 5 for deep conversion reaction of methane to obtain converted gas E, wherein the temperature of the converted gas E is 850 ℃, and the hydrocarbon conversion rate reaches about 98%;
step S6: and (5) conveying the converted gas E obtained in the step (S5) to a heat recovery device for heat recovery to obtain the synthesis gas.
The high-temperature gas in the invention enters the primary reformer 1 to provide ignition conditions for oxygen reaction in coalbed methane in the primary reformer 1 so as to achieve the purpose of removing oxygen, when the secondary reformer 4 adopts a van-type reformer, fuel gas enters the outside of a radiant section reformer tube of the secondary reformer 4 to burn, the heat released by the combustion provides heat for hydrocarbon reforming reaction in the reformer tube, and when the secondary reformer 4 adopts a heat exchange type reformer, the heat required by hydrocarbon reforming reaction in the heat exchange type reformer tube is provided by high-temperature reformer gas E at an outlet of the tertiary reformer 5, so that fuel gas consumption is saved; the oxygen-containing gas enters the three-stage reformer 5, and the oxygen and hydrogen and methane in the feed gas D at the inlet of the three-stage reformer 5 are combusted to release a large amount of heat, so that the heat required by the deep hydrocarbon conversion reaction is provided, and the methane content in the reformed gas E at the outlet of the three-stage reformer 5 is reduced to below 0.5% (volume, dry basis).
The foregoing examples merely represent specific embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, which fall within the protection scope of the present application.
Claims (9)
1. A hydrocarbon conversion process characterized by: the method comprises the following steps:
step S1: one-stage conversion: the raw material gas is subjected to combustion reaction of oxygen and hydrogen or methane in a primary reformer (1), and oxygen in the raw material gas is removed to obtain raw material gas A;
step S2: boosting the raw material gas A obtained in the step S1 after cooling to obtain raw material gas B;
step S3: desulfurizing the raw material gas B obtained in the step S2 to obtain a desulfurized gas C;
step S4: two-stage conversion: conveying the desulfurization gas C obtained in the step S3 into a furnace tube of a second-stage reformer (4) for hydrocarbon steam reforming reaction to obtain reformed gas D;
step S5: three-stage conversion: conveying the converted gas D obtained in the step S4 into a three-stage converter (5) to carry out deep conversion reaction of methane to obtain converted gas E;
step S6: and (5) carrying out heat recovery on the converted gas E obtained in the step (S5) to obtain the synthesis gas.
2. A hydrocarbon conversion process as claimed in claim 1, wherein: the specific steps of the one-stage conversion deoxidization process in the step S1 are as follows: when the raw material gas is conveyed into a primary reformer (1) to carry out the combustion reaction of oxygen and hydrogen or methane, the reaction pressure is between normal pressure and 1.0MpaG, the temperature is 600-1300 ℃, and the primary reformer (1) is a non-catalytic partial oxidation furnace without filling catalyst.
3. A hydrocarbon conversion process as claimed in claim 1, wherein: the booster device adopted in the step S2 is a reciprocating compressor or a centrifugal compressor, and the pressure after the booster device is boosted is 1.0-4.0MPaG.
4. A hydrocarbon conversion process as claimed in claim 1, wherein: in the step S2, dry desulfurization is adopted, specifically, a desulfurization catalyst is adopted to remove the total sulfur in the gas to below 0.2 ppm.
5. A hydrocarbon conversion process as claimed in any one of claims 1 to 4, wherein: in the step S4, the two-stage reformer (4) is a heat exchange reformer or a van reformer, the temperature of the reformed gas D is 600-900 ℃, and the two-stage reformer (4) adopts a fuel combustion heat supply and/or non-fuel combustion heat supply mode.
6. A hydrocarbon conversion process as claimed in any one of claims 1 to 4, wherein: in the step S5, the three-stage reformer (5) is a partial oxidation furnace filled with a catalyst, and the temperature of the reformed gas E is 800-1000 ℃.
7. A hydrocarbon conversion process as claimed in any one of claims 1 to 4, wherein: the feed gas in step S1 is a gaseous hydrocarbon including natural gas, coke oven gas, and coal bed gas.
8. A hydrocarbon conversion apparatus based on the hydrocarbon conversion process of any one of claims 1 to 7, characterized in that: comprises a primary reformer (1), a supercharging device (2), a desulfurizing device (3), a secondary reformer (4), a tertiary reformer (5), a heat recovery device (6) and a synthetic gas storage device (7) which are connected in sequence.
9. A hydrocarbon conversion apparatus as claimed in claim 8, wherein: the primary reformer (1) is not filled with a reaction catalyst, a long through port for introducing high-temperature gas is arranged on the primary reformer (1), and a plurality of raw gas inlets for introducing raw gas are also arranged on the primary reformer (1); the secondary reformer (4) is a van-type reformer and/or a heat exchange type reformer, and a reaction catalyst is filled in a reformer tube of the secondary reformer (4); the three-section reformer (5) is a partial oxidation furnace filled with a catalyst, the partial oxidation furnace is a self-heating reactor, a high-temperature mixer is arranged in the three-section reformer (5), and the high-temperature mixer is connected with an oxygen-containing gas input pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311853462.3A CN117735480A (en) | 2023-12-29 | 2023-12-29 | Hydrocarbon conversion method and device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311853462.3A CN117735480A (en) | 2023-12-29 | 2023-12-29 | Hydrocarbon conversion method and device |
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| Publication Number | Publication Date |
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| CN117735480A true CN117735480A (en) | 2024-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202311853462.3A Pending CN117735480A (en) | 2023-12-29 | 2023-12-29 | Hydrocarbon conversion method and device |
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| Country | Link |
|---|---|
| CN (1) | CN117735480A (en) |
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- 2023-12-29 CN CN202311853462.3A patent/CN117735480A/en active Pending
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