CN113880047B - Hydrogen production device and method for methane-containing raw material - Google Patents
Hydrogen production device and method for methane-containing raw material Download PDFInfo
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- CN113880047B CN113880047B CN202111315454.4A CN202111315454A CN113880047B CN 113880047 B CN113880047 B CN 113880047B CN 202111315454 A CN202111315454 A CN 202111315454A CN 113880047 B CN113880047 B CN 113880047B
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002994 raw material Substances 0.000 title claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 174
- 238000002407 reforming Methods 0.000 claims abstract description 113
- 238000010438 heat treatment Methods 0.000 claims abstract description 72
- 238000000926 separation method Methods 0.000 claims abstract description 61
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 52
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 51
- 238000002485 combustion reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000012495 reaction gas Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000005338 heat storage Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 239000002826 coolant Substances 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 112
- 239000001569 carbon dioxide Substances 0.000 claims description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 238000006057 reforming reaction Methods 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000009751 slip forming Methods 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims 1
- 239000003570 air Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000571 coke Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 239000003949 liquefied natural gas Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000012080 ambient air Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- 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
- C01B2203/12—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a hydrogen production device and method of a methane-containing raw material, at least comprising a combustion unit, a reforming reactor, a shift reactor, a cooling device and a separation device; the combustion unit is provided with a combustible mixture inlet, an air flow inlet and a first heated air flow outlet; the reforming reactor is provided with a synthesis gas flow outlet, a second heating gas flow outlet, a first heating gas flow inlet, a reaction gas flow inlet, a heat storage device and a catalytic device, wherein the first heating gas flow inlet is connected with the first heating gas flow outlet; the shift reactor may be configured with at least one catalyst and is provided with a synthesis gas stream inlet, a cooling medium inlet and a hydrogen-containing gas outlet, the synthesis gas stream inlet being connected to the synthesis gas stream outlet of the reactor; the cooling device is connected with the shift reactor through a cooling medium inlet; a separation device is also arranged at the downstream of the reforming reactor and the shift reactor. The invention provides a device capable of producing hydrogen on site, which has small size, low cost and small influence on environment.
Description
Technical Field
The invention relates to the field of hydrogen preparation, in particular to a hydrogen production device and method of a methane-containing raw material.
Background
In the production of hydrogen in a typical plant, a reforming process from a hydrocarbon-containing feedstock is typically used. One of the main sources for the production of hydrogen (H2) is natural gas, the main component of which is methane (CH 4). However, the currently known plants for processes that utilize steam reforming of methane-containing feedstock (CH 4) have a number of problems:
first, highly endothermic reforming reactions require high operating temperatures, typically provided by a tubular reactor, to facilitate heat exchange between the flame of a burner associated with the tubular reactor and a catalyst. In these known reactors, the decisive parameter for facilitating the heat exchange is the length of the tubes, which leads to an increase in the cost and size of the reactor itself, and reforming reactors of this type ensure that the temperatures required to support the endothermic reactions have a significant energy consumption and seriously affect the environment.
Secondly, when the reforming reactor is restarted after being shut down, it cannot start to operate immediately, but requires time and energy supply to preheat for a period of time, the time required to reach the temperature required for the reaction being longer; moreover, the large amount of fumes or coke produced during this process can cause damage to the equipment and result in poisoning of the catalyst, and fumes and coke discharged into the environment can also produce a significant amount of pollution to the environment.
In addition, current factories cannot produce hydrogen in real time to meet the real-time demands of users, and usually store the produced hydrogen in a dedicated storage tank or storage tank for transportation in a required place and time, while the hydrogen is easy to explode, and requires high conditions for storage and transportation, and a new and improved technology is urgently needed to solve the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a hydrogen production device and a hydrogen production method of a methane-containing raw material.
The invention is realized by the following technical measures, and comprises a hydrogen production device body, wherein the hydrogen production device body at least comprises a combustion unit, a reforming reactor, a shift reactor, a cooling device and a separation device; the combustion unit is provided with a combustible mixture inlet, an air flow inlet and a first heated air flow outlet; the reforming reactor is provided with a synthesis gas flow outlet, a second heating gas flow outlet, a first heating gas flow inlet, a reaction gas flow inlet, a heat storage device and a catalytic device, wherein the first heating gas flow inlet is connected with the first heating gas flow outlet; the shift reactor is provided with at least one catalyst and is provided with a synthesis gas flow inlet, a cooling medium inlet and a hydrogen-containing gas outlet, wherein the synthesis gas flow inlet is connected with the synthesis gas flow outlet of the reactor; the cooling device is connected with the shift reactor through a cooling medium inlet; and a separation device is arranged at the downstream of the reforming reactor and the shift reactor, and at least two heat exchangers and a cooler are arranged between the separation device and the reforming reactor and between the separation device and the shift reactor.
As a preferable mode, the first heating gas flow inlet, the synthesis gas flow outlet, the reaction gas flow inlet and the second heating gas flow outlet are respectively arranged at the upper end and the lower end of the reforming reactor; the catalytic device is arranged at one end close to the first heating airflow inlet and the synthetic airflow outlet, and the heat storage device is arranged at one end close to the reaction airflow inlet and the second heating airflow outlet; the first heating gas flow inlet, the reaction gas flow inlet, the second heating gas flow outlet and the synthesis gas flow outlet are all arranged in countercurrent.
As a preferable mode, the heat storage device is externally provided with a ceramic block, and ventilation holes are uniformly and continuously formed in the ceramic block.
Preferably, the separation device comprises a first separation device and a second separation device, wherein the first separation device is connected downstream of the reforming reactor, and the second separation device is connected downstream of the shift reactor; the first separation device comprises a second heating airflow inlet, a first atomization tower, an exhaust gas outlet, a first carbon dioxide fluid outlet and a separation membrane; the second separation device comprises a hydrogen-containing gas inlet, a second atomization tower, a hydrogen outlet, a second carbon dioxide fluid outlet and an extraction membrane.
As a preferred way, the reforming reactor comprises two, two of which are configured to perform the operation modes of heating and reforming in an alternating manner.
As a preferable mode, the reforming reactor is also provided with a control device, and the control device comprises a temperature sensor and a control valve; the temperature sensor is arranged along the length direction of the reforming reactor; the control valves are arranged at two ends of the reforming reactor and comprise a first control valve, a second control valve, a third control valve and a fourth control valve.
As a preferred mode, the first carbon dioxide fluid outlet and the second carbon dioxide fluid outlet are further connected with a liquefying unit, and the liquefying unit comprises a compressor, a gas-air exchanger and a hot third heat exchanger.
As a preferable mode, the number of the shift reactors is three, and the shift reactors comprise a first shift reactor, a second shift reactor and a third shift reactor, and the first shift reactor, the second shift reactor and the third shift reactor are connected in series with the reforming reactor.
A hydrogen production method based on reforming a methane-containing raw material, wherein a combustible mixture is input into a combustion unit to generate heating gas, the heating gas is input from one end of a reforming reactor, and the first separation device is used for extracting and treating waste gas and carbon dioxide flow generated by the reforming reactor; introducing a reaction gas stream containing methane and water vapor from the other end of the reforming reactor and then carrying out a reaction to obtain a synthesis gas stream, cooling the synthesis gas stream to a temperature capable of causing at least one water gas shift reaction, and introducing the synthesis gas stream into a shift reactor to be converted into a gas containing carbon dioxide and hydrogen, wherein the gas containing carbon dioxide and hydrogen is extracted into a carbon dioxide stream and a hydrogen stream through a second separation device; wherein the carbon dioxide stream enters a liquefaction zone for treatment.
As a preferred mode, any one of the reforming reactors has at least two operating configurations, including: a first heating configuration, the reforming reactor receiving heated gas from the combustion unit, the heated gas flowing from one end to the other; a second reforming configuration, wherein a second end of the reforming reactor receives the reactant gas stream and reforms the reactant gas stream to obtain a synthesis gas stream;
a washing device for removing impurities is arranged between the first heating arrangement and the second reforming arrangement.
The hydrogen production device and method based on reforming methane-containing raw materials at least comprises a combustion unit, a reforming reactor, a shift reactor, a cooling device and a separation device, wherein a plurality of parallel devices can be used for continuous reforming with high efficiency, and smoke or coke is not derived in the production process, so that the problem of environmental pollution is greatly reduced. Meanwhile, the device does not need to store the generated hydrogen and can be used as a real hydrogen distributor to continuously operate, can be directly connected to a natural gas station according to the needs of users and can produce hydrogen on site, and has the advantages of small size, low cost and suitability for popularization and use.
Drawings
FIG. 1 is a schematic diagram illustrating the operation of an embodiment of the present invention;
FIG. 2 is a schematic liquefaction diagram of an embodiment of the present invention.
In the figure, the label is numbered and the name: fa. air stream FI. is fed with gas fc, heating air stream FS. is exhaust gas fgs, synthesis gas stream fch4 is methane containing mixture fout, hydrogen and carbon dioxide containing gas fh2 is hydrogen stream fco2 is carbon dioxide stream
11. The combustion unit 13, the combustible mixture inlet 13 ', the secondary inlet 15, the first heated gas stream outlet 17, the first reforming reactor 17', the second reforming reactor 19, the first heated gas stream inlet 19 ', the first heated gas stream inlet
The reaction gas flow inlet 21 ', the reaction gas flow inlet 23 ', the second heating gas flow outlet 25, the synthesis gas flow outlet 25 ', the synthesis gas flow outlet 27, the catalytic device 27 ', the catalytic device 29, the thermal storage device 29 ', the thermal storage device
31. The first control valve 31 ', the first control valve 33', the second control valve 37, the third control valve 37 ', the third control valve 35, the fourth control valve 35', the fourth control valve 39, the cooling medium inlet
40. The synthesis gas stream inlet 41, the first shift reactor 43, the second shift reactor 45, the third reactor 47, the second separation device 49, the first separation device
51. First heat exchanger 53, second heat exchanger 55, second desuperheater 57, first desuperheater
61. A second atomizing tower 63, a hydrogen-containing gas inlet 65, a hydrogen outlet 67, a second carbon dioxide fluid outlet 69, and an extraction membrane
71. First atomizing tower 73, second heated gas stream inlet 76, exhaust outlet 77, first carbon dioxide fluid outlet 79, separation membrane
80. Liquefaction zone 90, liquefaction zone 81, compressor 85, gas-air exchanger 83, third heat exchanger 17a, first end 17b, second end 17 'a, first end 17' b, second end
Detailed Description
The invention will be described in further detail below with reference to examples and with reference to the accompanying drawings.
A hydrogen plant for methane-containing feedstock, referring to fig. 1 to 2, comprising a hydrogen plant body comprising at least one combustion unit 11, a reforming reactor, a shift reactor, a cooling device and a separation device;
the combustion unit 11 is provided with a combustible mixture inlet 13, an air flow Fa inlet and a first heated air flow outlet 15. The combustion unit 11 is provided with an inlet for the input of a fuel or gas mixture FI, an outlet for the output of the heated gas produced from the device and an ambient air flow Fa primary inlet 13 and a secondary inlet 13 ', which secondary inlet 13' is used for introducing a secondary flow of ambient air Fa according to the needs of the process performed by the device. The combustion unit 11 should comprise at least one burner for burning a combustible mixture, i.e. an input gas stream FI consisting of a methane stream FCH4 and an ambient air stream FA, for burning the mixture of input gas FI to produce a heated gas stream FC, the temperature of the heated gas FC from the combustion unit 11 being between 900 ℃ and 950 ℃, preferably between 910 ℃ and 950 ℃.
The reforming reactor is provided with a synthesis gas flow outlet 25, a second heating gas flow outlet 23, a first heating gas flow inlet 19, a reaction gas flow inlet 21, a heat storage device 29 and a catalytic device 27, wherein the first heating gas flow inlet 19 is connected with the first heating gas flow outlet 15. The reforming reactor contains at least one catalyst and is capable of generating a synthesis gas stream FGS by absorbing heat from the heated gas Fc. Referring to fig. 1, the reforming reactor includes a first end 17a and a second end 17b, a first heating gas flow inlet 19 of the reforming reactor is connected to a first heating gas flow outlet 15 of the combustion unit 11, the heating gas flow FC is outputted downstream from the first end 17a to the second end 17b of the reforming reactor, and a reaction gas flow Fr containing methane and steam raw materials required for the reforming reaction is outputted from the second end 17b to the first end 17a, and at this time, the heating gas flow FC and the reaction gas flow are disposed in countercurrent contact.
The shift reactor may be provided with at least one catalyst and is provided with a synthesis gas stream inlet 40, a cooling medium inlet 39 and a hydrogen-containing gas outlet, the synthesis gas stream inlet 40 being connected to the synthesis gas stream outlet 25 of the reactor. At least one shift reactor downstream of the reforming reactor, the inlet of the synthesis gas stream FGS on the shift reactor being in communication with the synthesis stream FGS outlet on the reforming reactor, the shift reactor being adapted to include at least one catalyst for performing a shift or water gas shift reaction to convert the synthesis gas stream FGS to a gaseous mixture comprising carbon dioxide and hydrogen;
in one embodiment, referring to fig. 1, the shift reactors are three, and the three shift reactors are connected in series with the reforming reactor. The apparatus comprises a shift reaction or water gas shift reaction in series with a first shift reactor 41 and a second shift reactor 43 downstream of the first reforming reactor 17 and the second reforming reactor 17', the first shift reactor 41 comprising a first metal catalyst such as platinum and cesium operating at a temperature of around 400 ℃, the second shift reactor 43 being in series downstream of the first shift reactor 41 and containing a second copper catalyst operating at a temperature of around 200 ℃. The first shift reactor 41 and the second shift reactor 43 produce a slightly exothermic reaction based on the water gas shift reaction, i.e., co+h2o=co2+h2; a third reactor 45 is also included, the third reactor 45 containing a metal-based catalyst, such as platinum and cesium, operating at a temperature of around 180 ℃ for removal of trace carbon monoxide left over from the shift reaction.
The cooling device is connected to the shift reactor through a cooling medium inlet 39, which generates a cooling medium capable of cooling the synthesis gas stream FGS from the reforming reactor to a temperature suitable for shift reaction, which can be selected from the water stream FH2O injection of the permeation water treatment plant for permeation, which is capable of effectively reducing the temperature of the first shift reactor 41 and the second shift reactor 43. Wherein the temperature of the synthesis gas stream FGS exiting the reforming reactor is about 850 c and a temperature of about 200 c to 400 c is required to effect the shift reaction.
A separation device is arranged at the downstream of the reforming reactor and the shift reactor, and at least two heat exchangers and a cooler are arranged between the separation device and the reforming reactor and between the separation device and the shift reactor; the separation device is used for separating the carbon dioxide flow generated in the reaction process, so as to avoid directly discharging the carbon dioxide flow to the atmosphere and causing environmental pollution;
the heat exchangers include a first heat exchanger 51 and a second heat exchanger 53 for heating and vaporizing the water stream from the cooling device to accelerate the flow and reaction of the reactant gas stream. The first heat exchanger 51 recovers heat from the heated gas stream Fc within the reforming reactor, the inlet temperature of the first heat exchanger 51 being about 150 c to provide the heat required to produce steam, and the outlet temperature being about 30 c. The second heat exchanger 53 is connected to the third reactor 45 to receive the above FOUT gas stream obtained from the series of shift reactions, the second heat exchanger 53 having an input temperature of about 180 c and an output temperature of about 30 c. The two heat exchangers can recycle and utilize the heat source generated by the heat exchangers, and reduce energy waste by improving the energy efficiency of the whole unit;
the desuperheater includes a first desuperheater 57 and a second desuperheater 55 for reducing the temperature of the FOUT and heating streams Fc to achieve separation of carbon dioxide from these streams, which is approximately 1 c.
The first heating gas flow inlet 19, the synthesis gas flow outlet 25, the reaction gas flow inlet 21 and the second heating gas flow outlet 23 are respectively arranged at the upper end and the lower end of the reforming reactor; the catalytic device 27 is arranged at one end near the first heating gas flow inlet 19 and the synthesis gas flow outlet 25, and the heat storage device 29 is arranged at one end near the reaction gas flow inlet 21 and the second heating gas flow outlet 23; the first and reactant gas inlets 19, 21, the second and synthesis gas outlets 23, 25 are all counter-current. The first heating gas flow inlet 19 and the synthesis gas flow outlet 25 are provided at the first end 17a of the reforming reactor, the reaction gas flow inlet 21 and the second heating gas flow outlet 23 are provided at the second end 17b, the catalytic device 27 is located at the first end 17a of the reforming reactor, the heat storage device 29 is located near the second end 17b17b of the reforming reactor, the heating gas flow Fc first heats the catalyst inside the catalyst when entering the reforming reactor, and then passes through the heat storage device 29, which is capable of absorbing and storing the heat of the heating gas Fc generated from the combustion unit 11, so as to activate the reforming reaction to provide the required heat after restarting the reforming reactor.
The heat storage device 29 is externally provided with a ceramic block, and ventilation holes are uniformly and continuously formed in the ceramic block. The thermal storage device 29 is made of a ceramic material, and the ceramic block is provided with micropores to allow passage of gas.
In an embodiment, referring to fig. 1, the separation device comprises a first separation device 49 and a second separation device 47, the first separation device 49 is connected downstream of the reforming reactor, the second separation device 47 is connected downstream of the shift reactor, and a plurality of separation modules placed in series can be provided in the present invention to realize a series of separation stages;
the first separation device 49 comprises a second heated gas stream inlet 73, a first atomizing tower 71, an exhaust gas outlet 76, a first carbon dioxide fluid outlet 77, and a separation membrane 79; the first separation device 49 is used for separating the exhaust gas FS and the carbon dioxide flow FCO2 generated in the process, the heated gas flow is cooled by the first cooler 57 and then enters the first atomization tower 71, and then the separation membrane 79 separates the carbon dioxide flow FCO2 and the exhaust gas flow FS;
the second separation device 47 comprises a hydrogen-containing gas inlet 63, a second atomization tower 61, a hydrogen outlet 65, a second carbon dioxide fluid outlet 67 and an extraction membrane 69, and the second separation device 47 is used for extracting a hydrogen gas stream and recovering a carbon dioxide stream FCO2 contained in the FOUT gas stream flowing out of the second cooler 55; downstream of the third reactor 45 is connected a second separation device 47, the second separation device 47 extracts carbon dioxide contained in the FOUT mixture from the third reactor 45 to obtain a hydrogen stream FH2 and a carbon dioxide stream FCO2, the FOUT stream after entering the second atomizing tower 61 separating the generated hydrogen stream FH2, and an extraction membrane 69 is used to extract the carbon dioxide stream FCO2.
The reforming reactor comprises two, two of which are configured to perform an operation mode of heating and reforming in an alternating manner. In an embodiment, two reforming reactors, including a first reforming reactor 17 and a second reforming reactor 17', are connected in parallel with the first heated gas flow outlet 15 of the combustion unit 11, which ensures the continuity of the reaction process at restart.
A control device is further arranged on the reforming reactor, and comprises a temperature sensor and a control valve; the control device can control and maintain the temperature in the reforming reactor at certain time intervals to avoid forming smoke or coke, and smoke or coke is easy to generate when the temperature in the reforming reactor exceeds 900 ℃, so that the reaction temperature is required to be kept between 850 ℃ and 890 ℃, and is generally 870 ℃. At this temperature, the methane introduced into the reforming reactor 17 is converted and the formation of fumes is avoided.
The temperature sensor is arranged along the length direction of the reforming reactor; the three temperature sensors preferably comprise a first temperature sensor, a second sensor and a third sensor, and the three temperature sensors are all arranged along the flowing direction of the heating airflow. Specifically, a first temperature sensor is provided near the first end 17a in the reforming reactor 17 to detect the temperature of the heating gas Fc when it enters the reforming reactor 17, which must be around 910 ℃ to provide the heat required for the reaction; a second temperature sensor, located at the thermal storage device 29, capable of detecting the temperature of the ceramic blocks in brick form, which is about 850 ℃; a third temperature sensor near the second end 17b of the reforming reactor for measuring the expected temperature of the bottom of the reactor, which must be kept around 150 ℃;
the control valves are provided at both ends of the reforming reactor, and include a first control valve 31, a second control valve 33, a third control valve 37, and a fourth control valve 35. When the temperature values detected by the respective temperature sensors satisfy the temperature conditions required for the reforming reaction, the flow of the heating gas Fc from the combustion unit 11 is interrupted by operating the first control means 31 provided at the first end 17 a; a second control valve 33 is provided at the second end 17b of the reforming reactor 17 for controlling the countercurrent flow of the reaction gas flow Fr; a third control valve 37 is provided at the first end 17a for releasing the synthesis gas stream FGS obtained from the reaction; a fourth control means is provided at the second end 17b for releasing the heating air flow Fc.
The first carbon dioxide fluid outlet 77 and the second carbon dioxide fluid outlet 67 are further connected with a liquefaction unit comprising a compressor 81, a gas-air exchanger 85, and a third heat exchanger 83. The liquefaction unit is used to liquefy the carbon dioxide gas stream FCO2 extracted by the two separation devices, in particular, referring to fig. 2, the carbon dioxide stream FCO2 coming from the first separation device 49 and the second separation device 47 has a pressure of about 0 ℃ and 5 bar. The carbon dioxide stream FCO2 is subjected to a first compression stage by a dedicated compressor 81, the compressor 81 allowing the carbon dioxide FCO2 to flow to a pressure of about 20 bar, during which compression stage the temperature of the carbon dioxide stream FCO2 rises to a temperature value of about 40 ℃. To liquefy the carbon dioxide stream FCO2, the carbon dioxide stream FCO2 is then cooled to-20 ℃ in a gas-air exchanger 85 and a third heat exchanger 83 downstream of the compressor 81. Liquid carbon dioxide FCO2 is obtained from the third heat exchanger 83.
A method for producing hydrogen from a methane-containing raw material, wherein a combustible mixture is fed into a combustion unit 11 to generate a heating gas, the heating gas is fed from one end of a reforming reactor, and the first separation device 49 extracts and processes an exhaust gas FS and a carbon dioxide stream generated by the reforming reactor; introducing a reaction gas stream containing methane and steam from the other end of the reforming reactor and then reacting to obtain a synthesis gas stream FGS, cooling said synthesis gas stream FGS to a temperature capable of causing at least one water gas shift reaction, said synthesis gas stream FGS being passed into a shift reactor to be converted into a carbon dioxide and hydrogen containing gas, said carbon dioxide and hydrogen containing gas being extracted into a carbon dioxide and hydrogen stream by a second separation means 47; wherein the carbon dioxide stream enters a liquefaction zone for treatment.
The combustion unit 11 is provided with a gaseous or combustible mixture Fi consisting of a methane FCH4 stream and a Fa air stream, the combustion unit 11 being equipped with at least one burner. To generate a heated gas stream Fc that is introduced into a reforming reactor connected to the output of the combustion unit 11 to activate the heat required for the reforming reaction.
Any of the reforming reactors has at least two operating configurations, including:
a first heating configuration, the reforming reactor receiving heated gas from the combustion unit 11, the heated gas flowing from one end to the other; a second reforming configuration, wherein the second end 17b of the reforming reactor receives the reactant gas stream for reforming to obtain a syngas stream FGS; a washing device for removing impurities is arranged between the first heating arrangement and the second reforming arrangement.
Two reforming reactors are placed in parallel downstream of the combustion unit 11 and are configured to perform at least two working configurations operating in an alternative manner to promote the continuity of the reform process. A first heating configuration: the reforming reactor receives the heating gas flow Fc and absorbs and stores heat of the heating gas; a second reconfiguration: the heating gas flow Fc is interrupted and the reactor is powered upstream by the reaction gas flow Fr to perform the reforming reaction.
The first reforming reactor 17 receives the heated gas Fc through a first control valve 3131, and the flow of heated gas passing through the reactor from the first end 17a to the second end 17b first heats the catalyst 27, then absorbs heat through a heat storage device 29 provided with ceramic blocks, and finally leaves the reforming reactor through a second heating outlet. During this heating phase, the temperature inside the reactor is detected by means of a temperature control system equipped with the reactor, when the temperature reaches about 850 ℃ in two thirds of the ceramic blocks 29, and about 150 ℃ at the bottom of the reactor 17, the reactor 17 is ready for reforming reactions, so that the flow of heated gas Fc from the combustion unit 11 can be interrupted. The second reactor 17' performs a reforming reaction when the first reactor is in the first operating configuration or the heating configuration. Thus, for the second reforming reactor 17', the heating gas flow FC is interrupted and the reactor is only opened from the second end 17b by the second control valve 33, receiving the Fr gas flow containing methane and water vapour for powering.
When switching between the two operating configurations, the two reforming reactors have a transition time interval of a few seconds for performing a washing or flow phase, i.e. a removal operation of unwanted substances contained in the heated gas, such as nitrogen. The flow operation is performed by operating the third control valve 37 of the synthesis gas stream outlet 25 at the first end 17a of the reforming reactor in order to divert the synthesis gas FGS containing hydrogen and carbon monoxide produced by the reactor in the reforming configuration, in which case the second reactor is placed on the reactor 17 where the heating stage has been completed. In addition, each reforming reactor also comprises detection means capable of detecting the absence of nitrogen in the respective reforming reactor and shutting down the flow.
Once the reforming reaction has been carried out in either one of the two reforming reactors, the synthesis gas stream FGS is cooled by injecting into the cooling device a stream of FH2O from the water treatment plant until the synthesis gas temperature has fallen to about 400 ℃, and then the synthesis gas stream FGS may be sent to the first shift reactor 41 to achieve the first stage of water gas shift to obtain carbon dioxide and hydrogen;
the gas stream obtained after the first stage cooling is cooled again by means of the water spray FH2O until a temperature of about 200 ℃ is reached, when which the gas stream is again subjected to the water gas shift stage in the second shift reactor 43;
after the second shift reaction, the gas stream from the second shift reactor 43 is fed to a third reactor 45, the third reactor 45 reactor containing a catalyst that operates at a temperature of about 180 ℃ to eliminate the last traces of carbon monoxide.
The FOUT fluid exiting the third reactor 45 enters a desuperheater, is cooled to the 1 ℃ temperature required to separate the carbon dioxide contained in this stream, and then the carbon dioxide is separated by a second separation device 47 to obtain a hydrogen FH2 stream and a carbon dioxide stream FCO2, while the carbon dioxide stream FCO2 will be liquefied by a corresponding liquefaction module downstream.
According to the hydrogen plant described above, the methane-containing feedstock FCH4 may be natural gas from a public distribution network. Thus, it is possible to connect to a natural gas distribution network, to be able to produce and supply hydrogen on site, such as a local hydrogen distributor, without the need to store or transport the produced hydrogen in tanks, which can avoid problems and operating costs caused by hydrogen storage and transportation. Furthermore, and still in accordance with this form of the invention, the plant also includes a pretreatment facility upstream of the plant for removing impurities contained in the network methane to avoid catalyst poisoning of the hydrogen plant. When the methane-containing FCH4 stream is in a liquid state (LNG), no pretreatment medium is typically required.
The pretreatment medium should include a pretreatment system based on the removal of inorganic components such as hydrogen sulfide and mercaptans using a dedicated catalyst. The pretreatment system may be subjected to at least two pretreatment stages and includes two reactors operating at low temperatures: the first reactor is equipped with a special catalyst for the main reduction of hydrogen sulphide and mercaptans and the second reactor is equipped with a special catalyst for the zeolite catalyst of organic components such as odorants and bisulphites.
In addition, when the methane-containing FCH4 stream is Liquid (LNG), the hydrogen plant includes a refrigerator recovery system, such as a plurality of third heat exchangers 83, made using methods and apparatus known to those skilled in the art. The refrigerator for a hydrogen plant, which is recovered from the evaporation of a liquefied natural gas stream during the conversion to the gaseous state, according to the present invention, can be effectively used to liquefy a carbon dioxide stream separated by a separation device, which must reach a temperature of about-20 degrees celsius for the liquefaction of carbon dioxide, and which provides about two-thirds of the energy required to reach the liquefaction temperature of carbon dioxide from the methane of liquefied natural gas
While the foregoing is illustrative of a hydrogen plant and method from a methane-containing feedstock in accordance with the present invention, it is to be understood that the invention is not limited to the specific embodiments disclosed herein, and that any changes, modifications, substitutions, combinations, or simplifications that do not depart from the principles of the invention are intended to be equivalent substitutes and are included within the scope of the invention.
Claims (9)
1. The hydrogen production device of the methane-containing raw material is characterized by comprising a hydrogen production device body, wherein the hydrogen production device body at least comprises a combustion unit, a reforming reactor, a shift reactor, a cooling device and a separation device;
the combustion unit is provided with a combustible mixture inlet, an air flow inlet and a first heated air flow outlet;
the reforming reactor is provided with a synthesis gas flow outlet, a second heating gas flow outlet, a first heating gas flow inlet, a reaction gas flow inlet, a heat storage device and a catalytic device, wherein the first heating gas flow inlet is connected with the first heating gas flow outlet, and the heat storage device can absorb and store the heat of the heating gas generated from the combustion unit so as to provide the needed heat for activating the reforming reaction after restarting the reforming reactor;
the shift reactor is provided with at least one catalyst and is provided with a synthesis gas flow inlet, a cooling medium inlet and a hydrogen-containing gas outlet, and the synthesis gas flow inlet is connected with the synthesis gas flow outlet of the reforming reactor;
the first heating gas flow inlet and the synthesis gas flow outlet, the reaction gas flow inlet and the second heating gas flow outlet are respectively arranged at the upper end and the lower end of the reforming reactor;
the catalytic device is arranged at one end close to the first heating airflow inlet and the synthetic airflow outlet, and the heat storage device is arranged at one end close to the reaction airflow inlet and the second heating airflow outlet;
the first heating gas flow inlet, the reaction gas flow inlet, the second heating gas flow outlet and the synthesis gas flow outlet are all arranged in a countercurrent mode;
the cooling device is connected with the shift reactor through a cooling medium inlet;
the separation device comprises a first separation device and a second separation device, the first separation device is connected to the downstream of the reforming reactor, the second separation device is connected to the downstream of the shift reactor, and a heat exchanger and a cooler are arranged between the first separation device and the reforming reactor and between the second separation device and the shift reactor.
2. The hydrogen production device of methane-containing raw materials according to claim 1, wherein ceramic blocks are arranged outside the heat storage device, and ventilation holes are uniformly and continuously formed in the ceramic blocks.
3. The hydrogen plant of claim 1, wherein the first separation device comprises a second heated gas stream inlet, a first atomizing tower, an exhaust gas outlet, a first carbon dioxide fluid outlet, and a separation membrane;
the second separation device comprises a hydrogen-containing gas inlet, a second atomization tower, a hydrogen outlet, a second carbon dioxide fluid outlet and an extraction membrane.
4. The hydrogen plant of claim 1, wherein the reforming reactor comprises two, the two reforming reactors configured to perform the heating and reforming modes of operation in an alternating manner.
5. The hydrogen plant of claim 1, wherein a control device is further provided on the reforming reactor, the control device comprising a temperature sensor and a control valve;
the temperature sensor is arranged along the length direction of the reforming reactor;
the control valves are arranged at two ends of the reforming reactor and comprise a first control valve, a second control valve, a third control valve and a fourth control valve.
6. A hydrogen plant as claimed in claim 3, wherein said first and second carbon dioxide fluid outlets are further connected to a liquefaction unit comprising a compressor, a gas-air exchanger and a third heat exchanger.
7. The hydrogen plant of claim 1 wherein said shift reactors are three, three of said shift reactors being connected in series with a reforming reactor.
8. A method of producing hydrogen using the apparatus of claim 1, wherein the combustible mixture is fed into a combustion unit to produce a heated gas, the heated gas being fed from one end of a reforming reactor, and wherein the first separation device performs an extraction process on the exhaust gas and carbon dioxide stream produced by the reforming reactor;
introducing a reaction gas stream containing methane and water vapor from the other end of the reforming reactor and then carrying out a reaction to obtain a synthesis gas stream, cooling the synthesis gas stream to a temperature capable of causing at least one water gas shift reaction, and introducing the synthesis gas stream into a shift reactor to be converted into a gas containing carbon dioxide and hydrogen, wherein the gas containing carbon dioxide and hydrogen is extracted into a carbon dioxide stream and a hydrogen stream through a second separation device;
wherein the carbon dioxide stream enters a liquefaction zone for treatment.
9. The method of claim 8, wherein the reforming reactor has at least two operating configurations, comprising:
a first heating configuration, the reforming reactor receiving heated gas from the combustion unit, the heated gas flowing from one end to the other;
a second reforming configuration, wherein a second end of the reforming reactor receives the reactant gas stream and reforms the reactant gas stream to obtain a synthesis gas stream;
a washing device for removing impurities is arranged between the first heating arrangement and the second reforming arrangement.
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| CN205115038U (en) * | 2015-11-05 | 2016-03-30 | 中国科学院广州能源研究所 | Synthetic reaction unit of methane chemistry chain system of reforming |
| CN207738447U (en) * | 2017-12-08 | 2018-08-17 | 江苏省冶金设计院有限公司 | A kind of system that catalytic reforming high temperature coke oven coal gas produces also Primordial Qi |
| CN110382406A (en) * | 2017-03-13 | 2019-10-25 | 乔治洛德方法研究和开发液化空气有限公司 | The method and apparatus of the efficiency of the reforming process of production synthesis gas and methanol is modified to while reducing the CO2 in gaseous flow |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN205115038U (en) * | 2015-11-05 | 2016-03-30 | 中国科学院广州能源研究所 | Synthetic reaction unit of methane chemistry chain system of reforming |
| CN110382406A (en) * | 2017-03-13 | 2019-10-25 | 乔治洛德方法研究和开发液化空气有限公司 | The method and apparatus of the efficiency of the reforming process of production synthesis gas and methanol is modified to while reducing the CO2 in gaseous flow |
| CN207738447U (en) * | 2017-12-08 | 2018-08-17 | 江苏省冶金设计院有限公司 | A kind of system that catalytic reforming high temperature coke oven coal gas produces also Primordial Qi |
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