CN116510460A - Fermentation tail gas recycling system, method and application - Google Patents
Fermentation tail gas recycling system, method and application Download PDFInfo
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- CN116510460A CN116510460A CN202310148804.5A CN202310148804A CN116510460A CN 116510460 A CN116510460 A CN 116510460A CN 202310148804 A CN202310148804 A CN 202310148804A CN 116510460 A CN116510460 A CN 116510460A
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- 238000000855 fermentation Methods 0.000 title claims abstract description 79
- 230000004151 fermentation Effects 0.000 title claims abstract description 79
- 238000004064 recycling Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 198
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 149
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 60
- 238000003795 desorption Methods 0.000 claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims description 33
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 239000000428 dust Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 abstract description 23
- 230000002860 competitive effect Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 26
- 239000003570 air Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000002912 waste gas Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002407 reforming Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002921 fermentation waste Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 241000894007 species Species 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 101000824979 Homo sapiens Transcription factor Sp4 Proteins 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 102100022446 Transcription factor Sp4 Human genes 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
-
- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with 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
- C01B3/02—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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to the technical field of tail gas treatment, in particular to a fermentation tail gas recycling system, a fermentation tail gas recycling method and application. The fermentation tail gas recycling system comprises a pretreatment system, an adsorption-desorption system and a catalytic reforming system; the pretreatment system is connected with the adsorption-desorption system, and the adsorption-desorption system is connected with the catalytic reforming system. According to the invention, pretreatment, adsorption and desorption, catalytic reforming and other functions are coupled to obtain a fermentation tail gas recycling system, and particles and liquid drops in the fermentation tail gas are removed through the pretreatment system, so that the blockage of adsorption-desorption equipment and the competitive adsorption of water and VOCs are prevented; and the desorbed VOCs are subjected to catalytic reforming through a catalytic reforming system to obtain hydrogen-rich mixed gas, and finally, the fermentation tail gas is efficiently converted into the hydrogen-rich mixed gas, so that the recycling utilization of the fermentation tail gas is realized.
Description
Technical Field
The invention relates to the technical field of tail gas treatment, in particular to a fermentation tail gas recycling system, a fermentation tail gas recycling method and application.
Background
Volatile Organic Compounds (VOCs) that affect the environment are emitted during yeast production. With the enhancement of environmental awareness, the industrial exhaust emission standard and the supervision are increasingly strict, and the direct emission of the fermentation exhaust without treatment can be forbidden and penalized by related departments, so that the fermentation exhaust is necessary to be treated.
The existing common VOCs treatment technology is roughly divided into two means of recovery and destruction. The recovery technique is applicable to single components, high concentration and components with higher recovery value, while the destruction technique is applicable to components with low concentration, complex components and no recovery value. The process name of the destroying technology is Regenerative Catalytic Oxidation (RCO), which uses a catalyst to activate VOCs, and can efficiently convert the VOCs into CO at a lower temperature (300-500 ℃) 2 And H 2 O, therefore, is widely used. However, this method cannot better realize the resource utilization of fermentation tail gas.
Disclosure of Invention
The concentration of the yeast fermentation tail gas is low, the components are complex and difficult to treat, and the main components of the VOCs are alcohols, esters and aldehydes, wherein the most ethanol exists. The inventor finds that the fermentation tail gas can be converted into hydrogen-rich mixed gas through a catalytic steam reforming technology. Compared with RCO, the method not only can solve the emission problem of VOCs, but also can open up a new way for the recycling of VOCs.
The invention aims to solve the technical problems: the invention provides a fermentation tail gas recycling system which can efficiently convert fermentation tail gas into available hydrogen-rich mixed gas and realize recycling of the fermentation tail gas.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention provides a fermentation tail gas recycling system which comprises a pretreatment system, an adsorption-desorption system and a catalytic reforming system, wherein the pretreatment system is used for carrying out pretreatment on the fermentation tail gas; the pretreatment system is connected with the adsorption-desorption system, and the adsorption-desorption system is connected with the catalytic reforming system.
Preferably, the pretreatment system comprises a dust removal and/or defogging device; preferably, the dust removal device is selected from tube bundle dust removal devices and/or filter screens.
Preferably, the adsorption-desorption system at least comprises two sets of ultrasonic adsorption-desorption fixed beds connected in parallel.
Preferably, the ultrasonic adsorption-desorption fixed bed comprises an adsorption layer and an ultrasonic support box, wherein the ultrasonic support box is arranged in the adsorption layer in an embedded mode, and an ultrasonic device is arranged in the ultrasonic support box.
Preferably, the adsorbent of the adsorption layer is selected from one or more of activated carbon, resin and molecular sieve.
Preferably, the ultrasonic adsorption-desorption system adopts a hot gas desorption form, and the desorption gas is selected from N 2 、CO 2 And one or two or more of He.
Preferably, the catalytic reforming system comprises a catalytic reforming device and a steam generating device, wherein the steam generating device is used for mixing the gasified water with the desorption tail gas and then entering the catalytic reforming device.
Preferably, the catalytic reforming device at least comprises two catalytic reforming reactors, and the inlets of the catalytic reforming reactors are respectively connected with the steam generating device through valves; preferably, the inlet of the catalytic reforming reactor is connected with the catalytic reforming tail gas conveying pipeline through a valve, and the outlet of the catalytic reforming reactor is connected with the catalytic reforming tail gas conveying pipeline through a valve respectively; more preferably, the outlets of the catalytic reforming reactors are connected by valves.
Preferably, the catalyst in the catalytic reforming reactor is selected from noble metal catalysts and/or non-noble metal catalysts; preferably, the catalyst is a noble metal catalyst; more preferably, the catalyst is one or more of granular, monolithic and powdered; further preferably, the catalytic reforming reactor is a fixed bed or a fluidized bed.
Preferably, the fermentation tail gas recycling system further comprises a heat exchange system, wherein one end of the heat exchange system is connected with the adsorption-desorption system, and the other end of the heat exchange system is connected with the catalytic reforming system and is used for preheating desorption tail gas and recovering heat of catalytic reforming tail gas; preferably, the heat exchange system comprises a plate heat exchanger and/or a shell heat exchanger.
Preferably, the fermentation tail gas recycling system further comprises a control system, wherein the control system comprises a computer control center, a human-computer interface and a programmable controller, the computer control center is in signal connection with the programmable controller, the computer control center is in communication connection with the human-computer interface, the human-computer interface is electrically connected with the programmable controller, and the programmable controller is electrically connected with the pretreatment system, the adsorption-desorption system and the catalytic reforming system.
Preferably, the fermentation tail gas recycling system further comprises an application system, wherein the application system is connected with the heat exchange system or the catalytic reforming system and is used for recycling the catalytic reforming tail gas; preferably, the recycling comprises one of biosynthesis, chemical synthesis or a hydrogen internal combustion engine.
The invention also provides a method for recycling the fermentation tail gas, which is performed by using the fermentation tail gas recycling system and comprises the following steps:
adopting a pretreatment system to treat fermentation tail gas; carrying out adsorption-desorption treatment on the pretreated tail gas; and carrying out catalytic reforming on the desorbed tail gas to obtain catalytic reforming tail gas.
Preferably, the method further comprises the step of heat exchanging and/or recycling the catalytic reforming tail gas.
Preferably, the method further comprises the step of in situ regeneration of the catalyst using the catalytic reformed tail gas.
Preferably, the in situ regeneration comprises the steps of: firstly, stopping introducing desorption tail gas into a catalytic reforming reactor to be regenerated, then introducing catalytic reforming tail gas from an outlet of the catalytic reforming reactor to be regenerated, and introducing the regenerated tail gas into a catalytic reforming tail gas conveying pipeline from an inlet of the catalytic reforming reactor to realize in-situ regeneration of the catalyst.
Preferably, the temperature of the catalytic reforming is 200-1000 ℃, preferably 400-700 ℃, more preferably 400-550 ℃; preferably, the molar ratio of the water vapour and the total hydrocarbons of the catalytic reforming is between 1 and 6, preferably between 2 and 4.
Preferably, the catalytic reforming tail gas comprises H 2 、CO、CO 2 And CH (CH) 4 The method comprises the steps of carrying out a first treatment on the surface of the Preferably in H 2 、CO、CO 2 And CH (CH) 4 H based on the total volume of (2) 2 Is 50-80% by volume.
The invention also provides an application of the fermentation tail gas recycling system or the method in treating low-concentration waste gas.
The invention has the beneficial effects that:
according to the invention, pretreatment, adsorption and desorption, catalytic reforming and other functions are coupled to obtain a fermentation tail gas recycling system, and particles and liquid drops in the fermentation tail gas are removed through the pretreatment system, so that the blockage of adsorption-desorption equipment and the competitive adsorption of water and VOCs are prevented; and the desorbed VOCs are subjected to catalytic reforming through a catalytic reforming system to obtain hydrogen-rich mixed gas, and finally, the fermentation tail gas is efficiently converted into the hydrogen-rich mixed gas, so that the recycling utilization of the fermentation tail gas is realized.
Drawings
FIG. 1 is a schematic diagram of a fermentation tail gas recycling system in example 1;
fig. 2 is a schematic diagram of the structure of an ultrasonic adsorption/desorption fixed bed in example 1.
The labels in the figures are illustrated below: 1-tube bundle dust collector, 11-first three-way valve, 21-first ultrasonic adsorption-desorption fixed bed, 22-second ultrasonic adsorption-desorption fixed bed, 211-first air inlet, 212-second air inlet, 213-first air outlet, 214-second air outlet, 215-first ultrasonic support box, 215 a-first ultrasonic device, 216-second ultrasonic support box, 216 a-second ultrasonic device, 221-third air inlet, 222-fourth air inlet, 223-third air outlet, 224-fourth air outlet, 23-second three-way valve, 3-heat exchanger, 4-catalytic reforming system, 40-steam generator, 41-first catalytic reforming reactor, 42-second catalytic reforming reactor, 43-third three-way valve, 44-first valve, 45-second valve, 46-third valve, 47-fourth valve, 48-fifth valve, 5-biosynthesis application system.
Detailed Description
In order to make the purposes, technical schemes and technical effects of the embodiments of the present invention more clear, the technical schemes in the embodiments of the present invention are clearly and completely described. The embodiments described below are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art without the benefit of the teachings of this invention, are intended to be within the scope of the invention.
The invention takes the fermented VOCs as raw materials to prepare the hydrogen-rich mixed gas by catalytic reforming, and the chemical reaction is complex, but the main reaction is as follows:
VOCs+H 2 O→CO+H 2 +CH 4 +CO 2 +C。
in a first aspect, in a specific embodiment of the present invention, the present invention provides a fermentation tail gas recycling system, including a pretreatment system, an adsorption-desorption system, and a catalytic reforming system; the pretreatment system is connected with the adsorption-desorption system, and the adsorption-desorption system is connected with the catalytic reforming system.
The pretreatment system can remove particles and liquid drops in the fermentation tail gas, and prevent the blockage of adsorption-desorption equipment and the competitive adsorption of water and VOCs.
The adsorption-desorption system can be used for adsorbing and desorbing the fermentation tail gas for concentration, so that the concentration of the fermentation tail gas is improved, and the operation efficiency of the system is improved.
The catalytic reforming system carries out catalytic reforming on the desorbed VOCs to obtain the hydrogen-rich mixed gas, and finally realizes the efficient conversion of the fermentation tail gas into the hydrogen-rich mixed gas and the recycling of the fermentation tail gas.
In some preferred embodiments of the present invention, the adsorption-desorption system includes an ultrasonic adsorption-desorption fixed bed, the ultrasonic adsorption-desorption fixed bed includes an adsorption layer and an ultrasonic support box, the ultrasonic support box is embedded in the adsorption layer, and an ultrasonic device is arranged in the ultrasonic support box. The ultrasonic device is embedded in the adsorption layer through the ultrasonic supporting box, so that the mass transfer efficiency is improved, and the concentration of VOCs in desorption gas is improved. For the fixed bed with an external ultrasonic device, the diameter of the fixed bed is generally 1.5-2m, and if the fixed bed is directly arranged outside the fixed bed, mass transfer to an inner layer is difficult; if the ultrasonic device is directly placed in the adsorption layer, the ultrasonic diffusing capacity is weakened, and the ultrasonic device is not easy to disassemble and is difficult to maintain. The ultrasonic adsorption and desorption fixed bed adopts an embedded design innovatively, so that the problems of uneven mass transfer, difficult maintenance and difficult practical application in practical application are avoided.
In the present invention, the adsorbent used as the adsorbent layer is not particularly limited, and may include, but is not limited to, one or two or more of adsorbent materials such as activated carbon, resin and molecular sieve.
In the invention, in order to improve the removal efficiency and the operation efficiency of the system, the fermentation tail gas recycling system can comprise two or more adsorption-desorption systems connected in series and/or in parallel, preferably at least two adsorption-desorption systems connected in parallel, so that one adsorption and one desorption can be realized, and the continuous operation of the system is realized.
In some preferred embodiments of the present invention, the catalytic reforming system includes a catalytic reforming device and a steam generating device, the steam generating device mixes the steam after vaporization with the desorption tail gas, and the mixed gas of the steam and the desorption tail gas enters the catalytic reforming device.
In the invention, the components of the fermentation tail gas are complex, so that catalyst poisoning and adverse effects on the operation of equipment and a system are easily caused, and the operation efficiency and the treatment effect of the system are reduced. In order to improve the operation efficiency and the treatment effect of the system, in some preferred embodiments of the invention, the catalytic reforming device at least comprises two catalytic reforming reactors, so as to realize in-situ regeneration of the catalyst; the catalytic reforming reactorThe inlet of the catalytic reforming reactor is connected with the catalytic reforming tail gas conveying pipeline through a valve respectively; the outlets of the catalytic reforming reactors are connected in pairs through valves. By the design, the reducing catalytic reforming tail gas (containing H 2 CO, etc.) to regenerate the catalyst in situ, greatly reducing the cost of catalyst regeneration and improving the operating efficiency and treatment effect of the system.
In some preferred embodiments of the invention, the fermentation tail gas recycling system further comprises a heat exchange system, one end of the heat exchange system is connected with the adsorption-desorption system, the other end of the heat exchange system is connected with the catalytic reforming system, and the heat exchange medium is catalytic reforming tail gas and is used for preheating desorption tail gas and recovering heat of the catalytic reforming tail gas, so that the aim of saving energy is achieved, and the running cost of the whole system is reduced.
In the present invention, the type of the heat exchanger in the heat exchange system is not particularly limited, and one or both of a plate heat exchanger and a shell heat exchanger are exemplified.
In some preferred embodiments of the present invention, the fermentation tail gas recycling system further comprises an application system coupled to the heat exchange system or the catalytic reforming system for recycling the catalytic reformed tail gas, the application system including, but not limited to, a biosynthetic, chemical synthesis, or hydrogen internal combustion engine.
In a second aspect, the present invention also provides a method for recycling fermentation tail gas by using the above method, which includes the following steps: adopting a pretreatment system to treat fermentation tail gas; carrying out adsorption-desorption treatment on the pretreated tail gas; and carrying out catalytic reforming on the desorbed tail gas to obtain catalytic reforming tail gas.
In order to save energy consumption and reduce operation cost, the method also comprises the step of carrying out heat exchange on the catalytic reforming tail gas; further, in order to realize the recycling of the catalytic reforming tail gas, the method further comprises the step of recycling the catalytic reforming tail gas.
In order to improve the system operation efficiency and the treatment effect, the method further comprises the step of in-situ regeneration of the catalyst in the catalytic reforming reactor by adopting catalytic reforming tail gas. Specifically, the desorption tail gas is stopped from being introduced into the catalytic reforming reactor to be regenerated, then the catalytic reforming tail gas is introduced from the outlet of the catalytic reforming reactor to be regenerated, and the regenerated tail gas enters the catalytic reforming tail gas conveying pipeline through the inlet of the catalytic reforming reactor to be regenerated, so that the in-situ regeneration of the catalytic reforming reactor is realized.
In order to improve the system operation efficiency and the treatment effect, when the conversion rate of total hydrocarbons (calculated as methane) in the catalytic reforming reaction is reduced to 60% or less, the catalyst in the catalytic reforming reactor needs to be regenerated in situ.
According to the present invention, the desorption temperature at the time of the adsorption-desorption treatment is 100 to 300 ℃, the desorption temperature is preferably selected according to the property of the adsorption material, and a suitable desorption temperature is selected according to the type of the adsorption material, for example, the desorption temperature is 90 to 120 ℃ when the adsorbent is activated carbon, and the desorption temperature is 200 to 250 ℃ when the adsorbent is zeolite.
According to the invention, the temperature of the catalytic reforming is 200-1000 ℃, preferably 400-700 ℃, more preferably 400-550 ℃, and the temperature is too high, the energy consumption is large, the temperature is too low, the conversion efficiency is low, and the waste gas treatment requirement cannot be met.
According to the invention, the catalyst in the catalytic reforming reactor is a noble metal catalyst, preferably, the weight percentage content of noble metal is 1-10% based on the weight of the catalyst, and the carrier is MgAl spinel or rare earth material; more preferably, the catalyst is one or more of granular, monolithic and powdery.
According to the invention, the molar ratio of the water vapor to the total hydrocarbon in the waste gas is 1-6, and the too high molar ratio of the water vapor to the total hydrocarbon in the waste gas causes high energy consumption, and the too low molar ratio of the water vapor to the total hydrocarbon in the waste gas causes CO and CO 2 And CH (CH) 4 The overall yield of (2) is low. The total hydrocarbon refers to the total hydrocarbon of the waste gas of the fixed pollution source, methane and non-methane under the specified measurement conditions as defined in HJ 38-2017 gas chromatography for measuring the total hydrocarbon of the non-methaneThe corresponding sum of gaseous organics is produced on the gas chromatograph hydrogen flame ionization detector, and the mass volume concentration of total hydrocarbons and the amount of species both refer to the mass volume concentration and the amount of species in terms of methane.
According to the invention, the catalytic reforming tail gas prepared by the method for recycling the fermentation tail gas comprises H 2 、CO、CO 2 And CH (CH) 4 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, H in the tail gas is catalytically reformed 2 、CO、CO 2 And CH (CH) 4 H based on the total volume of (2) 2 Is 50-80% by volume.
In a third aspect, the invention also provides an application of the fermentation tail gas recycling system or the method in treating low-concentration waste gas.
The advantageous effects of the present invention are further illustrated by the following specific examples.
The raw materials or reagents used in the present invention are all purchased from market mainstream factories, and the raw materials or reagents are all of a standard analytical grade without any particular limitation as long as they can function as intended, without any particular limitation.
In the examples, the sample analysis and detection of the gas were performed with reference to HJ 759-2015, sample of the measuring tank for the volatile organic compounds in the ambient air/gas chromatography-mass spectrometry.
The content of total hydrocarbons (calculated as methane) in the desorption tail gas in the examples was carried out with reference to HJ 38-2017 "gas chromatography for determination of total hydrocarbons of stationary pollution source exhaust, methane and non-methane.
Example 1
Referring to fig. 1 and 2, embodiment 1 provides a fermentation tail gas recycling system, which comprises a tube bundle dust remover 1, a first ultrasonic adsorption-desorption fixed bed 21 and a second ultrasonic adsorption-desorption fixed bed 22 which are connected in parallel, a heat exchanger 3, a catalytic reforming system 4 and a biosynthesis system 5; the catalytic reforming system comprises a water vapor generating device 40 and a first catalytic reforming fixed bed reactor 41 and a second catalytic reforming fixed bed reactor 42 which are connected in parallel; the first and second catalytic reforming reactors are filled with granular catalysts, and the catalytic reforming reactors adopt an electric heating mode;
wherein the first ultrasonic adsorption-desorption fixed bed 21 comprises a first air inlet 211, a second air inlet 212, a first air outlet 213 and a second air outlet 214, the second ultrasonic adsorption-desorption fixed bed 22 comprises a third air inlet 221, a fourth air inlet 222, a third air outlet 223 and a fourth air outlet 224, the first air inlet 211 and the third air inlet 221 are connected with the tube bundle dust collector 1 through a first three-way valve 11, the second air outlet 214 and the fourth air outlet 224 are connected with the inlet of the plate heat exchanger 3 through a second three-way valve 23, the outlet of the plate heat exchanger 3 is connected with the water vapor generating device 40, the medium outlet of the heat exchanger 3 is connected with the biosynthesis system 5 through a pipeline, and the medium inlet of the heat exchanger 3 is connected with the inlet and the outlet of the first catalytic reforming reactor 41 and the second catalytic reforming reactor 42 through a pipeline;
the inlets of the first catalytic reforming reactor 41 and the second catalytic reforming reactor 42 are connected with the steam generator 40 through a third three-way valve 43, the inlets of the first catalytic reforming reactor 41 and the second catalytic reforming reactor 42 are also respectively connected with the medium inlet of the heat exchanger 3 through pipelines, a first valve 44 is arranged on the pipeline between the inlet of the first catalytic reforming reactor 41 and the medium inlet of the heat exchanger 3, a second valve 45 is arranged on the pipeline between the inlet of the second catalytic reforming reactor 42 and the medium inlet of the heat exchanger 3, the outlets of the first catalytic reforming reactor 41 and the second catalytic reforming reactor 42 are communicated through the pipeline, a third valve 46 is arranged on the pipeline, a fourth valve 47 is arranged on the pipeline between the outlet of the first catalytic reforming reactor 41 and the medium inlet of the heat exchanger 3, and a fifth valve 48 is arranged on the pipeline between the outlet of the second catalytic reforming reactor 42 and the medium inlet of the heat exchanger 3;
the ultrasonic adsorption-desorption fixed bed comprises an adsorption layer, a first ultrasonic supporting box 215 and a second ultrasonic supporting box 216, wherein the first ultrasonic supporting box 215 and the second ultrasonic supporting box 216 are embedded in the activated carbon adsorption layer, a first ultrasonic device 215a is arranged in the first ultrasonic supporting box 215, and a second ultrasonic device 216a is arranged in the second ultrasonic supporting box 216. The ultrasonic adsorption-desorption fixed bed also comprises a jacket for cooling the ultrasonic adsorption-desorption fixed bed.
The method for recycling the fermentation tail gas by using the fermentation tail gas recycling system comprises the following steps:
firstly, the fermentation waste gas from a factory enters a tube-bundle dust remover to be subjected to dust removal treatment, dust is discharged from a solid outlet of the tube-bundle dust remover, a first three-way valve 11 is opened to allow gas to enter a first ultrasonic adsorption-desorption fixed bed 21, the gas adsorbed by the first ultrasonic adsorption-desorption fixed bed 21 is discharged from an air outlet 213, the first three-way valve 11 is switched to a second ultrasonic adsorption-desorption fixed bed 22 after adsorption saturation, the gas after dust removal enters the second ultrasonic adsorption-desorption fixed bed 22 to be subjected to adsorption operation, meanwhile, hot nitrogen is introduced into the first ultrasonic adsorption-desorption fixed bed 21 through a second air inlet 212 to reversely desorb the adsorption waste gas, a second three-way valve 23 is opened to allow the desorption gas to enter a heat exchanger 3, the second three-way valve 23 is switched to allow the second ultrasonic adsorption-desorption fixed bed to be communicated with the heat exchanger 3 after desorption is finished, the hot nitrogen is introduced into the second ultrasonic adsorption-desorption fixed bed 22 through the air inlet 222 to reversely desorb the adsorption waste gas, the first ultrasonic adsorption-desorption fixed bed 21 and the second ultrasonic adsorption-desorption fixed bed 22 are alternately adsorbed-desorbed by switching the first three-way valve 11 and the second three-way valve 23 to realize continuous operation, the desorbed tail gas enters the heat exchanger 3, enters the steam generator 40 after exchanging heat with the reformed tail gas, opens the third three-way valve 43, enables the desorbed tail gas to be mixed with steam and then enters the first catalytic reforming reactor 41, opens the valve 47, closes the valves 44, 45, 46 and 48, and the steam mixture is subjected to reforming reaction to obtain reformed tail gas which enters the biosynthesis application system 5 after entering the heat exchanger 3 through a pipeline to exchange heat.
When the total hydrocarbon conversion rate of the first catalytic reforming reactor 41 is reduced to below 60%, the third three-way valve 43 is switched to enable the desorption tail gas to be mixed with water vapor and then enter the second catalytic reforming reactor 42, the valves 44, 46 and 48 are opened, the valves 45 and 47 are closed, a part of gas enters the first catalytic reforming reactor 41 to regenerate the catalyst, the regenerated gas enters the heat exchanger 3 through the valve 44, the valves 44 and 46 are closed after regeneration is finished, when the total hydrocarbon conversion rate of the second catalytic reforming reactor 42 is reduced to 60%, the third three-way valve 43 is switched to enable the desorption tail gas to be mixed with water vapor and then enter the first catalytic reforming reactor 41, the valve 48 is closed, the valve 45, the valve 46 and the valve 47 are opened, a part of gas enters the second catalytic reforming reactor 42 to regenerate the catalyst, the regenerated gas enters the heat exchanger 3 through the valve 45, the valves 45 and 46 are closed after regeneration is finished, and the process is repeated to ensure the high-efficiency operation of the system.
Example 2
The influence of different catalytic reforming temperatures on the treatment effect is examined by adopting the recycling method of the fermentation tail gas in example 1, and the analysis and detection show that the total hydrocarbon content in the fermentation tail gas is 600mg/m from the fermentation tail gas in the low-sugar yeast production process of Angel Yichang factories 3 。
The fermentation waste gas is firstly treated with 2m 3 Introducing the flow rate of/h into a tube bundle dust remover for pretreatment, introducing the pretreated tail gas into a first ultrasonic adsorption-desorption fixed bed for adsorption treatment, wherein the pipe diameter of an adsorption pipe is 80mm, the adsorbent is an activated carbon adsorbent, the loading amount is 30g, saturation is achieved after adsorption for 60min, the adsorbed tail gas is discharged after reaching standards, then desorbing the adsorption saturated ultrasonic adsorption-desorption fixed bed by using nitrogen at 100 ℃ with nitrogen at 36L/h, and sampling, analyzing and detecting that the total hydrocarbon content of the desorbed gas is 1200mg/m 3 Wherein the ethanol contains 500mg/m 3 Acetaldehyde content of 100mg/m 3 Then the desorption gas enters a catalytic reforming device for catalytic reforming, the pipe diameter of the catalytic reforming reactor is 30mm, the catalyst is a noble metal catalyst (SPR-1 model is Liaoning Haitai technology development Co., ltd.), the filling amount is 3g, and the catalytic reforming reaction conditions are as follows: the molar ratio of the water vapor to the total hydrocarbon (calculated by methane) in the desorption waste gas is 3, the reaction temperature is 400 ℃,450 ℃,500 ℃ and 550 ℃, the gas components and the content in the catalytic reforming tail gas are sampled and tested from the outlet of the catalytic reforming reactor, and the CO in the reforming tail gas are calculated according to the following formula 2 And CH (CH) 4 Is characterized by the total yield of CO and CO in the reformed tail gas 2 、CH 4 And H 2 The volume content of each gas (COCO 2 、CH 4 And H 2 Based on the total volume of (c) and the results are shown in table 1,
1) Reforming CO and CO in tail gas 2 And CH (CH) 4 Is of the total yield of (2)
Wherein:
Y-CO in reformed tail gas 2 And CH (CH) 4 Total yield,%;
n co -the amount, mol, of CO material in the reformed tail gas;
n co2 CO in the reformed tail gas 2 The amount of the substance, mol;
n CH4 reforming CH in tail gas 4 The amount of the substance, mol;
n before the reaction The amount of material that desorbs the total hydrocarbons (in methane) in the gas.
2) Reforming CO and CO in tail gas 2 、CH 4 And H 2 Each gas occupies CO and CO 2 、CH 4 And H 2 Percentage of total volume
Wherein: g H2 ——H 2 Occupying CO and CO 2 、CH 4 And H 2 Percentage of total volume;
G CO ——CO occupies CO and CO 2 、CH 4 And H 2 Percentage of total volume;
G CO2 ——CO 2 occupying CO and CO 2 、CH 4 And H 2 Percentage of total volume;
G CH4 ——CH 4 occupying CO and CO 2 、CH 4 And H 2 Percentage of total volume.
TABLE 1 influence of different reforming temperatures on catalytic reforming effect
Example 3
The effect of the molar ratio of different water vapor to total hydrocarbon (calculated as methane) in the desorption exhaust gas on the treatment effect was examined by using the fermentation exhaust gas recycling method of example 1, and the difference between example 2 is that the catalytic reforming reaction conditions are as follows: the reaction temperature was 500 ℃, the molar ratio of steam to total hydrocarbon (calculated as methane) in the exhaust gas was 1,2,3,4, and the gas components and the content in the catalytic reforming tail gas were sampled and tested from the outlet of the catalytic reforming reactor, and the CO and CO in the reforming tail gas were calculated according to the calculation formula in example 2 2 And CH (CH) 4 Overall yield of (C) and CO 2 、CH 4 And H 2 Is expressed as volume percent of CO (CO) 2 、CH 4 And H 2 Total volume of (b) and the results are shown in table 2:
TABLE 2 influence of the molar ratios of different steam to total hydrocarbons in the exhaust gas on the catalytic reforming effect
As can be seen from tables 1 and 2, the fermentation tail gas recycling system of the invention is used for treating the fermentation tail gas, and CO in the reformed tail gas 2 And CH (CH) 4 The total yield of the catalyst reaches more than 75 percent and even reaches 100 percent, and the reformed tail gas contains CO and CO 2 、CH 4 And H 2 In the form of CO and CO 2 、CH 4 And H 2 Is used for the total volume of the (c) and (d),H 2 the volume percentage of the reformed tail gas is 62.9-74%, and the reformed tail gas can be used in the fields of biosynthesis, chemical synthesis or hydrogen internal combustion engine and the like, thereby realizing the resource utilization of fermentation tail gas.
Example 4
The CEA program was used to simulate the component ratios of each product of the fermentation VOCs at different temperatures during reforming. Ethanol is considered to be the primary product in fermenting VOCs, and therefore is used as a model compound. Among these, CEA (chemical equilibrium with application) is a chemical equilibrium computer program developed by the s.gordon doctor, b.j.mcbride doctor and NASA Glenn research center. The procedure may simulate the gas composition of a chemical reaction when chemical equilibrium is reached under different temperature and pressure conditions.
The simulation conditions were as follows: the reaction temperature is 100-800 deg.c and the pressure is normal pressure. S/c=3 (S represents the amount of water vapor substance, C represents the amount of carbon atom substance in ethanol; 3 represents the ratio of the two), and the simulation results are shown in table 3:
TABLE 3 ethanol conversion and the volume percent of each gas in the product and molar carbon content during steam reforming of ethanol at different reaction temperatures
As can be seen from Table 3, ethanol has a higher conversion in the reaction zone of 100-800 ℃. The ratio of the components of each product gas is different at different reaction temperatures, and the hydrogen accounts for 73 percent at most under the reaction condition of 350 ℃, and the CO 2 The ratio of (c) was 8.06% and 19.0%, respectively, and the amount of carbon deposition (Cgr) produced was almost 0. The separation can obtain high-purity hydrogen gas, and the hydrogen gas can be used as a hydrogen energy source.
Example 5
The CEA program is adopted to simulate the component proportion of each product of the fermentation VOCs in the reforming process under different water-carbon ratios, and ethanol is adopted as a model compound.
The simulation conditions were as follows: s/c=1-5, pressure: normal pressure, temperature: the simulation results are shown in Table 4 at 300 ℃ below:
TABLE 4 conversion of ethanol and ratio of the components of the respective product gases during steam reforming of ethanol under different Water-carbon ratios (S/C)
As can be seen from table 4, as S/C increases, the hydrogen ratio increases, and when S/c=5, the hydrogen ratio in the produced gas is 42%, the methane ratio is 34%, and the pretreatment can be used for power generation of the internal combustion engine.
In summary, the pretreatment, adsorption and desorption, catalytic reforming and other functions are coupled to obtain the fermentation tail gas recycling system, and the pretreatment system is used for removing particles and liquid drops in the fermentation tail gas to prevent the blockage of adsorption-desorption equipment and the competitive adsorption of water and VOCs; and the desorbed VOCs are subjected to catalytic reforming through a catalytic reforming system to obtain hydrogen-rich mixed gas, and finally, the fermentation tail gas is efficiently converted into the hydrogen-rich mixed gas, so that the recycling utilization of the fermentation tail gas is realized.
Finally, it is noted that the above-mentioned preferred embodiments are only intended to illustrate rather than limit the invention, and that, although the invention has been described in detail by means of the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (19)
1. The fermentation tail gas recycling system is characterized by comprising a pretreatment system, an adsorption-desorption system and a catalytic reforming system; the pretreatment system is connected with the adsorption-desorption system, and the adsorption-desorption system is connected with the catalytic reforming system.
2. The fermentation tail gas recycling system according to claim 1, wherein the pretreatment system comprises a dust removal and/or defogging device; preferably, the dust removal device is selected from tube bundle dust removal devices and/or filter screens.
3. The fermentation tail gas recycling system according to claim 1 or 2, wherein the adsorption-desorption system comprises at least two sets of ultrasonic adsorption-desorption fixed beds connected in parallel.
4. The fermentation tail gas recycling system according to claim 3, wherein the ultrasonic adsorption-desorption fixed bed comprises an adsorption layer and an ultrasonic support box, the ultrasonic support box is embedded in the adsorption layer, and an ultrasonic device is arranged in the ultrasonic support box.
5. The fermentation tail gas recycling system according to claim 4, wherein the adsorbent of the adsorption layer is one or more selected from the group consisting of activated carbon, resin and molecular sieve adsorption material.
6. The fermentation tail gas recycling system according to any one of claims 1 to 5, wherein the ultrasonic adsorption-desorption system takes the form of thermal gas desorption, and the desorption gas is selected from N 2 、CO 2 And one or two or more of He.
7. The fermentation tail gas recycling system according to any one of claims 1 to 6, wherein the catalytic reforming system comprises a catalytic reforming device and a steam generating device, wherein the steam generating device gasifies water and mixes the gasified water with the desorption tail gas, and then enters the catalytic reforming device.
8. The fermentation tail gas recycling system according to claim 7, wherein the catalytic reforming device comprises at least two catalytic reforming reactors; the inlet of the catalytic reforming reactor is connected with the steam generating device through a valve respectively; preferably, the inlet of the catalytic reforming reactor is connected with the catalytic reforming tail gas conveying pipeline through a valve, and the outlet of the catalytic reforming reactor is connected with the catalytic reforming tail gas conveying pipeline through a valve respectively; more preferably, the outlets of the catalytic reforming reactors are connected by valves.
9. The fermentation tail gas recycling system according to claim 7 or 8, wherein the catalyst in the catalytic reforming reactor is selected from noble metal catalysts and/or non-noble metal catalysts; preferably, the catalyst is a noble metal catalyst; more preferably, the catalyst is one or more of granular, monolithic and powdered; further preferably, the catalytic reforming reactor is of the fixed bed or fluid bed type.
10. The fermentation tail gas recycling system according to any one of claims 1 to 9, further comprising a heat exchange system, one end of which is connected to the adsorption-desorption system and the other end of which is connected to the catalytic reforming system, for preheating the desorption tail gas and recovering heat of the catalytic reforming tail gas; preferably, the heat exchange system comprises a plate heat exchanger and/or a shell heat exchanger.
11. The fermentation tail gas recycling system according to any one of claims 1-10, further comprising a control system, wherein the control system comprises a computer control center, a human-machine interface and a programmable controller, wherein the computer control center is in signal connection with the programmable controller, the computer control center is in communication with the human-machine interface, the human-machine interface is electrically connected with the programmable controller, and the programmable controller is electrically connected with the pretreatment system, the adsorption-desorption system and the catalytic reforming system.
12. The fermentation tail gas recycling system according to any one of claims 1 to 11, further comprising an application system, wherein the application system is connected with a heat exchange system or a catalytic reforming system for recycling the catalytic reforming tail gas; preferably, the recycling comprises one of biosynthesis, chemical synthesis or a hydrogen internal combustion engine.
13. A method for recycling fermentation tail gas, which is characterized by using the fermentation tail gas recycling system according to any one of claims 1-12, and comprising the following steps:
adopting a pretreatment system to treat fermentation tail gas; carrying out adsorption-desorption treatment on the pretreated tail gas; and carrying out catalytic reforming on the desorbed tail gas to obtain catalytic reforming tail gas.
14. The method of claim 13, further comprising the step of heat exchanging and/or recycling the catalytic reforming tail gas.
15. The method of claim 13 or 14, further comprising the step of regenerating the catalyst in situ using the catalytic reformed tail gas.
16. The method of claim 15, wherein the in situ regeneration comprises the steps of: firstly, stopping introducing desorption tail gas into a catalytic reforming reactor to be regenerated, then introducing catalytic reforming tail gas from an outlet of the catalytic reforming reactor to be regenerated, and introducing the regenerated tail gas into a catalytic reforming tail gas conveying pipeline from an inlet of the catalytic reforming reactor to realize in-situ regeneration of the catalyst.
17. The method according to any one of claims 13-16, wherein the catalytic reforming is carried out at a temperature of 200-1000 ℃, preferably 400-700 ℃, more preferably 400-550 ℃; preferably, the molar ratio of the water vapour and the total hydrocarbons of the catalytic reforming is between 1 and 6, preferably between 2 and 4.
18. The method of any one of claims 13-17, wherein the catalytic reformed tail gas comprises H 2 、CO、CO 2 And CH (CH) 4 The method comprises the steps of carrying out a first treatment on the surface of the Preferably in H 2 、CO、CO 2 And CH (CH) 4 H based on the total volume of (2) 2 Is 50-80% by volume.
19. Use of the fermentation tail gas recycling system of any one of claims 1-12 or the method of any one of claims 13-18 for treating low concentration exhaust gases.
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