CN110639330B - System and method for treating volatile organic compound-containing gas and preparing carbon nano material - Google Patents
System and method for treating volatile organic compound-containing gas and preparing carbon nano material Download PDFInfo
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
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- 238000000034 method Methods 0.000 title claims abstract description 20
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- 239000007788 liquid Substances 0.000 claims abstract description 54
- 238000000926 separation method Methods 0.000 claims abstract description 43
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- 238000010438 heat treatment Methods 0.000 claims description 7
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
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- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The system comprises a gas adsorption/desorption subsystem, a gas-liquid separation subsystem and a tail gas carbonization subsystem; the method for treating the gas containing the volatile organic compounds and preparing the carbon nano material by using the system realizes the adsorption of the gas containing the volatile organic compounds through the gas adsorption/desorption subsystem, and the gas of the gas adsorption/desorption subsystem is discharged after reaching the standard; condensing the organic matters desorbed by the gas adsorption/desorption subsystem through a gas-liquid separation subsystem to obtain liquid, and collecting, recycling or retreating the liquid; and (4) the tail gas from the gas-liquid separation subsystem enters a tail gas carbonization subsystem to generate a carbon nano material at high temperature, and the tail gas is combined with the tail gas from the gas adsorption/desorption subsystem and then is discharged after reaching the standard. The invention realizes the gradient utilization of volatile organic compounds, and has high safety through the carbonization process; and the light volatile organic compounds which are difficult to treat are changed into carbon nano materials, so that the cost of the adsorbent is reduced.
Description
Technical Field
The invention belongs to the technical field of chemical industry and environmental protection, and particularly relates to a system and a method for treating volatile organic compound-containing gas and preparing a carbon nano material by an adsorption method.
Background
In the chemical production process, the material processing industry, the catering industry and the oil storage, loading and unloading process, a large amount of Volatile Organic Compounds (VOCs) are often generated, and the oil-based fuel oil has the actual current situations of strong dispersity, more components, large molecular weight difference, large physical property difference and the like. Methods for treating volatile organic compound-containing gases generally include condensation, adsorption, absorption, oxidation, and the like. Wherein, the adsorption method is commonly used for various porous materials (such as active carbon and silica gel), and has the characteristics of simple and safe process and the like. If the activated carbon material is used in the adsorption method, the cyclic use performance is poor because of the large number of micropores. However, if mesoporous materials such as carbon nanotubes and graphene are used, the mesoporous materials can be repeatedly adsorbed and desorbed for recycling. The medium used in desorption is high-temperature steam or high-temperature gas, and the energy consumption in desorption is the most important restriction link of the adsorption method.
However, after adsorption and concentration, a part of the organic matters after desorption can be changed into a liquid phase, so that the organic matters can be conveniently separated and recycled or treated by other methods. However, most of the gas still remains as gas at normal temperature and pressure, which is inconvenient for storage and can not be discharged at will. Processing must continue. On the other hand, carbon nanomaterials are expensive and also a major obstacle to their adsorption applications.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a system and a method for treating volatile organic compound-containing gas by an adsorption method and converting organic compounds into carbon nano materials, so that the problem that gaseous organic compounds after concentration and desorption are difficult to treat is solved, the heat recovery and utilization of tail gas are realized, the energy consumption is reduced, and the added value of products is improved. And the carbon nano material can be made into the adsorbent, so that the cost of the adsorbent can be greatly reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the system for treating the gas containing the volatile organic compounds and preparing the carbon nano material comprises a gas adsorption/desorption subsystem 1, a gas-liquid separation subsystem 2 and a tail gas carbonization subsystem 3, wherein the top of the gas adsorption/desorption subsystem 1 is provided with a gas inlet 4 containing the volatile organic compounds, the bottom of the gas adsorption/desorption subsystem 1 is provided with an adsorbed gas outlet 5 and a desorbed gas outlet 6, and the desorbed gas outlet 6 of the gas adsorption/desorption subsystem 1 is communicated with a middle inlet 7 of the gas-liquid separation subsystem 2; the bottom of the gas-liquid separation subsystem 2 is provided with a condensed organic liquid outlet 8), and an organic gas outlet 9 at the top of the gas-liquid separation subsystem 2 is communicated with a bottom inlet 10 of the tail gas carbonization subsystem 3; a carbonized tail gas outlet 13 at the top of the tail gas carbonization subsystem 3 is connected with an adsorbed gas outlet 5 at the bottom of the gas adsorption/desorption subsystem 1; when the gas-liquid separation subsystem 2 is not needed, the desorbed gas outlet 6 at the bottom of the gas adsorption/desorption subsystem 1 is connected with the bottom inlet 10 of the tail gas carbonization subsystem 3; the exhaust gas carbonization subsystem 3 is further provided with a catalyst inlet 11 and a carbon material outlet 12.
The gas adsorption/desorption subsystem 1 is filled with an easily-regenerated adsorbent which is made of one or more of carbon, molecular sieve or alumina.
The carbon is one or more of activated carbon, carbon fiber, carbon nanotube and graphene.
And the organic liquid and the organic gas in the gas-liquid separation subsystem 2 are respectively discharged from the bottom and the top after being condensed and separated.
The catalyst filled in the tail gas carbonization subsystem 3 is metal and/or oxide, the metal comprises one or more of iron, cobalt, nickel, copper, manganese, zinc, molybdenum and tungsten, and the oxide comprises one or more of alumina, silica, magnesia and zirconia; the mass fraction of the metal is 0-100%; the catalyst cracks the organic matter at the temperature of 500 plus materials and 1000 ℃, and the mass space velocity of the organic matter is 0.001-20h-1Carbon nano-materials are generated, and the components of the generated tail gas are hydrogen and methane.
The system for treating the volatile organic compound-containing gas and preparing the carbon nano material comprises the following steps:
a) a gas adsorption/desorption subsystem 1, a gas-liquid separation subsystem 2 and a tail gas carbonization subsystem 3 are connected in sequence;
b) introducing gas containing volatile organic compounds from a gas inlet 4 of the gas adsorption/desorption subsystem 1, adsorbing the organic compounds on the adsorbent after passing through the adsorbent layer in the gas adsorption/desorption subsystem 1, and discharging the adsorbed gas from an adsorbed gas outlet 5 at the bottom of the gas adsorption/desorption subsystem 1;
c) when the adsorption layer of the gas adsorption/desorption subsystem 1 is saturated, stopping introducing the gas containing volatile organic compounds, heating the gas adsorption/desorption subsystem 1 to 90-250 ℃ to desorb the gas on the adsorbent, and discharging the gas from a desorbed gas outlet 6 at the bottom of the gas adsorption/desorption subsystem 1;
d) if the gas discharged from the desorbed gas outlet 6 of the gas adsorption/desorption subsystem 1 does not have the separation and recycling value, the gas is directly introduced into the tail gas carbonization subsystem 3 through the bottom inlet 10 of the tail gas carbonization subsystem 3; generating a carbon nanotube material on the catalyst of the tail gas carbonization subsystem 3 at 500-;
e) if the gas discharged from the desorbed gas outlet 6 of the gas adsorption/desorption subsystem 1 has a recycling value, the gas is introduced into the gas-liquid separation subsystem 2 through the middle inlet 7 of the gas-liquid separation subsystem 2; condensing at-20-10 deg.c to separate organic liquid from organic gas; valuable organic liquid is discharged from a condensed organic liquid outlet 8) at the bottom of the gas-liquid separation subsystem 2, so that direct recycling or continuous separation recycling is realized; the tail gas containing organic matters discharged from an organic matter gas outlet 9 at the top of the gas-liquid separation subsystem 2 enters the tail gas carbonization subsystem 3 through a bottom inlet 10, and a carbon nanotube material is generated on a catalyst of the tail gas carbonization subsystem 3;
f) the tail gas of the tail gas carbonization subsystem 3 is discharged through a carbonized tail gas outlet 13, is mixed with the adsorbed gas of the adsorbed gas outlet 5 at the bottom of the gas adsorption/desorption subsystem 1, and is directly discharged or continuously used on the premise of confirming that the total standard is reached;
g) after the carbon material in the tail gas carbonization subsystem 3 reaches a certain volume, the carbon material is removed through the carbon material outlet 12, and the catalyst is replenished from the catalyst inlet 11.
When the sub-gas adsorption/desorption system 1 executes the adsorption operation, the temperature is-25-20 ℃, and the pressure is 0.1-2 MPa; the adsorption effect is as follows: the organic content in the inert gas is less than 50ppm, and the aromatic hydrocarbon is less than 4 ppm; when the desorption operation is carried out, the temperature is 50-250 ℃, the pressure is-0.09-1.95 MPa, and the desorption rate is more than 95 percent.
The main body of the volatile organic compound-containing gas is inert gas, the concentration of the organic compound is 50-200000ppm, and the volatile organic compound-containing gas comprises organic compounds with the molecular weight of 26-300.
The carbon nano-materials generated in the exhaust gas carbonization subsystem 3 include one or more of carbon nano-particles, carbon nano-fibers, carbon nano-tubes and graphene.
Compared with the prior art, the invention has the beneficial effects that:
(1) the system and method of the present invention converts very complex, concentrated organic gases into carbon nanomaterials. The carbon nano material can be used as an adsorbent for treating volatile organic compounds, so that the great problem of treating concentrated organic gas is solved, and the cost of the adsorbent is reduced by 80-90%.
(2) The system and the method can recycle the organic components with recovery value after concentration, desorption and gas-liquid separation, can reduce the cost by 5-30 percent and reduce CO25-50% of discharge.
Drawings
FIG. 1 is a block diagram of a system including three subsystems (including subsystems (1), (2) and (3))
FIG. 2 is a block diagram of a system of the present invention that does not require a gas-liquid separation subsystem
Wherein, 1, the gas adsorption/ desorption subsystems 1 and 2, the gas- liquid separation subsystems 2 and 3, the tail gas carbonization subsystems 3 and 4, and a gas inlet containing volatile organic compounds; 5. the device comprises an adsorbed gas outlet, 6 a desorbed gas outlet, 7 a middle inlet, 8 a condensed organic liquid outlet, 9 an organic gas outlet, 10 a bottom inlet, 11 a catalyst inlet, 12 a carbon material outlet and 13 a carbonized tail gas outlet.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
As shown in fig. 1, a gas adsorption/desorption subsystem 1, a gas-liquid separation subsystem 2 and a tail gas carbonization subsystem 3 are connected in sequence;
introducing gas containing volatile organic compounds (the main gas is nitrogen, and the organic compounds are 5000ppm of C2-C10 hydrocarbon) from a gas inlet 4 containing the volatile organic compounds of the gas adsorption/desorption subsystem 1, wherein the adsorption temperature is-20 ℃, the pressure is 2MPa, the organic compounds are adsorbed on an adsorbent (50% of carbon nano tubes and 50% of molecular sieves in mass fraction) after passing through an adsorbent layer in the gas adsorption/desorption subsystem 1, and waste gas discharged after the treated argon gas (the organic compounds are lower than 50ppm and the aromatic hydrocarbons are lower than 4ppm) reaches the standard is discharged from an adsorbed gas outlet 5 of the gas adsorption/desorption subsystem 1;
when the adsorption layer of the gas adsorption/desorption subsystem 1 is saturated, stopping introducing the gas containing volatile organic compounds, heating the gas adsorption/desorption subsystem 1 to 250 ℃, wherein the desorption pressure is 1.95MPa, so that the gas on the adsorbent is desorbed, the desorption rate is more than 95%, and the gas is discharged from the desorbed gas outlet 6 of the gas adsorption/desorption subsystem 1; enters the gas-liquid separation subsystem 2 through a middle inlet 7 of the gas-liquid separation subsystem 2. Condensation is carried out at-20 ℃ to separate C6-C10 hydrocarbons from C2-C5 hydrocarbons. C6-C10 hydrocarbons are discharged from the condensed organic liquid outlet 8 and recycled.
The tail gas containing C2-C5 organic matters discharged from an organic matter gas outlet 9 at the top of the gas-liquid separation subsystem 2 enters a tail gas carbonization subsystem 3 through a bottom inlet 10, and is cracked on a catalyst (a pure nickel catalyst) at 800 ℃, wherein the mass space velocity of the organic matters is 0.001h-1Generating carbon nano-tubes; the tail gas (mainly H2, CH4) of the tail gas carbonization subsystem 3 is carbonized, and then the carbonized tail gas outlet 13 is mixed with the gas of the adsorbed gas outlet 5 at the bottom of the gas adsorption/desorption subsystem 1, so that the standard emission is realized.
After the carbon material in the tail gas carbonization subsystem 3 reaches a certain volume, the carbon material is removed through the carbon material outlet 12, and the catalyst is replenished from the catalyst inlet 11.
Example 2
As shown in fig. 2, a gas adsorption/desorption subsystem 1, a gas-liquid separation subsystem 2, and a tail gas carbonization subsystem 3 are connected in sequence;
volatile organic compound-containing gas (argon as main gas and 20000ppm of C as organic compound)1-C3Mixture of alcohol and epichlorohydrin in any proportion) is introduced from a gas inlet 4 of the gas adsorption/desorption subsystem 1, which contains volatile organic compounds, the adsorption temperature is-25-0 ℃, the pressure is 2MPa, the organic compounds are adsorbed on an adsorbent (20% of activated carbon and 80% of graphene) after passing through an adsorbent layer in the gas adsorption/desorption subsystem 1, the treated argon (the organic compounds are lower than 1.5ppm), and the exhaust gas which reaches the standard and is discharged from an adsorbed gas outlet 5 of the gas adsorption/desorption subsystem 1;
when the adsorption layer of the gas adsorption/desorption subsystem 1 is saturated, stopping introducing the gas containing volatile organic compounds, heating the gas adsorption/desorption subsystem 1 to 50 ℃, and desorbing at a pressure of 1MPa to desorb the gas on the adsorbent at a desorption rate>99.5% from the gas adsorption/desorption subsystem 1The desorbed gas is discharged from the gas outlet 6, enters the tail gas carbonization subsystem 3 through the bottom inlet 10 of the tail gas carbonization subsystem 3, and is cracked on a catalyst (1 percent of Mo-19 percent of Co-20 percent of Zn-60 percent of MgO) at 500 ℃, and the mass space velocity of the organic matter is 20h-1Generating a mixture of carbon nanotubes, carbon nanofibers and graphene; the tail gas (mainly H2, CH4) of the tail gas carbonization subsystem 3 is carbonized, and then the carbonized tail gas outlet 13 is mixed with the gas of the adsorbed gas outlet 5 at the bottom of the gas adsorption/desorption subsystem 1, so that the standard emission is realized.
After the carbon material in the tail gas carbonization subsystem 3 reaches a certain volume, the carbon material is removed through the carbon material outlet 12, and the catalyst is replenished from the catalyst inlet 11.
Example 3
As shown in fig. 2, a gas adsorption/desorption subsystem 1, a gas-liquid separation subsystem 2, and a tail gas carbonization subsystem 3 are connected in sequence;
introducing argon containing volatile organic compound gas (the main gas is any mixture of hydrogen and CO, the organic compound is crude oil component with the molecular weight of 200000ppm and 200-300) from a gas inlet 4 containing the volatile organic compound of the gas adsorption/desorption subsystem 1, the adsorption temperature is 20 ℃, the pressure is 0.3MPa, the organic compound is adsorbed on an adsorbent (graphene) after passing through an adsorbent layer in the gas adsorption/desorption subsystem 1, and the waste gas discharged after the treated mixture of CO and H2 (the organic compound is lower than 10ppm) reaches the standard is discharged from an adsorbed gas outlet 5 of the gas adsorption/desorption subsystem 1;
when the adsorption layer of the gas adsorption/desorption subsystem 1 is saturated, stopping introducing the gas containing volatile organic compounds from the top, introducing high-temperature gas into the gas adsorption/desorption subsystem 1, heating to 250 deg.C, and desorbing at-0.09 MPa to desorb the gas on the adsorbent at a desorption rate>95 percent, discharged from a desorbed gas outlet 6 of the gas adsorption/desorption subsystem 1, enters the tail gas carbonization subsystem 3 through a bottom inlet 10 of the tail gas carbonization subsystem 3, and is subjected to catalytic reaction (5 percent of Ni-70 percent of Mn-25 percent of ZrO) at the temperature of 1000 DEG C2) The mass space velocity of the organic matter is 1.5h-1A mixture of carbon nanotubes and graphene is generated. The tail gas (mainly H2, CH4) of the tail gas carbonization subsystem 3 is carbonized and then dischargedThe port 13 is mixed with the gas of the adsorbed gas outlet 5 at the bottom of the gas adsorption/desorption subsystem 1 to be discharged after reaching the standard.
After the carbon material of the exhaust gas carbonizing subsystem 3 reaches a certain volume, the carbon material is removed from the carbon material outlet 12, and the catalyst is supplemented from the catalyst inlet 11.
Example 4
As shown in fig. 2, a gas adsorption/desorption subsystem 1, a gas-liquid separation subsystem 2, and a tail gas carbonization subsystem 3 are connected in sequence;
the gas containing volatile organic compounds (the main gas is CO)2200ppm, propane, gasoline, pyridine, cumene, phenetole, furan) is introduced from the gas inlet 4 of the gas adsorption/desorption subsystem 1, the adsorption temperature is 0 ℃, and the pressure is 1 MPa. After passing through the adsorbent layer in the gas adsorption/desorption subsystem 1, the organic substances are adsorbed on the adsorbent (20% alumina, 50% carbon fiber, 30% activated carbon), and the treated CO is obtained2(organic matter is less than 40PPm, aromatic hydrocarbon substance is less than 4PPm), is discharged from the gas outlet 5 after adsorption of the gas adsorption/desorption subsystem 1;
when the adsorption layer of the gas adsorption/desorption subsystem 1 is saturated, stopping introducing the gas containing volatile organic compounds, introducing high-temperature gas into the gas adsorption/desorption subsystem 1, heating to 50 ℃, and desorbing at a pressure of 0.5MPa to desorb the gas on the adsorbent, wherein the desorption rate is higher than that of the gas>98.5 percent, and is discharged from a post-desorption gas outlet 6 of the gas adsorption/desorption subsystem 1. Enters the tail gas carbonization subsystem 3 through the bottom inlet 10 of the tail gas carbonization subsystem 3, and the mass space velocity of the organic matter is 12.5h at 900 DEG C-1In the presence of catalyst (48% Ni-2% W-20% MgO-30% SiO)2) And (4) cracking to generate a mixture of carbon nanofibers and carbon nanoparticles. The tail gas (mainly H2, CH4) of the tail gas carbonization subsystem 3 is carbonized, and then the carbonized tail gas outlet 13 is mixed with the gas of the adsorbed gas outlet 5 at the bottom of the gas adsorption/desorption subsystem 1, so that the standard emission is realized.
After the carbon material of the exhaust gas carbonizing subsystem 3 reaches a certain volume, the carbon material is removed from the carbon material outlet 12, and the catalyst is supplemented from the catalyst inlet 11.
Example 5
As shown in fig. 1, a gas adsorption/desorption subsystem 1, a gas-liquid separation subsystem 2 and a tail gas carbonization subsystem 3 are connected in sequence;
introducing nitrogen containing volatile organic gas (50ppm, mixture of butane and dinitrotoluene at arbitrary ratio) from inlet 4 of gas adsorption/desorption subsystem 1, adsorbing at 5 deg.C and 0.5MPa, adsorbing organic substances on alumina adsorbent, and treating CO2(organic matter is less than 3PPm, aromatic hydrocarbon substance is less than 2PPm), the exhaust gas which reaches the standard is discharged from the gas outlet 5 of the gas adsorption/desorption subsystem 1 after adsorption;
when the adsorption layer of the gas adsorption/desorption subsystem 1 of the subsystem is saturated, stopping introducing gas containing volatile organic compounds, introducing high-temperature gas into the gas adsorption/desorption subsystem 1, heating to 90 ℃, and desorbing at the pressure of 0.9MPa to desorb the gas on the adsorbent, wherein the desorption rate is more than 98.5%, and the gas is discharged from a desorbed gas outlet 6 of the gas adsorption/desorption subsystem 1; enters the gas-liquid separation subsystem 2 through a middle inlet 7 of the gas-liquid separation subsystem 2. The dinitrotoluene is condensed at 10 ℃ and separated from the propane gas. Dinitrotoluene is discharged from the condensed organic liquid outlet 8 and recycled.
The butane-containing tail gas discharged from an organic gas outlet 9 at the top of the gas-liquid separation subsystem 2 enters a tail gas carbonization subsystem 3 through a bottom inlet 10, and is subjected to catalytic reaction at 950 ℃ (60% SiO)2-20％MgO-20％Al2O3) The mass space velocity of the organic matter is 5h-1And generating a mixture of carbon nanoparticles and graphene. The tail gas (mainly H2, CH4) of the tail gas carbonization subsystem 3 is carbonized, and then the carbonized tail gas outlet 13 is mixed with the gas of the adsorbed gas outlet 5 at the bottom of the gas adsorption/desorption subsystem 1, so that the standard emission is realized.
After the carbon material of the exhaust gas carbonizing subsystem 3 reaches a certain volume, the carbon material is removed from the carbon material outlet 12, and the catalyst is supplemented from the catalyst inlet 11.
Claims (6)
1. The system for treating the gas containing volatile organic compounds and preparing the carbon nano-material is characterized in that: the system comprises a gas adsorption/desorption subsystem (1), a gas-liquid separation subsystem (2) and a tail gas carbonization subsystem (3), wherein the top of the gas adsorption/desorption subsystem (1) is provided with a gas inlet (4) containing volatile organic compounds, the bottom of the gas adsorption/desorption subsystem is provided with an adsorbed gas outlet (5) and a desorbed gas outlet (6), and the desorbed gas outlet (6) of the gas adsorption/desorption subsystem (1) is communicated with a middle inlet (7) of the gas-liquid separation subsystem (2); a condensed organic liquid outlet (8) is arranged at the bottom of the gas-liquid separation subsystem (2), and an organic gas outlet (9) at the top of the gas-liquid separation subsystem (2) is communicated with a bottom inlet (10) of the tail gas carbonization subsystem (3); a carbonized tail gas outlet (13) at the top of the tail gas carbonization subsystem (3) is connected with an adsorbed gas outlet (5) at the bottom of the gas adsorption/desorption subsystem (1); when the gas-liquid separation subsystem (2) is not needed, a desorbed gas outlet (6) at the bottom of the gas adsorption/desorption subsystem (1) is connected with a bottom inlet (10) of the tail gas carbonization subsystem (3); the tail gas carbonization subsystem (3) is also provided with a catalyst inlet (11) and a carbon material outlet (12); the catalyst filled in the tail gas carbonization subsystem (3) cracks organic matters at the temperature of 500-;
the carbon nano-materials generated in the tail gas carbonization subsystem (3) comprise one or more of carbon nano-particles, carbon nano-fibers, carbon nano-tubes and graphene;
the catalyst filled in the tail gas carbonization subsystem (3) is metal and/or oxide, the metal comprises one or more of iron, cobalt, nickel, copper, manganese, zinc, molybdenum and tungsten, and the oxide comprises one or more of alumina, silica, magnesia and zirconia; if the catalyst is metal and oxide, the mass fraction of the metal is 40-75%; the catalyst cracks the organic matter, the mass space velocity of the organic matter is 12.5-20 h-1；
The main body of the gas containing volatile organic compounds is inert gas, the concentration of the organic compounds is 50-200000ppm, and the gas contains the organic compounds with the molecular weight of 26-300.
2. The system for processing volatile organic compound-containing gas and producing carbon nanomaterial according to claim 1, wherein: the gas adsorption/desorption subsystem (1) is filled with an easily-regenerated adsorbent which is made of one or more of carbon, molecular sieve or alumina.
3. The system for processing volatile organic compound-containing gas and producing carbon nanomaterial according to claim 2, wherein: when the adsorbent material is carbon, the carbon is one or more of activated carbon, carbon fiber, carbon nanotube and graphene.
4. The system for processing volatile organic compound-containing gas and producing carbon nanomaterial according to claim 1, wherein: and organic liquid and organic gas in the gas-liquid separation subsystem (2) are respectively discharged from the bottom and the top after being condensed and separated.
5. The method for processing volatile organic compound-containing gas and producing carbon nanomaterial by using the system of any one of claims 1 to 4, comprising the steps of:
a) a gas adsorption/desorption subsystem (1), a gas-liquid separation subsystem (2) and a tail gas carbonization subsystem (3) are connected in sequence;
b) introducing gas containing volatile organic compounds from a gas inlet (4) of the gas adsorption/desorption subsystem (1), adsorbing the organic compounds on an adsorbent after passing through an adsorbent layer in the gas adsorption/desorption subsystem (1), and discharging the adsorbed gas from an adsorbed gas outlet (5) at the bottom of the gas adsorption/desorption subsystem (1);
c) when the adsorption layer of the gas adsorption/desorption subsystem (1) is saturated, stopping introducing the gas containing volatile organic compounds, heating the gas adsorption/desorption subsystem (1) to 90-250 ℃ to desorb the gas on the adsorbent, and discharging the gas from a desorbed gas outlet (6) at the bottom of the gas adsorption/desorption subsystem (1);
d) if the gas discharged from the desorbed gas outlet (6) of the gas adsorption/desorption subsystem (1) does not have the separation and recycling value, the gas is directly introduced into the tail gas carbonization subsystem (3) through a bottom inlet (10) of the tail gas carbonization subsystem (3); generating a carbon nanotube material on the catalyst of the tail gas carbonization subsystem (3) at 500-;
e) if the gas discharged from the desorbed gas outlet (6) of the gas adsorption/desorption subsystem (1) has recovery value, the gas is introduced into the gas-liquid separation subsystem (2) through a middle inlet (7) of the gas-liquid separation subsystem (2); condensing at-20-10 deg.c to separate organic liquid from organic gas; valuable organic liquid is discharged from a condensed organic liquid outlet (8) at the bottom of the gas-liquid separation subsystem (2) to realize direct recycling or continuous separation recycling; organic-containing tail gas discharged from an organic gas outlet (9) at the top of the gas-liquid separation subsystem (2) enters the tail gas carbonization subsystem (3) through a bottom inlet (10), and a carbon nanotube material is generated on a catalyst of the tail gas carbonization subsystem (3);
f) the tail gas of the tail gas carbonization subsystem (3) is discharged through a carbonized tail gas outlet (13), is mixed with the gas adsorbed by an adsorbed gas outlet (5) at the bottom of the gas adsorption/desorption subsystem (1), and is directly discharged or continuously used on the premise of confirming that the total standard is reached;
g) after the carbon material in the tail gas carbonization subsystem (3) reaches a certain volume, the carbon material is removed through a carbon material outlet (12), and the catalyst is supplemented from a catalyst inlet (11).
6. The method of claim 5, wherein: when the gas adsorption/desorption subsystem (1) executes adsorption operation, the temperature is-25-20 ℃, and the pressure is 0.1-2 MPa; the adsorption effect is as follows: the organic content in the inert gas is less than 50ppm, and the aromatic hydrocarbon is less than 4 ppm; when the desorption operation is carried out, the temperature is 50-250 ℃, the pressure is-0.09-1.95 MPa, and the desorption rate is more than 95 percent.
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