CN105771562A - System and method for recycling volatile organic compounds - Google Patents
System and method for recycling volatile organic compounds Download PDFInfo
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- CN105771562A CN105771562A CN201610256210.6A CN201610256210A CN105771562A CN 105771562 A CN105771562 A CN 105771562A CN 201610256210 A CN201610256210 A CN 201610256210A CN 105771562 A CN105771562 A CN 105771562A
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004064 recycling Methods 0.000 title abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 268
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 134
- 238000002955 isolation Methods 0.000 claims abstract description 46
- 238000009833 condensation Methods 0.000 claims abstract description 35
- 230000005494 condensation Effects 0.000 claims abstract description 35
- 238000011084 recovery Methods 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims description 80
- 239000002912 waste gas Substances 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000012466 permeate Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- -1 anhydrides compound Chemical class 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 231100000331 toxic Toxicity 0.000 claims description 2
- 230000002588 toxic effect Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 13
- 239000007789 gas Substances 0.000 abstract description 13
- 239000005416 organic matter Substances 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 abstract 1
- 238000011272 standard treatment Methods 0.000 abstract 1
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 description 44
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- 125000002769 thiazolinyl group Chemical group 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 10
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 6
- 229950000845 politef Drugs 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 150000007530 organic bases Chemical group 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 230000008676 import Effects 0.000 description 3
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 2
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 2
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 description 2
- IEEHKTFVUIVORU-UHFFFAOYSA-N 2-methylpropanedioyl dichloride Chemical compound ClC(=O)C(C)C(Cl)=O IEEHKTFVUIVORU-UHFFFAOYSA-N 0.000 description 2
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 2
- AMPZBWRBSNODSO-UHFFFAOYSA-N C(C(CCCCC(C(CCCC)C(=O)O)C(=O)O)C(=O)O)C(=O)O Chemical compound C(C(CCCCC(C(CCCC)C(=O)O)C(=O)O)C(=O)O)C(=O)O AMPZBWRBSNODSO-UHFFFAOYSA-N 0.000 description 2
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- XJMMNTGIMDZPMU-UHFFFAOYSA-N beta-methylglutaric acid Natural products OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- HGEVGSTXQGZPCL-UHFFFAOYSA-N nonanedioyl dichloride Chemical compound ClC(=O)CCCCCCCC(Cl)=O HGEVGSTXQGZPCL-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
-
- 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
- B01D53/002—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 condensation
-
- 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
- B01D2257/708—Volatile organic compounds V.O.C.'s
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a system and a method for recycling volatile organic compounds, and belongs to the field of organic matter recovery. According to the method, dual aims of recovery of VOCs and up-to-standard treatment are achieved by adopting a nitrogen permselective isolation film and a condensation technology. The method is high in VOCs treatment efficiency, mild in operating condition and low in energy consumption; meanwhile, according to the application of the nitrogen permselective isolation film, VOCs leakage caused by equipment failures can be solved, the safety degree is high, and the method can be widely applied to the fields such as treatment of organized VOCs discharge process, such as discharge gas of petrochemical engineering technology, discharge gas of tank breathing valves and the like.
Description
Technical field
The invention belongs to Organic substance and reclaim field, be specifically related to a kind of volatile organic compounds recovery and process system and method.
Background technology
Volatile organic matter (VOCs) is one of reason of causing haze weather to be formed, also it is the principal element of ozone formation, therefore being the part needing emphasis prevention and control in prevention and control of air pollution, country has also put into effect multiple laws and regulations and has strictly limited VOCs discharge.
Also two big class technology are developed: Prevention Processing technology and end treatment technology are to reduce the discharge of VOCs for this researcher.Prevention Processing technology is to utilize green matter such as water to replace VOCs, fundamentally solves the emission problem of VOCs.But due to the restriction by technical factor, can't replacing VOCs in some technique, therefore its volatilization inevitably occurs.Therefore end treatment technology becomes the current VOCs mainstream technology processed.
Wherein membrane separation technique adapts to strong owing to having material concentration, and treatment effect is stable, and low power consumption and other advantages is considered as most promising isolation technics, and widely studied by people.Prior art process in patent about VOCs embrane method, what use is all preferential VOCs film thoroughly, such as a kind of embrane method condensation combined type oil gas recovery system (application number: CN201310221235.9), the recovery technology (application number: CN02137836.3) of volatile organic matter in mixing gas.And applied research and patent to preferential nitrogen film thoroughly is also less at present, the device for recovering oil and gas (application number: 201410342676.9) based on Glassy polymer separations-absorption technique adopts the integrated absorption techniques of Glassy polymer of preferentially saturating nitrogen to carry out the recovery of oil gas；Two-stage embrane method device for recovering oil and gas and recovery method (application number: 201510278802.3) thereof utilize rubbery state film and Glassy polymer two stages for the treatment of to realize VOCs and purify discharge and reclaim purpose, and this patent remains side concentration waste gas out from Glassy polymer and oil storage tank pressure release can be caused slow also into oil storage tank；It reclaims the mode being to adopt absorption tower and carries out, and absorption efficiency is relatively low, and the waste gas that absorption tower is out there is also problem not up to standard.
Summary of the invention
For the technical problem of above-mentioned existence, the present invention adopts embrane method and gathers condensation technology, utilizes preferential nitrogen film thoroughly to realize separating of VOCs and nitrogen, and utilizes condensation technology to collect VOCs, it is achieved VOCs reclaims the dual purpose with qualified discharge.Whole system is a closed system simultaneously, even if equipment downtime, without there is the VOCs danger revealed, has the advantages that stability is high, safe and reliable, and strong with the integration of other equipment.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preferential nitrogen film thoroughly and condensation combined volatile organic compound recovery and processing system, this system includes blower fan, nitrogen film separation system and condenser, output channel containing VOCs waste gas is connected with nitrogen film separation system by blower fan, the per-meate side of described nitrogen film separation system is connected with air, the side that retains of described nitrogen film separation system is connected with condenser, and the outfan of condenser is connected with the output channel containing VOCs waste gas；Described nitrogen separation system is provided with nitrogen isolation film.
In technical solution of the present invention: described nitrogen isolation film is preferential nitrogen isolation film thoroughly, and described preferential nitrogen isolation film thoroughly is the composite materials containing three dish alkene, composite separating film prepared by fluorine material or perfluorinated material.
In some preferred technical schemes: described nitrogen isolation film is to be prepared via a method which to obtain: the method with the compound shown in formula I and containing the compound of active group for monomer, under the effect of acid binding agent, polyreaction 0.5～60h when-10～150 DEG C, reaction obtains film liquid after terminating；Being coated on solvent resistant counterdie by the film liquid obtained, vacuum crosslinking is dry, obtains preferential nitrogen isolation film thoroughly；
The described compound containing active group at least one in acyl chloride compound, anhydrides compound or Pyromellitic Acid；
The described structural formula of compound shown in formula I is as follows:
Wherein, R1, R2And R3It is separately H, Cl, Br, I, OH, NH2, any one in COOH, n1=1～4, n2=1～4, n3=1～4；R4And R5It is separately H or the alkyl containing 1～3 carbon atom；
And: the compound shown in formula I: the mol ratio of the compound containing active group is 2:1～1:5, it is preferable that the compound shown in formula I: the mol ratio of the compound containing active group is 1:2～1:3；Acid binding agent: the mol ratio of the compound shown in formula I is 6:1～1:1；
Preferred: VOCs rejection is 60～99.99% by nitrogen isolation film, it is preferred that VOCs rejection is 91～99.99% by nitrogen isolation film.
In some preferred technical schemes: described acid binding agent is organic base or inorganic base, described organic base is selected from triethylamine or pyridine, and described inorganic base is selected from sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide or potassium hydroxide；
Preferred acyl chloride compound is selected from any one in benzene diacid chloride, ethanedioly chloride, glutaryl chlorine, succinyl chloride, sebacoyl chloride, azelaoyl chloride, suberoyl chlorine, phenylphosphonyl dichloride, fumaryl chloride, methyl malonyl chloride, ethyl ethanedioly chloride ester and 1,7-pimeloyl chloride；
nullPreferred anhydrides compounds is selected from hexafluorodianhydride (6FDA)、3-methylglutaric acid acid anhydride、Ethylenediaminetetraacetic acid dianhydride、Cyclobutanetetracarboxylic dianhydride、1,2,3,4-ring penta tetracarboxylic dianhydride、3,4,9,10-tetracarboxylic acid dianhydride、1,2,4,5-cyclohexanetetracarboxylic acid dianhydride、3,3,4,4-bibenzene tetracarboxylic dianhydride、3,3,4,4-bibenzene tetracarboxylic dianhydride、3,34,4-benzophenone tetracarboxylic dianhydride、Meso-butane-1,2,3,4-tetracarboxylic dianhydride、Pungent-7-the alkene-2 of dicyclo [2.2.2],3,5,6-tetracarboxylic dianhydride、1,2,3,4-tetramethyl-1,2,3,4-Tetramethylene. tetracarboxylic dianhydride、Three rings [6.4.0.0 (2,7)] dodecane-1,2,7,8-tetracarboxylic acid dianhydride、Bisphenol A dianhydride.
The temperature of polyreaction is-10～150 DEG C.
Solvent used by polyreaction is selected from methyl pyrrolidone, dimethylformamide, dimethyl acetylamide, dichloromethane, ether, carbon tetrachloride or toluene.
In some most preferred technical schemes: the compound shown in formula I is selected from any one in following compound:
2,3-diaminourea triptycene；Or 2,3-dihydroxy triptycene；
Or 2,6-diaminourea triptycene；Or 2,6-dihydroxy triptycene；Or 2,6-dichloro triptycene；Or 2,6-diiodo-triptycene；Or 2,6-dibromo triptycene；
Or 2,7-diaminourea triptycene；Or 2,7-dihydroxy triptycene；Or 2,7-diiodo-triptycene；Or 2,7-dibromo triptycene；Or 2,7-dichloro triptycene；
Or 2,6,14-tri-iodo triptycene；Or 2,6,14-tribromo triptycene；Or 2,6,14-trihydroxy triptycene；Or 2,6,14-triamido triptycene；
Or 2,7,14-tri-iodo triptycene；Or 2,7,14-tribromo triptycene；Or 2,7,14-triamido triptycene；Or 2,7,14-trihydroxy triptycene；
Or 2,3,6,7-tetrahydroxy three dish alkene；Or 2,3,6,7-tetramino three dish alkene；Or 2,3,6,7-tetracarboxylic acid triptycene；
Or 2,3,6,7,14,15-six amino triptycene；Or 2,3,6,7,14,15-hexahydroxy triptycene；Or 2,3,6,7,14,15-hexabromo base triptycene；Or 2,3,6,7,14,15-hexaiodo base triptycene；Or 2,3,6,7,14,15-chlordene base triptycene；
Or 9,10-diethyl-2,3,6,7,12,13-hexahydroxy triptycene.
A kind of method utilizing above-mentioned system to realize volatile organic compounds recovery process, the method is lower than 120g/m by VOCs concentration3Waste gas by blower fan enter nitrogen film separation system, from nitrogen film separation system per-meate side output concentration lower than 120mg/m3Waste gas as toxic emission up to standard, retain the waste gas of side output from nitrogen film separation system and enter condenser and condense, from condenser, concentration out is lower than 120g/m3Waste gas be back to fans entrance.
In the method that above-mentioned volatile organic compounds recovery processes: condensation temperature is-80～20 DEG C, it is preferable that condensation temperature is-40～10 DEG C.
Present invention also offers another kind of preferential nitrogen film thoroughly and condensation combined volatile organic compound recovery and processing system, specific as follows:
A kind of preferential nitrogen film thoroughly and condensation combined volatile organic compound recovery and processing system, this system includes blower fan, nitrogen film separation system and condenser, output channel containing VOCs waste gas is connected with condenser, the outfan of condenser is connected with nitrogen film separation system by blower fan, the per-meate side of described nitrogen film separation system is connected with air, the side that retains of described nitrogen film separation system is connected with the output channel containing VOCs waste gas, is provided with nitrogen isolation film in described nitrogen separation system.
Described nitrogen isolation film is preferential nitrogen isolation film thoroughly, and described preferential nitrogen isolation film thoroughly is the composite materials containing three dish alkene, composite separating film prepared by fluorine material or perfluorinated material.
Described nitrogen isolation film is to be prepared via a method which to obtain: the method with the compound shown in formula I and containing the compound of active group for monomer, under the effect of acid binding agent, polyreaction 0.5～60h when-10～150 DEG C, reaction obtains film liquid after terminating；Being coated on solvent resistant counterdie by the film liquid obtained, vacuum crosslinking is dry, obtains preferential nitrogen isolation film thoroughly；
The described compound containing active group at least one in acyl chloride compound, anhydrides compound or Pyromellitic Acid；
The described structural formula of compound shown in formula I is as follows:
Wherein, R1, R2And R3It is separately H, Cl, Br, I, OH, NH2, any one in COOH, n1=1～4, n2=1～4, n3=1～4；R4And R5It is separately H or the alkyl containing 1～3 carbon atom；
And: the compound shown in formula I: the mol ratio of the compound containing active group is 2:1～1:5, it is preferable that the compound shown in formula I: the mol ratio of the compound containing active group is 1:2～1:3；Acid binding agent: the mol ratio of the compound shown in formula I is 6:1～1:1；
Preferred: VOCs rejection is 60～99.99% by nitrogen isolation film, it is preferred that VOCs rejection is 91～99.99% by nitrogen isolation film.
In some preferred technical schemes: described acid binding agent is organic base or inorganic base, described organic base is selected from triethylamine or pyridine, and described inorganic base is selected from sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide or potassium hydroxide；
Preferred acyl chloride compound is selected from any one in benzene diacid chloride, ethanedioly chloride, glutaryl chlorine, succinyl chloride, sebacoyl chloride, azelaoyl chloride, suberoyl chlorine, phenylphosphonyl dichloride, fumaryl chloride, methyl malonyl chloride, ethyl ethanedioly chloride ester and 1,7-pimeloyl chloride；
nullPreferred anhydrides compounds is selected from hexafluorodianhydride (6FDA)、3-methylglutaric acid acid anhydride、Ethylenediaminetetraacetic acid dianhydride、Cyclobutanetetracarboxylic dianhydride、1,2,3,4-ring penta tetracarboxylic dianhydride、3,4,9,10-tetracarboxylic acid dianhydride、1,2,4,5-cyclohexanetetracarboxylic acid dianhydride、3,3,4,4-bibenzene tetracarboxylic dianhydride、3,3,4,4-bibenzene tetracarboxylic dianhydride、3,34,4-benzophenone tetracarboxylic dianhydride、Meso-butane-1,2,3,4-tetracarboxylic dianhydride、Pungent-7-the alkene-2 of dicyclo [2.2.2],3,5,6-tetracarboxylic dianhydride、1,2,3,4-tetramethyl-1,2,3,4-Tetramethylene. tetracarboxylic dianhydride、Three rings [6.4.0.0 (2,7)] dodecane-1,2,7,8-tetracarboxylic acid dianhydride、Bisphenol A dianhydride.
The temperature of polyreaction is-10～150 DEG C.
Solvent used by polyreaction is selected from methyl pyrrolidone, dimethylformamide, dimethyl acetylamide, dichloromethane, ether, carbon tetrachloride or toluene.
In some most preferred technical schemes: the compound shown in formula I is selected from any one in following compound:
2,3-diaminourea triptycene；Or 2,3-dihydroxy triptycene；
Or 2,6-diaminourea triptycene；Or 2,6-dihydroxy triptycene；Or 2,6-dichloro triptycene；Or 2,6-diiodo-triptycene；Or 2,6-dibromo triptycene；
Or 2,7-diaminourea triptycene；Or 2,7-dihydroxy triptycene；Or 2,7-diiodo-triptycene；Or 2,7-dibromo triptycene；Or 2,7-dichloro triptycene；
Or 2,6,14-tri-iodo triptycene；Or 2,6,14-tribromo triptycene；Or 2,6,14-trihydroxy triptycene；Or 2,6,14-triamido triptycene；
Or 2,7,14-tri-iodo triptycene；Or 2,7,14-tribromo triptycene；Or 2,7,14-triamido triptycene；Or 2,7,14-trihydroxy triptycene；
Or 2,3,6,7-tetrahydroxy three dish alkene；Or 2,3,6,7-tetramino three dish alkene；Or 2,3,6,7-tetracarboxylic acid triptycene；
Or 2,3,6,7,14,15-six amino triptycene；Or 2,3,6,7,14,15-hexahydroxy triptycene；Or 2,3,6,7,14,15-hexabromo base triptycene；Or 2,3,6,7,14,15-hexaiodo base triptycene；Or 2,3,6,7,14,15-chlordene base triptycene；
Or 9,10-diethyl-2,3,6,7,12,13-hexahydroxy triptycene.
A kind of aforesaid system realizes the method that volatile organic compounds recovery processes, and the method is higher than 120g/m by VOCs concentration3Waste gas enter in condenser and condense, from condenser, the outfan concentration out VOCs waste gas lower than 120g/m3 is delivered to nitrogen separation system by blower fan, the per-meate side of described nitrogen film separation system is connected with air, and the side that retains of described nitrogen film separation system is connected with condenser.
Described condensation temperature is-80～20 DEG C, it is preferable that condensation temperature is-40～10 DEG C.
Nitrogen isolation film of the present invention is preferential nitrogen isolation film thoroughly, and namely nitrogen preferentially passes through, and VOCs is trapped.
The rejection computing formula of described nitrogen isolation film is as follows:
Wherein: Pp is the VOCs concentration (ppm) through side, and Pb is feed side VOCs concentration (ppm), R is rejection.
Beneficial effects of the present invention:
1, the difference according to VOCs concentration, VOCs waste gas enters different operating units, it is possible to achieve optimum treatment effeciency, completes the target of qualified discharge and recovery.
2, this technique is a closed system, even if equipment downtime is without the VOCs danger revealed occurs, safe coefficient is high.
3, owing to dynamic equipment is less, having stable advantage, energy consumption is relatively low simultaneously.
4, this system can be not only used for the industry VOCs such as petrochemical industry, medicine and coating and printing and discharges the recycling of waste gas in a organized way, it is also possible to for the recycling of the VOCs waste gas that solvent tank Big and Small Breath causes.
5, this inventive structure is simple, compact, install and safeguard that easy and other equipment integration is strong.
Accompanying drawing explanation
Fig. 1 concentration is lower than 120g/m3The schematic diagram of VOCs recovery and processing system.
Fig. 2 concentration is higher than 120g/m3The schematic diagram of VOCs recovery and processing system.
Wherein: 1 is blower fan；2 is nitrogen separation system；3 is condenser.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but protection scope of the present invention is not limited to this:
Such as Fig. 1, a kind of preferential nitrogen film thoroughly and condensation combined volatile organic compound recovery and processing system, this system includes blower fan (1), nitrogen film separation system (2) and condenser (3), output channel containing VOCs waste gas is connected with nitrogen film separation system (2) by blower fan (1), the per-meate side of described nitrogen film separation system (2) is connected with air, the side that retains of described nitrogen film separation system (2) is connected with condenser (3), and the outfan of condenser (3) is connected with the output channel containing VOCs waste gas；Described nitrogen separation system (2) is provided with nitrogen isolation film.
One utilizes said system to realize volatile organic compounds recovery processing method, such as embodiment 1～3.
Embodiment 1
The present embodiment nitrogen isolation film adopts 2, 6, 14-triamido triptycene, sebacoyl chloride is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, it specifically comprises the following steps that the 2 of 1mol, 6, 14-triamido triptycene, the pyridine of 3mol, the sebacoyl chloride of 2mol joins stirring and dissolving in methylpyrrolidone solution, it is under 2 DEG C of (nitrogen protection) conditions in temperature, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on politef counterdie and prepares into composite membrane, the composite membrane of coating is put into 70 DEG C of drying in vacuum drying oven, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size retaining type polymer separation film through the BET three dish thiazolinyl VOCs that prepare of test is 2.8nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/hexamethylene for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.30L/m2During min, after membrance separation, per-meate side concentration is reduced to 1750ppm, and rejection is more than 91.25%.
Concentration is 2g/m3VOCs waste gas by blower fan send into nitrogen film separation system, nitrogen film separation system per-meate side concentration 6mg/m3Waste gas qualified discharge；Nitrogen film separation system retains side concentration 10g/m3Waste gas enter condensation in condenser and collect, condensation temperature is-50 DEG C；Uncooled concentration is 2g/m3VOCs waste gas return to fan inlet.
Embodiment 2
The present embodiment nitrogen isolation film adopts 2, 7, 14-triamido triptycene, sebacoyl chloride is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, it specifically comprises the following steps that the 2 of 1mol, 7, 14-triamido triptycene, the pyridine of 5mol, the sebacoyl chloride of 3mol joins stirring and dissolving in methylpyrrolidone solution, it is under 2 DEG C of (nitrogen protection) conditions in temperature, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on politef counterdie and prepares into composite membrane, the composite membrane of coating is put into 70 DEG C of drying in vacuum drying oven, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size retaining type polymer separation film through the BET three dish thiazolinyl VOCs that prepare of test is 2.2nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/hexamethylene for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.27L/m2During min, after membrance separation, per-meate side concentration is reduced to 1240ppm, and rejection is more than 93.8%.
Concentration is 10g/m3VOCs waste gas by blower fan send into nitrogen film separation system, nitrogen film separation system per-meate side concentration 100mg/m3Waste gas qualified discharge；Nitrogen film separation system retains side concentration 30g/m3Waste gas enter condensation in condenser and collect, condensation temperature is-30 DEG C；Uncooled concentration is 10g/m3VOCs waste gas return to fan inlet.
Embodiment 3
The present embodiment nitrogen isolation film adopts 2, 3, 6, 7-tetrahydroxy three dish alkene, 1, 7-pimeloyl chloride is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, it specifically comprises the following steps that the 2 of 1.5mol, 3, 6, 7-tetrahydroxy three dish alkene, the pyridine of 3mol, the 1 of 4.5mol, 7-pimeloyl chloride joins stirring and dissolving in methylpyrrolidone solution, it is under 2 DEG C of (nitrogen protection) conditions in temperature, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on politef counterdie and prepares into composite membrane, the composite membrane of coating is put into 70 DEG C of drying in vacuum drying oven, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size retaining type polymer separation film through the BET three dish thiazolinyl VOCs that prepare of test is 2.0nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/hexamethylene for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.26L/m2During min, after membrance separation, per-meate side concentration is reduced to 1530ppm, and rejection is more than 92.35%.
Concentration is 100g/m3VOCs waste gas by blower fan send into nitrogen film separation system, nitrogen film separation system per-meate side concentration 75mg/m3Waste gas qualified discharge；Nitrogen film separation system retains side concentration 200g/m3Waste gas enter condensation in condenser and collect, condensation temperature is 5 DEG C；Uncooled concentration is 100g/m3VOCs waste gas return to fan inlet.
Such as Fig. 2, a kind of preferential nitrogen film thoroughly and condensation combined volatile organic compound recovery and processing system, this system includes blower fan (1), nitrogen film separation system (2) and condenser (3), output channel containing VOCs waste gas is connected with condenser (3), the outfan of condenser (3) is connected with nitrogen film separation system (2) by blower fan (1), the per-meate side of described nitrogen film separation system (2) is connected with air, the side that retains of described nitrogen film separation system (2) is connected with the output channel containing VOCs waste gas, described nitrogen separation system is provided with nitrogen isolation film.
One utilizes said system to realize volatile organic compounds recovery processing method, such as embodiment 4～6.
Embodiment 4
The present embodiment nitrogen isolation film adopts 2, 3, 6, 7, 14, 15-six amino triptycene, suberoyl chlorine is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, it specifically comprises the following steps that the 2 of 1mol, 3, 6, 7, 14, 15-six amino triptycene, the pyridine of 3.5mol, the suberoyl chlorine of 3mol joins stirring and dissolving in methylpyrrolidone solution, it is under 2 DEG C of (nitrogen protection) conditions in temperature, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on politef counterdie and prepares into composite membrane, the composite membrane of coating is put into 70 DEG C of drying in vacuum drying oven, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size retaining type polymer separation film through the BET three dish thiazolinyl VOCs that prepare of test is 1.6nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/hexamethylene for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.15L/m2During min, after membrance separation, per-meate side concentration is reduced to 710ppm, and rejection is more than 96.45%.
Concentration is 150g/m3VOCs waste gas enter condensation in condenser and collect, condensation temperature is 5 DEG C；Uncooled concentration is 100g/m3VOCs waste gas with blower fan send into nitrogen film separation system import, nitrogen film separation system per-meate side concentration 75mg/m3Waste gas qualified discharge；Nitrogen film separation system retains side concentration 150g/m3Return to condenser inlet.
Embodiment 5
The present embodiment nitrogen isolation film adopts 9, 10-diethyl-2, 3, 6, 7, 12, 13-hexahydroxy triptycene, suberoyl chlorine is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, it specifically comprises the following steps that the 9 of 1mol, 10-diethyl-2, 3, 6, 7, 12, 13-hexahydroxy triptycene, the pyridine of 3.5mol, the suberoyl chlorine of 3mol joins stirring and dissolving in methylpyrrolidone solution, it is under 2 DEG C of (nitrogen protection) conditions in temperature, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on politef counterdie and prepares into composite membrane, the composite membrane of coating is put into 70 DEG C of drying in vacuum drying oven, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.Retaining type polymer separation film average pore size through the BET three dish thiazolinyl VOCs that prepare of test is 1.3nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/hexamethylene for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.10L/m2During min, after membrance separation, per-meate side concentration is reduced to 630ppm, and rejection is more than 96.85%.
Concentration is 250g/m3VOCs waste gas enter condensation in condenser and collect, condensation temperature is-7 DEG C；Uncooled concentration is 50g/m3VOCs waste gas with blower fan send into nitrogen film separation system import, nitrogen film separation system per-meate side concentration 75mg/m3Waste gas qualified discharge；Nitrogen film separation system retains side concentration 250g/m3Return to condenser inlet.
Embodiment 6
The present embodiment nitrogen isolation film adopts 2, 6, 14-triamido triptycene, sebacoyl chloride is as the principal monomer of synthesis, pyridine is as acid binding agent, methyl pyrrolidone carries out synthetic reaction as solvent, it specifically comprises the following steps that the 2 of 1mol, 6, 14-triamido triptycene, the pyridine of 3mol, the sebacoyl chloride of 2mol joins stirring and dissolving in methylpyrrolidone solution, it is under 2 DEG C of (nitrogen protection) conditions in temperature, reaction 3.5h, the homopolycondensation mixed liquor of reaction is coated on politef counterdie and prepares into composite membrane, the composite membrane of coating is put into 70 DEG C of drying in vacuum drying oven, namely obtain three dish thiazolinyl VOCs and retain type polymer separation film.The average pore size retaining type polymer separation film through the BET three dish thiazolinyl VOCs that prepare of test is 2.8nm.
Test condition is: under 25 DEG C of conditions, and with nitrogen/hexamethylene for separate raw materials gas, concentration is 20000ppm, and under pressure 10kpa, seepage velocity is at 0.30L/m2During min, after membrance separation, per-meate side concentration is reduced to 1750ppm, and rejection is more than 91.25%.
Concentration is 400g/m3VOCs waste gas enter condensation in condenser and collect, condensation temperature is-7 DEG C；Uncooled concentration is 50g/m3VOCs waste gas with blower fan send into nitrogen film separation system import, nitrogen film separation system per-meate side concentration 115mg/m3Waste gas qualified discharge；Nitrogen film separation system retains side concentration 350g/m3Return to condenser inlet.
Above example is only the technological thought that the present invention is described, it is impossible to limits protection scope of the present invention, every technological thought proposed according to the present invention, any change done on technical scheme basis with this, each falls within scope；The technology that the present invention is not directed to all can be passed through prior art and be realized.
Claims (10)
1. a preferential nitrogen film thoroughly and condensation combined volatile organic compound recovery and processing system, it is characterized in that: this system includes blower fan, nitrogen film separation system and condenser, output channel containing VOCs waste gas is connected with nitrogen film separation system by blower fan, the per-meate side of described nitrogen film separation system is connected with air, the side that retains of described nitrogen film separation system is connected with condenser, and the outfan of condenser is connected with the output channel containing VOCs waste gas；Described nitrogen separation system is provided with nitrogen isolation film.
2. preferential nitrogen film thoroughly according to claim 1 and condensation combined volatile organic compound recovery and processing system, it is characterized in that: described nitrogen isolation film is preferential nitrogen isolation film thoroughly, and described preferential nitrogen isolation film thoroughly is the composite materials containing three dish alkene, composite separating film prepared by fluorine material or perfluorinated material.
3. preferential nitrogen film thoroughly according to claim 2 and condensation combined volatile organic compound recovery and processing system, it is characterized in that: described nitrogen isolation film is to be prepared via a method which to obtain: the method with the compound shown in formula I and containing the compound of active group for monomer, under the effect of acid binding agent, polyreaction 0.5～60h when-10～150 DEG C, reaction obtains film liquid after terminating；Being coated on solvent resistant counterdie by the film liquid obtained, vacuum crosslinking is dry, obtains preferential nitrogen isolation film thoroughly；
The described compound containing active group at least one in acyl chloride compound, anhydrides compound or Pyromellitic Acid；
The described structural formula of compound shown in formula I is as follows:
Wherein, R1, R2And R3It is separately H, Cl, Br, I, OH, NH2, any one in COOH, n1=1～4, n2=1～4, n3=1～4；R4And R5It is separately H or the alkyl containing 1～3 carbon atom；
And: the compound shown in formula I: the mol ratio of the compound containing active group is 2:1～1:5, it is preferable that the compound shown in formula I: the mol ratio of the compound containing active group is 1:2～1:3；Acid binding agent: the mol ratio of the compound shown in formula I is 6:1～1:1；
Preferred: VOCs rejection is 60～99.99% by nitrogen isolation film, it is preferred that VOCs rejection is 91～99.99% by nitrogen isolation film.
4. one kind utilizes the system described in claim 1 to realize the method that volatile organic compounds recovery processes, it is characterised in that: the method is lower than 120g/m by VOCs concentration3Waste gas by blower fan enter nitrogen film separation system, from nitrogen film separation system per-meate side output concentration lower than 120mg/m3Waste gas as toxic emission up to standard, retain the waste gas of side output from nitrogen film separation system and enter condenser and condense, from condenser, concentration out is lower than 120g/m3Waste gas be back to fans entrance.
5. the method that volatile organic compounds recovery according to claim 4 processes, it is characterised in that: condensation temperature is-80～20 DEG C, it is preferable that condensation temperature is-40～10 DEG C.
6. a preferential nitrogen film thoroughly and condensation combined volatile organic compound recovery and processing system, it is characterized in that: this system includes blower fan, nitrogen film separation system and condenser, output channel containing VOCs waste gas is connected with condenser, the outfan of condenser is connected with nitrogen film separation system by blower fan, the per-meate side of described nitrogen film separation system is connected with air, the side that retains of described nitrogen film separation system is connected with the output channel containing VOCs waste gas, is provided with nitrogen isolation film in described nitrogen separation system.
7. preferential nitrogen film thoroughly according to claim 6 and condensation combined volatile organic compound recovery and processing system, it is characterized in that: described nitrogen isolation film is preferential nitrogen isolation film thoroughly, and described preferential nitrogen isolation film thoroughly is the composite materials containing three dish alkene, composite separating film prepared by fluorine material or perfluorinated material.
8. preferential nitrogen film thoroughly according to claim 7 and condensation combined volatile organic compound recovery and processing system, it is characterized in that: described nitrogen isolation film is to be prepared via a method which to obtain: the method with the compound shown in formula I and containing the compound of active group for monomer, under the effect of acid binding agent, polyreaction 0.5～60h when-10～150 DEG C, reaction obtains film liquid after terminating；Being coated on solvent resistant counterdie by the film liquid obtained, vacuum crosslinking is dry, obtains preferential nitrogen isolation film thoroughly；
The described compound containing active group at least one in acyl chloride compound, anhydrides compound or Pyromellitic Acid；
The described structural formula of compound shown in formula I is as follows:
Wherein, R1, R2And R3It is separately H, Cl, Br, I, OH, NH2, any one in COOH, n1=1～4, n2=1～4, n3=1～4；R4And R5It is separately H or the alkyl containing 1～3 carbon atom；
And: the compound shown in formula I: the mol ratio of the compound containing active group is 2:1～1:5, it is preferable that the compound shown in formula I: the mol ratio of the compound containing active group is 1:2～1:3；Acid binding agent: the mol ratio of the compound shown in formula I is 6:1～1:1；
Preferred: VOCs rejection is 60～99.99% by nitrogen isolation film, it is preferred that VOCs rejection is 91～99.99% by nitrogen isolation film.
9. one kind utilizes the system described in claim 1 to realize the method that volatile organic compounds recovery processes, it is characterised in that: the method is higher than 120g/m by VOCs concentration3Waste gas enter in condenser and condense, from condenser, the outfan concentration out VOCs waste gas lower than 120g/m3 is delivered to nitrogen separation system by blower fan, the per-meate side of described nitrogen film separation system is connected with air, and the side that retains of described nitrogen film separation system is connected with condenser.
10. the method that volatile organic compounds recovery according to claim 9 processes, it is characterised in that: condensation temperature is-80～20 DEG C, it is preferable that condensation temperature is-40～10 DEG C.
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