CN114471084A - Aromatic hydrocarbon-containing organic waste gas absorbent and preparation method and application thereof - Google Patents
Aromatic hydrocarbon-containing organic waste gas absorbent and preparation method and application thereof Download PDFInfo
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- CN114471084A CN114471084A CN202011167982.5A CN202011167982A CN114471084A CN 114471084 A CN114471084 A CN 114471084A CN 202011167982 A CN202011167982 A CN 202011167982A CN 114471084 A CN114471084 A CN 114471084A
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- 239000002250 absorbent Substances 0.000 title claims abstract description 102
- 230000002745 absorbent Effects 0.000 title claims abstract description 102
- 239000007789 gas Substances 0.000 title claims abstract description 31
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 21
- 239000010815 organic waste Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 89
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002608 ionic liquid Substances 0.000 claims abstract description 35
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 22
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 22
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 22
- 229960003178 choline chloride Drugs 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 142
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 44
- 239000012855 volatile organic compound Substances 0.000 claims description 26
- 239000002912 waste gas Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 230000008929 regeneration Effects 0.000 claims description 12
- 238000011069 regeneration method Methods 0.000 claims description 12
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003795 desorption Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- -1 tetrafluoroborate Chemical compound 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride 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
- B01D53/14—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 absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
- B01D53/14—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 absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
- B01D53/14—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 absorption
- B01D53/1487—Removing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to an aromatic hydrocarbon-containing organic waste gas absorbent and a preparation method thereof, wherein the absorbent mainly comprises ionic liquid, choline chloride and citric acid, and the preparation steps are as follows: mixing choline chloride and citric acid in proportion, heating and stirring uniformly; then adding ionic liquid for reaction, and cooling to obtain the absorbent. The absorbent provided by the invention can quickly and effectively absorb aromatic hydrocarbon organic matters in organic waste gas, and has high selectivity and good absorption effect.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to an aromatic hydrocarbon-containing organic waste gas absorbent, and a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) can be classified into aromatic hydrocarbons (benzene, toluene, xylene), ketones, aldehydes, amines, halides, unsaturated hydrocarbons, etc. according to their chemical structure. According to the regulation of the Integrated emission Standard of atmospheric pollutants (GB16297-1996), the concentration of special organic pollutants at the discharge port of VOCs has clear requirements, and the emission limit of 33 kinds of atmospheric pollutants is regulated, wherein benzene is less than or equal to 17mg/m3Toluene is less than or equal to 60mg/m3Xylene is less than or equal to 90mg/m3Nitrobenzene is less than or equal to 20 mg/m3。
In the prior art, techniques for controlling the discharge of VOCs may be classified into destructive methods (chemical oxidation, biological oxidation), absorption/adsorption methods, condensation and membrane separation methods, and the like. Compared with the destructive method, the absorption method has attracted much attention because of its advantages of simplicity, safety, low cost, recyclability, and the like. In the technology of controlling VOCs by an absorption method, an absorbent is of great importance, and high absorption rate and good recyclability are the first choice for removing VOCs. Commonly used absorbents for VOCs include mainly vegetable oil-water emulsions, silicone oil-water emulsions, di (2-ethylhexyl) adipate, diisobutyl phthalate, and the like. The recycling and reusing of the rich absorbent are beneficial to improving the economical efficiency of VOCs treatment, but most of the absorbent cannot be recycled and reused, and the utilization rate is low. Therefore, the development of the absorbent which has high absorptivity, low volatility, high thermal stability and good recoverability has important significance for effectively removing the VOCs.
The ionic liquid is an environment-friendly solvent with stable property, and has wide application prospect in the field of gas absorption. However, due to differences in the properties of different ionic liquids themselves, selectivity and absorption capacity for different absorbing species is limited.
CN105582786A discloses a method for removing volatile organic compounds from gas by using ionic liquid. The absorption tower is operated at 0-100 deg.C and 0.1-10MPa, and the theoretical plate number is 5-20. The contents of VOCs methanol, ethanol and toluene in the gas product at the top of the tower are all less than 2000 ppm; the gas-liquid separator is operated at normal temperature and normal pressure, and the high-temperature flash tank is operated at 50-200 ℃ and 0.01-0.9 atm. The cation in the ionic liquid used in the invention is selected from imidazoles, pyridines and quaternary ammonium salts, and the anion is selected from bis (trifluoromethanesulfonimide), tetrafluoroborate, hexafluorophosphate, acetate and diethyl sulfate, but the absorption pressure is set to be higher, the absorption energy consumption is improved, and the selectivity to aromatic hydrocarbon pollutants in VOCs is not strong.
CN102924333A discloses a preparation method of an ionic liquid for absorbing low-boiling halohydrocarbon gas and an application of the ionic liquid in absorbing low-boiling halohydrocarbon gas, wherein one of aluminum chloride, zinc chloride or lithium chloride is uniformly mixed with one or two of citric acid, urea, acetamide, propionamide, butyramide or caprolactam according to a molar ratio of 1:1-10 or 1:0.5-3:1-7, the mixture is reacted for 1-10 hours at 70-150 ℃, and then the obtained solution is dried for 1-5 hours in vacuum at 40-80 ℃ to obtain the ionic liquid. The ionic liquid is mainly used for absorbing low-boiling-point halogenated hydrocarbon gas, and has low selectivity on aromatic hydrocarbon pollutants in VOCs. In addition, the absorbent adopts an amide substance, which causes secondary pollution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an aromatic hydrocarbon-containing organic waste gas absorbent, and a preparation method and application thereof. The absorbent provided by the invention can quickly and effectively absorb aromatic hydrocarbon organic matters in VOCs, and has high selectivity and good absorption effect.
The invention provides an absorbent for organic waste gas containing aromatic hydrocarbon in a first aspect, which mainly comprises ionic liquid, choline chloride and citric acid, wherein the ionic liquid is [ Bmim ]][PF6]、[Bmim][Cl]、[Bmim][BF4]、[Bmim] [SCN]、[Bmim] [NTf2]Etc., preferably [ Bmim ]][PF6]。
In the absorbent, the molar ratio of the ionic liquid to the choline chloride to the citric acid is 1: 1-3: 1-6, preferably 1: 2-3: 4-6.
The second aspect of the invention provides a preparation method of an aromatic hydrocarbon-containing organic waste gas absorbent, which mainly comprises the following steps:
(1) mixing choline chloride and citric acid in proportion, heating and stirring uniformly;
(2) adding ionic liquid to react, and cooling to obtain the absorbent.
In the preparation method, the mol ratio of the choline chloride to the citric acid in the step (1) is 1-3: 1-6, and preferably 2-3: 4-6.
In the preparation method, the heating temperature in the step (1) is 60-100 ℃, the stirring speed is 100-200 r/min, and the reaction time is 1-2 h.
In the preparation method of the invention, step (2) isThe ionic liquid is [ Bmim ]][PF6]、[Bmim][Cl]、[Bmim][BF4]、[Bmim] [SCN]、[Bmim] [NTf2]Etc., preferably [ Bmim ]][PF6]。
In the preparation method, the molar ratio of the ionic liquid and the choline chloride in the step (2) is 1: 1-3, preferably 1: 2-3.
In the preparation method, the reaction temperature in the step (2) is 50-80 ℃, and the reaction time is 0.5-1 h.
In a third aspect of the invention, the application of the absorbent for the aromatic-containing organic waste gas is provided, and the waste gas containing the aromatic-containing VOCs is contacted with the absorbent.
In the application of the invention, the absorbent mainly comprises ionic liquid, choline chloride and citric acid, wherein the ionic liquid is [ Bmim ]][PF6]、[Bmim][Cl]、[Bmim][BF4]、[Bmim] [SCN]、[Bmim] [NTf2]Etc., preferably [ Bmim ]][PF6]. The molar ratio of the ionic liquid to the choline chloride to the citric acid is 1: 1-3: 1-6, and preferably 1: 2-3: 4-6.
In the application of the invention, in the waste gas containing aromatic hydrocarbon VOCs, the aromatic hydrocarbon is mainly at least one of benzene, toluene, xylene, styrene, phenol, chlorobenzene, nitrochlorobenzene and the like.
In the application of the invention, the contact condition of the waste gas containing the aromatic hydrocarbon VOCs and the absorbent is as follows: the pressure is 0.1-0.3 MPa, the temperature is 10-30 ℃, and the liquid-gas ratio is 4-6L/m3。
In the application of the invention, the absorbent is contacted with the waste gas, regeneration is carried out after absorption balance, and a heating or/and pressure reduction regeneration mode is adopted, wherein the regeneration temperature is 100-150 ℃, and the regeneration pressure is 10 kPa-0.1 MPa. Further, it is preferable that N is2The regeneration is carried out in the atmosphere, and the regenerated absorbent can be recycled.
Compared with the prior art, the invention has the following beneficial effects:
(1) the absorbent provided by the invention mainly comprises ionic liquid, choline chloride and citric acid, and three components in the absorbent act synergistically, so that the absorbent has good selectivity and absorption performance on aromatic hydrocarbons in VOCs at normal temperature, and has the advantages of quick absorption, high efficiency, strong selectivity and the like.
(2) The absorbent prepared by the invention can realize high-efficiency regeneration by heating or/and reducing pressure, and the regenerated absorbent can be recycled and has good absorption stability.
(3) The absorbent prepared by the invention has the advantages of rich raw material sources, environmental protection, low cost, simple synthesis and large-scale production, and is an efficient, green and environment-friendly absorbent.
Detailed Description
The absorbent and its effects of the present invention will be further described with reference to the following specific examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
Example 1
Choline chloride and citric acid are taken according to the molar ratio of 1:3 and added into a reactor, and the mixture is stirred and reacted for 2 hours at 100 ℃ and 150r/min to obtain uniform liquid. According to ionic liquids [ Bmim ]][PF6]Adding the mixture into the liquid at a molar ratio of 1:2, stirring and reacting at 70 ℃ for 1h, and cooling to room temperature to obtain the absorbent.
Absorbing the waste gas containing the toluene VOCs and the absorbent in an absorption tower, controlling the absorption temperature to be 25 ℃, the absorption pressure to be 0.1MPa and the liquid-gas ratio to be 5L/m3. After the absorption reached equilibrium, the weight before and after absorption was measured by gravimetric method and the amount of toluene absorbed per gram of absorbent was calculated to be 362 mg.
And (3) carrying out reduced pressure regeneration on the rich absorbent with the absorption balance, wherein the pressure is 0.01MPa, and the desorption time is 1 h. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing waste gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 351 mg.
Example 2
Choline chloride and citric acid are taken according to the molar ratio of 1:1 and added into a reactor, and the mixture is stirred and reacted for 1h at 80 ℃ and 150r/min to obtain uniform liquid. According to ionic liquids [ Bmim ]][PF6]Adding the mixture into the uniform liquid at a molar ratio of 1:1, stirring and reacting at 50 ℃ for 1h, and cooling to room temperature to obtain the absorbent.
Absorbing the waste gas containing the toluene VOCs and the absorbent in an absorption tower, controlling the absorption temperature to be 25 ℃, the absorption pressure to be 0.1MPa and the liquid-gas ratio to be 5L/m3. After the absorption reached equilibrium, the weight before and after absorption was determined by gravimetric method, calculating that the absorption of toluene per gram of absorbent was 283 mg.
And (3) heating the rich absorbent with balanced absorption, decompressing and regenerating at 100 ℃ under 0.1MPa for 1 h. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing off-gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 276 mg.
Example 3
According to the molar ratio of 1:2, choline chloride and citric acid are taken and added into a reactor, and stirred and reacted for 1 hour at the temperature of 60 ℃ and at the speed of 200r/min to obtain uniform liquid. According to ionic liquids [ Bmim ]][PF6]Adding the mixture into the uniform liquid at a molar ratio of 1:2, stirring at 90 ℃ for reaction for 0.5h, and cooling to room temperature to obtain the absorbent.
Absorbing the waste gas containing the toluene VOCs and the absorbent in an absorption tower, controlling the absorption temperature to be 25 ℃, the absorption pressure to be 0.1MPa and the liquid-gas ratio to be 5L/m3. After the absorption reached equilibrium, the weight before and after absorption was measured gravimetrically and the amount of toluene absorbed per gram of absorbent was calculated to be 304 mg.
And (3) heating the rich absorbent with balanced absorption, decompressing and regenerating at the heating temperature of 120 ℃, under the pressure of 0.01MPa and for 0.5 h. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing waste gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 293 mg.
Example 4
Choline chloride and citric acid are taken according to the molar ratio of 1:4 and added into a reactor, and stirred and reacted for 2 hours at 100 ℃ and 200r/min to obtain uniform liquid. According to ionic liquids [ Bmim ]][PF6]Adding the mixture into the uniform liquid at a molar ratio of 1:3, stirring and reacting at 70 ℃ for 1h, and cooling to room temperature to obtain the absorbent.
Absorbing the waste gas containing toluene VOCs and the absorbent in an absorption tower, controlling the absorption temperature at 30 ℃, the absorption pressure at 0.1MPa and the liquid-gas ratio at 4L/m3. After the absorption reached equilibrium, the weight before and after absorption was measured gravimetrically and the amount of toluene absorbed per gram of absorbent was calculated to be 295 mg.
Heating and decompressing the rich absorbent with balanced absorption, wherein the pressure is 0.01MPa, the temperature is 150 ℃, and the desorption time is 20 min. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing waste gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 287 mg.
Example 5
The same as example 1, except that: with [ Bmim ]][Cl]Substitution of ionic liquid for [ Bmim ]][PF6]And preparing the absorbent. After absorption reached equilibrium, the absorption of toluene per gram of absorbent was measured and calculated to be 336 mg. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing off-gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 324 mg.
Example 6
The difference from example 1 is that: with [ Bmim ]][BF4]Substitution of ionic liquid for [ Bmim ]][PF6]And preparing the absorbent. After the absorption reached equilibrium, the absorption of toluene per gram of absorbent was detected and calculated to be 341 mg. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing off-gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 329 mg.
Example 7
The difference from example 1 is that: with [ Bmim ]][SCN]Substitution of ionic liquid for [ Bmim ]][PF6]And preparing the absorbent. After the absorption reaches equilibrium, the absorption is examinedThe toluene absorbed per gram of absorbent was found to be 356 mg. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing waste gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 343 mg.
Example 8
The difference from example 1 is that: with [ Bmim ]][NTf2]Substitution of ionic liquid for [ Bmim ]][PF6]And preparing the absorbent. After the absorption reached equilibrium, the amount of toluene absorbed per gram of absorbent was determined and calculated to be 328 mg. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing waste gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 316 mg.
Example 9
The difference from example 1 is that: mixing [ Bmim ] in the same ratio][PF6]The choline chloride and the citric acid are directly mixed according to the proportion of 1:2:6, and are stirred to be uniform at the temperature of 80 ℃ to obtain the absorbent. After the absorption reached equilibrium, the absorption of toluene per gram of absorbent was measured and calculated to be 253 mg. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the absorption of the same toluene-containing gas under the same operating conditions, and the amount of toluene absorbed per gram of absorbent was 185 mg.
It can be seen that [ Bmim ]][PF6]The initial absorption effect of the direct mixing of the choline chloride and the citric acid according to the proportion is improved, but the absorption stability is to be improved after the multiple regeneration.
Comparative example 1
The difference from example 1 is that: the absorbent is prepared without using choline chloride. After the absorption reached equilibrium, the absorption of toluene per gram of absorbent was detected and calculated to be 133 mg. After 10 cycles of absorption and desorption, 118mg of toluene were absorbed per gram of absorbent.
Comparative example 2
The difference from example 1 is that: citric acid is not used in the preparation of the absorbent. After the absorption reached equilibrium, the absorption of toluene per gram of absorbent was measured and calculated to be 109 mg. After 10 cycles of absorption and desorption, 98mg of toluene were absorbed per gram of absorbent.
Comparative example 3
The same as example 1, except that: no ionic liquid is used in the preparation of the absorbent. After the absorption reached equilibrium, 154mg of toluene was detected and calculated per gram of absorbent. After 10 cycles of absorption and desorption, the amount of toluene absorbed per gram of absorbent was 136 mg.
Comparative example 4
The difference from example 1 is that: the absorbent prepared in example 1 of CN105582786A was used. After absorption reached equilibrium, toluene absorbed per gram of absorbent was detected and calculated to be less than 205 mg.
Comparative example 5
The difference from example 1 is that: the absorbent prepared in example 1 of CN102924333A was used. After absorption reaches equilibrium, the absorption of toluene per gram of absorbent is detected and calculated to be less than 214 mg.
Test example 1
The absorbents prepared in examples 1-8 were used for the absorption of different aromatic-containing materials under the following absorption conditions: the pressure is 0.1MPa, the temperature is 25 ℃, and the liquid-gas ratio is 5L/m3. The absorption effect is shown in table 1.
TABLE 1 absorption Effect of examples 1 to 8 (unit: mg/g absorbent)
Test example 2
The waste gas of VOCs discharged from a certain chemical plant mainly contains VOCs such as toluene, propane and styrene, and the concentration of non-methane total hydrocarbon is 5326mg/m3The sum of the toluene and styrene concentrations is 2147mg/m3. The absorbent of examples 1 to 8 was used for absorption at an absorption pressure of 0.1MPa, a temperature of 25 ℃ and a liquid-gas ratio of 5L/m3。
After absorption, the concentration of non-methane total hydrocarbon in the outlet waste gas is 4010-3The concentration of toluene and styrene VOCs is 422mg/m3In the meantime. Toluene and styrene are absorbed by more than 80%, and the absorption rate of other organic matters is lower than 15%. Therefore, the absorbent provided by the invention has good selectivity.
Claims (13)
1. The absorbent for the organic waste gas containing aromatic hydrocarbon is characterized by mainly comprising ionic liquid, choline chloride and citric acid, wherein the ionic liquid is [ Bmim ]][PF6]、[Bmim][Cl]、[Bmim][BF4]、[Bmim] [SCN]、[Bmim] [NTf2]Etc., preferably [ Bmim ]][PF6]。
2. The absorbent of claim 1, wherein: the molar ratio of the ionic liquid to the choline chloride to the citric acid is 1: 1-3: 1-6, and preferably 1: 2-3: 4-6.
3. The process for producing an absorbent for an aromatic-hydrocarbon-containing organic waste gas as described in any one of claims 1 to 2, which comprises the steps of: (1) mixing choline chloride and citric acid in proportion, heating and stirring uniformly; (2) adding ionic liquid for reaction, and cooling to obtain the absorbent.
4. The method of claim 3, wherein: the mol ratio of the choline chloride to the citric acid in the step (1) is 1-3: 1-6, and preferably 2-3: 4-6.
5. The method of claim 3, wherein: the heating temperature in the step (1) is 60-100 ℃, the stirring speed is 100-200 r/min, and the reaction time is 1-2 h.
6. The method of claim 3, wherein: the ionic liquid in the step (2) is [ Bmim ]][PF6]、[Bmim][Cl]、[Bmim][BF4]、[Bmim] [SCN]、[Bmim] [NTf2]Etc., preferably [ Bmim ]][PF6]。
7. The method according to claim 3 or 6, characterized in that: the mol ratio of the ionic liquid to the choline chloride in the step (2) is 1: 1-3, preferably 1: 2-3.
8. The method of claim 3, wherein: the reaction temperature in the step (2) is 50-80 ℃, and the reaction time is 0.5-1 h.
9. Use of the absorbent according to any of claims 1-2, characterized in that the waste gas containing aromatics VOCs is contacted with the absorbent.
10. Use according to claim 9, characterized in that: in the aromatic hydrocarbon-containing organic waste gas, the aromatic hydrocarbon is mainly at least one of benzene, toluene, xylene, styrene, phenol, chlorobenzene, nitrochlorobenzene and the like.
11. Use according to claim 9, characterized in that: the contact condition of the aromatic hydrocarbon-containing organic waste gas and the absorbent is as follows: the pressure is 0.1-0.3 MPa, the temperature is 10-30 ℃, and the liquid-gas ratio is 4-6L/m3。
12. Use according to claim 9, characterized in that: and after absorption and balance, regeneration is carried out, and heating or/and pressure reduction regeneration is adopted, wherein the regeneration temperature is 100-150 ℃, and the regeneration pressure is 10 kPa-0.1 MPa.
13. Use according to claim 12, characterized in that: in N2And (4) performing in an atmosphere, and recycling the regenerated absorbent.
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Effective date of registration: 20231204 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |