CN114471084B - 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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- CN114471084B CN114471084B CN202011167982.5A CN202011167982A CN114471084B CN 114471084 B CN114471084 B CN 114471084B CN 202011167982 A CN202011167982 A CN 202011167982A CN 114471084 B CN114471084 B CN 114471084B
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- 239000002250 absorbent Substances 0.000 title claims abstract description 103
- 230000002745 absorbent Effects 0.000 title claims abstract description 103
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010815 organic waste Substances 0.000 title abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims abstract description 80
- 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 31
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 25
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 25
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 25
- 229960003178 choline chloride Drugs 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 144
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 38
- 239000012855 volatile organic compound Substances 0.000 claims description 29
- 239000002912 waste gas Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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 13
- 239000000203 mixture Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 150000002500 ions Chemical class 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
- 150000005826 halohydrocarbons Chemical class 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
- 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 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
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 238000002474 experimental method Methods 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
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 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
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 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
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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
- B01D53/14—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
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, a preparation method and application thereof.
Background
Volatile Organic Compounds (VOCs) can be classified into aromatic hydrocarbons (benzene, toluene, xylene), ketones, aldehydes, amines, halogenated hydrocarbons, unsaturated hydrocarbons, etc. according to their chemical structures. According to the specification of integrated emission standard of atmospheric pollutants (GB 16297-1996), the specific requirement on the concentration of organic special pollutants at the discharge port of VOCs is specified, and the discharge limit of 33 atmospheric pollutants is specified, wherein benzene is less than or equal to 17mg/m 3 Toluene is less than or equal to 60mg/m 3 Xylene is less than or equal to 90mg/m 3 Nitrobenzene is less than or equal to 20 mg/m 3 。
In the prior art, techniques for controlling the emission of VOCs can be classified into destructive methods (chemical oxidation method, biological oxidation method), absorption/adsorption method, condensation and membrane separation method, etc. Compared with the destructive method, the absorption method has received a great deal of attention because of the 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 the absorption method has high absorptivity and good recoverability and is the first choice for removing the VOCs. The absorbents commonly used for VOCs mainly include vegetable oil-water emulsions, silicone oil-water emulsions, di (2-ethylhexyl) adipate, diisobutyl phthalate, and the like. The recycling and recycling of the rich absorbent are beneficial to improving the economy of VOCs treatment, but most of the absorbent cannot be recycled and reused, and the utilization rate is low. Therefore, developing the absorbent with high absorptivity, low volatility, high thermal stability and good recoverability has important significance for effectively removing VOCs.
The ionic liquid is an environment-friendly solvent with stable properties, and has wide application prospect in the field of gas absorption. However, due to the differences in properties of the different ionic liquids themselves, the selectivity and absorption capacity for different absorbing substances are limited.
CN105582786a discloses a method for removing volatile organic compounds from gases by using an ionic liquid. The absorption tower is operated at 0-100 deg.c and 0.1-10MPa and has theoretical plate number of 5-20. The content of VOCs methanol, ethanol and toluene in the tower top gas product is less than 2000ppm; 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 cations in the ionic liquid used in the invention are selected from imidazoles, pyridines and quaternary ammonium salts, and the anions are selected from bistrifluoromethane sulfonyl imide, tetrafluoroborate, hexafluorophosphate, acetate and diethyl sulfate, but the absorption pressure is set higher, so that the absorption energy consumption is improved, and the selectivity of the ionic liquid for aromatic hydrocarbon pollutants in VOCs is not strong.
CN102924333a discloses a method for preparing ionic liquid for absorbing low boiling point halohydrocarbon gas and its application in absorbing low boiling point halohydrocarbon gas, which is to uniformly mix one of aluminum chloride, zinc chloride or lithium chloride with one or two of citric acid, urea, acetamide, propionamide, butyramide or caprolactam in a molar ratio of 1:1-10 or 1:0.5-3:1-7, react for 1-10 hours at 70-150 ℃, and then vacuum dry the obtained solution at 40-80 ℃ for 1-5 hours to obtain ionic liquid. The ionic liquid is mainly used for absorbing low-boiling-point halohydrocarbon gas, and has low selectivity on aromatic hydrocarbon pollutants in VOCs. In addition, the absorbent adopts amide substances, which can cause 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 first aspect of the invention provides an aromatic hydrocarbon-containing organic compoundThe absorbent of the waste gas mainly comprises ionic liquid, choline chloride and citric acid, wherein the ionic liquid is [ Bmim ]][PF 6 ]、[Bmim][Cl]、[Bmim][BF 4 ]、[Bmim] [SCN]、[Bmim] [NTf 2 ]At least one of the above, preferably [ Bmim ]][PF 6 ]。
In the absorbent of the invention, 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 method for preparing 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 of the invention, the molar ratio of the choline chloride to the citric acid in the step (1) is 1-3:1-6, 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 1-2h.
In the preparation method of the invention, the ionic liquid in the step (2) is [ Bmim ]][PF 6 ]、[Bmim][Cl]、[Bmim][BF 4 ]、[Bmim] [SCN]、[Bmim] [NTf 2 ]At least one of the following, preferably [ Bmim ]][PF 6 ]。
In the preparation method of the invention, 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 0.5-1h.
In a third aspect, the invention provides the use of an aromatic hydrocarbon-containing organic waste gas absorbent by contacting an aromatic hydrocarbon-containing VOCs waste gas with the absorbent of the invention.
In the application of the invention, the absorbent mainly comprises ionic liquid, choline chloride and citric acid, and the ionic liquid is [ Bmim ]][PF 6 ]、[Bmim][Cl]、[Bmim][BF 4 ]、[Bmim] [SCN]、[Bmim] [NTf 2 ]At least one of the above, preferably [ Bmim ]][PF 6 ]. 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.
In the application of the invention, in the aromatic hydrocarbon-containing VOCs waste gas, 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 conditions for contacting the aromatic hydrocarbon-containing VOCs waste gas with the absorbent are as follows: the pressure is 0.1-0.3 MPa, the temperature is 10-30 ℃, and the liquid-gas ratio is 4-6L/m 3 。
In the application of the invention, the absorbent is contacted with waste gas, regenerated after the absorption is balanced, and the regeneration temperature is 100-150 ℃ and the regeneration pressure is 10-0.1 MPa by adopting a heating or/and decompression regeneration mode. Further, it is preferable that the ratio is N 2 The process is carried out in 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 the three components in the absorbent are synergistic, so that the absorbent has good selectivity and absorption performance on aromatic hydrocarbon in VOCs at normal temperature, and has the advantages of rapid absorption, high efficiency, strong selectivity and the like.
(2) The absorbent prepared by the invention can realize high-efficiency regeneration by heating or/and decompression, and the regenerated absorbent can be recycled and has good absorption stability.
(3) The absorbent prepared by the method has the advantages of abundant raw material sources, environment friendliness, low cost, simple synthesis and capability of large-scale production, and is an efficient, environment-friendly and environment-friendly absorbent.
Detailed Description
The absorbent of the present invention and its effects are further described below in conjunction with specific examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Example 1
Adding choline chloride and citric acid into a reactor according to a molar ratio of 1:3, and stirring and reacting at 100 ℃ for 2 hours at 150r/min to obtain uniform liquid. According to ionic liquids [ Bmim][PF 6 ]Adding the mixture into the liquid in a molar ratio of 1:2 with choline chloride, stirring and reacting for 1h at 70 ℃, and cooling to room temperature to obtain the absorbent.
Absorbing the waste gas containing toluene VOCs with the absorbent in an absorption tower, controlling the absorption temperature to 25 ℃, the absorption pressure to 0.1MPa and the liquid-gas ratio to 5L/m 3 . After the absorption reached equilibrium, the weight before and after the absorption was measured by a gravimetric method, and toluene absorbed per gram of the absorbent was calculated to be 362mg.
And (3) carrying out decompression regeneration on the rich absorbent with balanced absorption, wherein the pressure is 0.01MPa, and the desorption time is 1h. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing waste gas under the same operating conditions, with 351mg of toluene absorbed per gram of absorbent.
Example 2
Adding choline chloride and citric acid into a reactor according to a molar ratio of 1:1, and stirring and reacting at 80 ℃ for 1h at 150r/min to obtain uniform liquid. According to ionic liquids [ Bmim][PF 6 ]Adding the mixture into the uniform liquid with the molar ratio of 1:1 with choline chloride, stirring and reacting for 1h at 50 ℃, and cooling to room temperature to obtain the absorbent.
Absorbing the waste gas containing toluene VOCs with the absorbent in an absorption tower, controlling the absorption temperature to 25 ℃, the absorption pressure to 0.1MPa and the liquid-gas ratio to 5L/m 3 . After the absorption reached equilibrium, the weight before and after the absorption was measured by a gravimetric method, and toluene absorbed per gram of the absorbent was calculated to be 283mg.
And (3) heating and decompressing the rich absorbent with balanced absorption, wherein the heating temperature is 100 ℃, the pressure is 0.1MPa, and the regeneration time is 1h. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing waste gas under the same operating conditions, with 276mg of toluene absorbed per gram of absorbent.
Example 3
Adding choline chloride and citric acid into a reactor according to a molar ratio of 1:2, and stirring and reacting at 60 ℃ and 200r/min for 1h to obtain uniform liquid. According to ionic liquids [ Bmim][PF 6 ]Adding the mixture into the uniform liquid with the molar ratio of 1:2 with choline chloride, stirring and reacting for 0.5h at 90 ℃, and cooling to room temperature to obtain the absorbent.
Absorbing the waste gas containing toluene VOCs with the absorbent in an absorption tower, controlling the absorption temperature to 25 ℃, the absorption pressure to 0.1MPa and the liquid-gas ratio to 5L/m 3 . After the absorption reached equilibrium, the weight before and after absorption was measured by a gravimetric method, and 304mg of toluene was calculated to be absorbed per gram of absorbent.
And (3) heating and decompressing the rich absorbent with balanced absorption, wherein the heating temperature is 120 ℃, the pressure is 0.01MPa, and the regeneration time is 0.5h. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing waste gas under the same operating conditions, with 293mg of toluene absorbed per gram of absorbent.
Example 4
Adding choline chloride and citric acid into a reactor according to a molar ratio of 1:4, and stirring and reacting at 100 ℃ and 200r/min for 2 hours to obtain uniform liquid. According to ionic liquids [ Bmim][PF 6 ]Adding the mixture into the uniform liquid with the molar ratio of the mixture to the choline chloride being 1:3, stirring the mixture at 70 ℃ for reaction for 1h, and cooling the mixture to room temperature to obtain the absorbent.
Absorbing the waste gas containing toluene VOCs with the absorbent in an absorption tower, controlling the absorption temperature to be 30 ℃, the absorption pressure to be 0.1MPa, and the liquid-gas ratio to be 4L/m 3 . After the absorption reached equilibrium, the weight before and after absorption was measured by a gravimetric method, and toluene absorbed per gram of absorbent was calculated to be 295mg.
And heating and decompressing the rich absorbent with balanced absorption, wherein the pressure is 0.01MPa, the temperature is 150 ℃, and the desorption time is 20min. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing waste gas under the same operating conditions, with 287mg of toluene being absorbed per gram of absorbent.
Example 5
The difference from example 1 is that: in [ Bmim ]][Cl]Ion liquid substitution [ Bmim ]][PF 6 ]The absorbent is obtained. After the absorption reached equilibrium, 336mg of toluene was detected and calculated to be absorbed per gram of absorbent. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing waste gas under the same operating conditions, with 324mg of toluene absorbed per gram of absorbent.
Example 6
The difference from example 1 is that: in [ Bmim ]][BF 4 ]Ion liquid substitution [ Bmim ]][PF 6 ]The absorbent is obtained. After the absorption reached equilibrium, 341mg of toluene was detected and calculated to be absorbed per gram of absorbent. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing waste gas under the same operating conditions, with 329mg of toluene absorbed per gram of absorbent.
Example 7
The difference from example 1 is that: in [ Bmim ]][SCN]Ion liquid substitution [ Bmim ]][PF 6 ]The absorbent is obtained. After the absorption reached equilibrium, 356mg of toluene was detected and calculated to be absorbed per gram of absorbent. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing waste gas under the same operating conditions, with 343mg of toluene absorbed per gram of absorbent.
Example 8
The difference from example 1 is that: in [ Bmim ]][NTf 2 ]Ion liquid substitution [ Bmim ]][PF 6 ]The absorbent is obtained. After the absorption reached equilibrium, 328mg of toluene was detected and calculated to be absorbed per gram of absorbent. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing waste gas under the same operating conditions, with 316mg of toluene absorbed per gram of absorbent.
Example 9
The difference from example 1 is that: will be [ Bmim ] in the same proportion][PF 6 ]The choline chloride and the citric acid are directly mixed according to the proportion of 1:2:6, and are stirred at 80 ℃ until being uniform, thus obtaining the absorbent. After the absorption reached equilibrium, 253mg of toluene was detected and calculated to be absorbed per gram of absorbent. After 10 cycles of absorption and desorption, the regenerated absorbent was used for the same absorption of toluene-containing gas under the same operating conditions, with 185mg of toluene absorbed per gram of absorbent.
It follows that [ Bmim ] will][PF 6 ]The initial absorption effect of the choline chloride and the citric acid which are directly mixed in proportion is improved, but the absorption stability is required to be improved after multiple regenerations.
Comparative example 1
The difference from example 1 is that: choline chloride is not used in the preparation of the absorbent. After the absorption reached equilibrium, the toluene absorbed per gram of absorbent was detected and calculated to be 133mg. After 10 cycles of absorption and desorption, 118mg of toluene was 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 toluene absorbed per gram of absorbent was detected and calculated to be 109mg. After 10 cycles of absorption and desorption, 98mg of toluene was absorbed per gram of absorbent.
Comparative example 3
The difference from example 1 is that: no ionic liquid is used in the preparation of the absorbent. After the absorption reached equilibrium, 154mg of toluene was detected and calculated to be absorbed per gram of absorbent. After 10 cycles of absorption and desorption, 136mg of toluene was absorbed per gram of absorbent.
Comparative example 4
The difference from example 1 is that: the absorbent prepared in example 1 of CN105582786a was used. After the absorption reaches equilibrium, toluene absorbed per gram of absorbent is detected and calculated to be below 205mg.
Comparative example 5
The difference from example 1 is that: the absorbent prepared in example 1 of CN102924333a was used. After the absorption reaches equilibrium, toluene absorption per gram of absorbent is detected and calculated to be less than 214mg.
Test example 1
The absorbents prepared in examples 1 to 8 were used for the absorption of various aromatic hydrocarbon-containing substances under the following conditions: the pressure is 0.1MPa, the temperature is 25 ℃, and the liquid-gas ratio is 5L/m 3 . The absorption effect is shown in Table 1.
TABLE 1 absorption Effect of examples 1-8 (unit: mg/g absorbent)
Test example 2
The VOCs waste gas discharged from a certain chemical plant mainly contains VOCs such as toluene, propane, styrene and the like, and the concentration of non-methane total hydrocarbon is 5326mg/m 3 The sum of toluene and styrene concentrations was 2147mg/m 3 . The absorbents of examples 1 to 8 were used for absorption at a pressure of 0.1MPa and a temperature of 25℃and a liquid-gas ratio of 5L/m, respectively 3 。
After absorption, the concentration of non-methane total hydrocarbon in the outlet waste gas is 4010-4650mg/m 3 The concentration of toluene and styrene VOCs is between 401 and 422mg/m 3 Between them. 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 (8)
1. An absorbent for selectively absorbing aromatic hydrocarbon in VOCs is characterized by comprising an ionic liquid, choline chloride and citric acid, wherein the ionic liquid is [ Bmim ]][PF 6 ]、[Bmim][Cl]、[Bmim][BF 4 ]、[Bmim] [SCN]、[Bmim] [NTf 2 ]At least one of the ionic liquid, the choline chloride and the citric acid in a molar ratio of 1:1-3:1-6; the preparation method of the absorbent comprises the following steps: (1) Mixing choline chloride and citric acid in proportion, heating and stirring uniformly; the heating temperature is 60-100 ℃, the stirring speed is 100-200 r/min, and the reaction time is 1-2h; (2) adding ionic liquid for reaction, and cooling to obtain an absorbent; the reaction temperature is 50-80 ℃ and the reaction time is 0.5-1h.
2. The absorbent of claim 1, wherein: the ionic liquid is [ Bmim ]][PF 6 ]。
3. The absorbent according to claim 1 or 2, characterized in that: the molar ratio of the ionic liquid to the choline chloride to the citric acid is 1:2-3:4-6.
4. Use of an absorbent according to any one of claims 1-3, characterized in that the aromatic hydrocarbon-containing VOCs off-gas is contacted with the absorbent.
5. The use according to claim 4, characterized in that: in the aromatic hydrocarbon-containing VOCs waste gas, the aromatic hydrocarbon is at least one of benzene, toluene, xylene, styrene, phenol and chlorobenzene.
6. The use according to claim 4, characterized in that: the conditions for contacting the aromatic hydrocarbon-containing VOCs waste gas with the absorbent are as follows: the pressure is 0.1-0.3 MPa, the temperature is 10-30 ℃, and the liquid-gas ratio is 4-6L/m 3 。
7. The use according to claim 4, characterized in that: and after the absorption is balanced, the regeneration is carried out, and the heating or/and the decompression regeneration is adopted, wherein the regeneration temperature is 100-150 ℃, and the regeneration pressure is 10 kPa-0.1 MPa.
8. The use according to claim 7, characterized in that: at N 2 The process is carried out in atmosphere, and the regenerated absorbent is recycled.
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| CN102702166A (en) * | 2012-05-15 | 2012-10-03 | 北京林业大学 | Method for preparing glycerin shrinkage benzaldehyde |
| EP2692413A1 (en) * | 2012-07-31 | 2014-02-05 | Lenzing Aktiengesellschaft | Ionic liquids for selective sulfur dioxide absorption |
| CN103929962A (en) * | 2011-08-16 | 2014-07-16 | 巴斯夫欧洲公司 | Composition comprising active ingredient, oil and ionic liquid |
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| CN107569973A (en) * | 2016-07-05 | 2018-01-12 | 北京化工大学苏州（相城）研究院 | The absorption processing method and system of VOC organic exhaust gas |
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| CN102702166A (en) * | 2012-05-15 | 2012-10-03 | 北京林业大学 | Method for preparing glycerin shrinkage benzaldehyde |
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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. |