CN114748986B - Synchronous defluorination and denitration method for composite absorbent - Google Patents
Synchronous defluorination and denitration method for composite absorbent Download PDFInfo
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- 239000002250 absorbent Substances 0.000 title claims abstract description 38
- 230000002745 absorbent Effects 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 11
- 238000006115 defluorination reaction Methods 0.000 title claims description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 50
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000000746 purification Methods 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract 2
- 239000012528 membrane Substances 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- -1 methacryloyloxyethyl trimethyl ammonium tetrafluoroborate Chemical compound 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229920002301 cellulose acetate Polymers 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 28
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 24
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002367 phosphate rock Substances 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920006284 nylon film Polymers 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- CXERBOODJDWFQL-UHFFFAOYSA-N 2,2-dicyanoethenylideneazanide Chemical compound [N-]=C=C(C#N)C#N CXERBOODJDWFQL-UHFFFAOYSA-N 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- VHFBTKQOIBRGQP-UHFFFAOYSA-N fluoro nitrate Chemical compound [O-][N+](=O)OF VHFBTKQOIBRGQP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002341 toxic gas 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
- B01D53/22—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
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2047—Hydrofluoric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a method for synchronously defluorinating and denitrating a composite absorbent, which is characterized in that the composite absorbent consisting of a hydrophobic ion liquid film and an alkaline aqueous solution is used for treating tail gas containing fluorine and nitrate, so that synchronous purification and selective separation of NO and HF are realized; the hydrophobic ionic liquid film is prepared by immersing a massive dry film body into the hydrophobic ionic liquid, standing, separating solid from liquid, drying and crushing; compared with the prior art, the composite absorbent has the advantages of simple synthesis, small solvent loss, large absorption capacity, good absorption effect and the like, the ion liquid film has strong penetration selectivity to NO, the water in the composite absorbent has high absorption effect to HF, the purification of NO and HF can be realized at the same time, and the two gases can be separated.
Description
Technical Field
The invention relates to a method for synchronous defluorination and denitration by using a composite absorbent, belonging to the field of environmental protection and gas purification.
Background
The atmosphere, which is an environmental element on which humans live, is increasingly serious in environmental pollution with the continuous development of industry and society, and thus presents serious challenges for the survival and development of humans.
The phosphorite resources in China are rich, the reserves are the second worldwide, and 2% -4% of fluorine resources are associated on average. Phosphate in the phosphorite can be recycled through a plurality of special treatment methods, and can be processed into products such as phosphate fertilizer, phosphate-containing feed and the like. Global phosphoric acid is produced mainly by wet process. The hydrochloric acid method, the sulfuric acid method, the nitric acid method and the like are main methods for producing wet-process phosphates, and each of the three production processes has advantages. The method uses phosphorite and nitric acid as main raw materials in the using process, and because the phosphorite contains a large amount of calcium fluophosphate (Ca 5F(PO4)3), hydrogen Fluoride (HF) is generated in the reaction process, and gaseous substances such as NO and the like are released, and although the method can recycle phosphorus resources in the phosphorite, harmful gases are released in the production process, and the harmful gases are continuously accumulated in the environment and directly or indirectly initiate warning for human safety and ecological balance.
The massive emission of NO easily causes frequent occurrence of acid rain and haze, and forms a great threat to human health and ecological environment. HF is a toxic gas pollutant, and excessive fluorine intake by human body can cause diseases such as fluoridation and the like to harm human health, and excessive fluorine absorption by plants can cause serious consequences such as plant yield reduction and even dead, and HF in air can cause serious corrosion to buildings or equipment along with rainwater falling, so that the service life of the buildings or equipment is influenced.
NO has the property of being indissolvable in water, and the treatment technology is divided into a dry method and a wet method according to the treatment process, wherein the dry denitration comprises the following steps: catalytic Reduction (SCR), non-catalytic reduction (SNCR), plasma, adsorption, absorption, etc.; wet denitration includes alkali absorption, acid absorption, complexing absorption and the like. The dry denitration technology has low treatment efficiency on NO gas, only about 40%, and has low applicability in industrial production although the dry treatment energy consumption is good. At present, the most common wet denitration method is to use complexing agents to absorb NO or oxidizing agents such as NaClO to absorb NO, so that the consumption of the complexing agents and the oxidizing agents is high, and the cost is high.
HF is very soluble in water, and common treatment techniques at present are absorption, adsorption, membrane separation and the like. The adsorption method has strict selection of the adsorbent, the common adsorbents include activated alumina, sodium fluoride, activated carbon and the like, and the membrane separation method has strict selection of the membrane material. Although adsorption and membrane separation have certain effects on HF removal, the cost of the adsorbent and membrane materials is high, and industrial application cannot be truly realized.
Chinese patent publication No. CN112138500 a discloses a "vehicle-mounted sulfur-nitro-dust-fluorine integrated deep purification device and use method", the method mainly adopts a spray coupling corona discharge mode to remove nitro and fluorine, and the used absorbent is mainly a complexing agent containing cobalt, ferrous iron and the like or an oxidizing agent containing NaClO 2、KMnO4、H2O2 and the like, a microemulsion absorbent and the like, and the absorbent used in the method has higher cost and is unfavorable for recycling the absorbent. The Chinese patent publication No. CN 208032296U discloses a gas purifying tower and gas purifying equipment, and the main innovation of the equipment is that a cutting device is arranged in a tank body, the device not only can refine a filler, but also can effectively improve the contact area between bubbles and liquid medicine, but also is a traditional chemical reaction absorption method in essence, has low purifying efficiency on gases such as fluorine, nitrate and the like, cannot adapt to various complex working conditions, and cannot realize the integrated and efficient removal of harmful components such as sulfur, nitrate, dust, fluorine and the like.
In view of the above, for synchronous denitration and defluorination technology, there is still a need to develop a simple, more effective and lower-cost synergistic treatment method.
Disclosure of Invention
The invention provides a composite absorbent and a synchronous defluorination and denitration method thereof, which are characterized in that a massive dry film body is immersed into a hydrophobic ionic liquid, and is kept stand, and is dried and crushed after solid-liquid separation to prepare a hydrophobic ionic liquid film, then the hydrophobic ionic liquid film powder is mixed with an alkaline aqueous solution to form the composite absorbent, finally, gas containing NO and HF is introduced into the composite absorbent, HF is absorbed by the alkaline aqueous solution at 20-85 ℃, and NO is absorbed by the hydrophobic ionic liquid film, so that synchronous purification and selective separation of NO and HF are realized, and thus, the denitration and defluorination with high efficiency and low cost are realized.
The mass ratio of the ionic liquid film to the alkaline aqueous solution in the composite absorbent formed by the ionic liquid film and the alkaline aqueous solution is 1-1.5:3-4.
The membrane body is one or more of a polyethersulfone membrane, an acetate fiber membrane, a polyvinylidene fluoride membrane, a nylon membrane and a polytetrafluoroethylene membrane.
The cation of the hydrophobic ionic liquid is selected from one or more of alkyl substituted imidazole cation, pyridine cation, quaternary ammonium cation, quaternary phosphine cation, thiazole cation and pyrroline cation, and the anion is selected from one or more of [Tf2N]-、[AsF6]-、[PF6]-、[BF4]-、[TCM]-、 carboxylate, amino acid radical and [ CH 3S8O3]-、[CF3COO]- ].
The alkaline aqueous solution is one or more of NH 3·H2 O solution, ca (OH) 2 solution, naOH solution and Na 2CO3 solution with the concentration of 0.05-5 mol/L.
The concentration of HF in the gas containing NO and HF is 500-1500 ppm, and the concentration of NO is 700-2500 ppm; the air flow is 300-1000 mL/min.
The invention has the advantages that:
1. The organic film in the hydrophobic ionic liquid film has wide sources, low cost, corrosion resistance and high temperature resistance, and is not easy to react with aqueous solution; the ionic liquid film has good stability and convenient operation;
2. The hydrophobic ionic liquid has stronger hydrophobicity, has higher purification effect on NO and NO absorption effect on HF, can release NO in a desorption mode after absorbing NO, can be recycled, and can be used as industrial raw materials for recycling;
3. the water in the composite absorbent composed of the ionic liquid film and the aqueous solution has a strong absorption effect on HF, and the ionic liquid film has a high permeability selectivity on NO. The composite absorbent has the advantages of small consumption, large absorption capacity and lower energy consumption, and is suitable for synchronous removal of the fluorine-nitrate tail gas.
Drawings
FIG. 1 is a schematic diagram of a simulation apparatus for carrying out the method of the present invention.
Detailed Description
The present invention will be described in further detail by way of examples, but the scope of the present invention is not limited to the following examples.
Example 1: the method for synchronously denitrating and defluorinating the composite absorbent comprises the following steps:
1. Preparation of hydrophobic ionic liquid film: the organic film body is a polyethersulfone film, the hydrophobic ionic liquid is [ C 8F13MIM][Tf2 N ] (the ionic liquid [ C 8F13MIM][Tf2 N ] in the invention is prepared by adopting a method of ：Baltus R E , Counce R M , Culbertson B H , et al. Examination of the Potential of Ionic Liquids for Gas Separations[J]. Separation Science and Technology, 2005, 40(1):525-541.）,, the mass of the film body is 18g, the film thickness is 200 mu m by referring to the method of the following document, the dried polyethersulfone film is immersed into the hydrophobic ionic liquid [ C 8F13MIM][Tf2 N ], and stands for 5 hours, so that the pore canal of the film body is fully filled with the ionic liquid;
2. As shown in figure 1, according to the mass ratio of 1:2, the hydrophobic ion liquid film is crushed and fully mixed with 0.1mol/L NH 3·H2 O aqueous solution to form a composite absorbent, the composite absorbent is placed in a reaction device, the reaction device is placed in a constant-temperature water bath, the reaction temperature is set to be 60 ℃, nitrogen is used as carrier gas, N 2, HF and NO are respectively introduced into a gas mixing chamber from a gas tank to prepare mixed gas containing 500ppm of HF and 700ppm of NO, the mixed gas is introduced into the reaction device filled with the composite absorbent at the flow rate of 500mL/min, the gas is fully contacted with the composite absorbent, the concentration of NO and HF before and after the reaction is timely measured by using a flue gas analyzer every 20min, the measured NO purification efficiency reaches 95% after continuous purification for 3h, and the HF absorption efficiency reaches 100%; and (3) recovering the reacted ionic liquid [ C 8F13MIM][Tf2 N ] in a desorption mode of nitrogen purging, wherein the recovery rate of the ionic liquid reaches 90%.
Example 2: the method for synchronously denitrating and defluorinating the composite absorbent comprises the following steps:
1. Preparation of hydrophobic ionic liquid film: the organic film body is a nylon film, the hydrophobic ionic liquid is [ MATMA ] [ BF 4 ] (the ionic liquid [ MATMA ] [ BF 4 ] in the invention is prepared by drying and weighing a blocky nylon film with the mass of 20g and the film thickness of 300 mu m according to the following literature method ：Jianbin T , Tang H , Sun W , et al. Poly(ionic liquid)s: a new material with enhanced and fast CO2absorption[J]. Chemical Communications, 2005(26):3325-3327.）,, immersing the dried nylon film in the hydrophobic ionic liquid [ MATMA ] [ BF 4 ], standing for 9 hours to fully fill the pore canal of the support body, lightly wiping the superfluous ionic liquid on the outer surface of the film body by ink absorbing paper, weighing to obtain the loading amount of the ionic liquid as 50%, and drying the ionic liquid film in a vacuum drying box at 75 ℃ for 15 hours and then crushing for use;
2. Fully mixing a hydrophobic ion liquid film with 0.2mol/L NaOH aqueous solution according to the mass ratio of 1:3 to form a composite absorbent, placing the composite absorbent in a reaction device, placing the reaction device in a constant-temperature water bath, setting the reaction temperature to 65 ℃, using nitrogen as carrier gas, introducing N 2, HF and NO into a gas mixing chamber from a gas tank respectively to prepare mixed gas containing 450ppm of HF and 650ppm of NO, introducing the mixed gas into the reaction device filled with the composite absorbent at the flow rate of 500mL/min, fully contacting the gas with the composite absorbent, timely measuring the concentration of NO and HF before and after the reaction by using a flue gas analyzer every 20min, and continuously purifying for 7h to obtain the NO purification efficiency up to 96%, wherein the HF absorption efficiency is up to 98%; the ionic liquid [ MATMA ] [ BF4] after the reaction is recovered by a desorption mode of nitrogen purging, and the recovery rate of the ionic liquid reaches 97%.
Example 3: the method for synchronously denitrating and defluorinating the composite absorbent comprises the following steps:
1. Preparation of hydrophobic ionic liquid film: the organic film body is polyvinylidene fluoride film, the hydrophobic ionic liquid is [ RMIM ] [ TCM ] (the ionic liquid [ RMIM ] [ TCM ] in the invention is prepared by drying and weighing a block-shaped polyvinylidene fluoride film according to the following literature method ：Tzialla O , Labropoulos A , Panou A , et al. Phase behavior and permeability of Alkyl-Methyl-Imidazolium Tricyanomethanide ionic liquids supported in nanoporous membranes[J]. Separation and Purification Technology, 2014, 135:22–34.）,, the mass of the film body is 16g, the film thickness is 400 mu m, immersing the dried polyvinylidene fluoride film into the hydrophobic ionic liquid [ RMIM ] [ TCM ], standing for 7h, lightly wiping the superfluous ionic liquid on the outer surface of the film body by using ink absorbing paper, weighing to obtain the loading amount of the ionic liquid as 60%, and drying the ionic liquid film in a vacuum drying oven at 80 ℃ for 20h and then crushing the ionic liquid film;
2. Fully mixing a hydrophobic ion liquid film with 0.3mol/L Na 2CO3 aqueous solution according to a mass ratio of 1:4 to form a composite absorbent, placing the composite absorbent in a reaction device, placing the reaction device in a constant-temperature water bath, setting the reaction temperature to be 55 ℃, using nitrogen as carrier gas, respectively introducing N 2, HF and NO into a gas mixing chamber from a gas tank to prepare mixed gas containing 600ppm of HF and 800ppm of NO, introducing the mixed gas into the reaction device filled with the composite absorbent at a flow rate of 500mL/min, fully contacting the gas with the composite absorbent, timely measuring the concentration of NO and HF before and after the reaction every 20min by using a flue gas analyzer, and continuously purifying for 6h, wherein the measured NO purification efficiency reaches 93%, and the HF absorption efficiency reaches 99%; the ionic liquid [ RMIM ] [ TCM ] after the reaction is recovered by a desorption mode of nitrogen purging, and the recovery rate of the ionic liquid reaches 95%.
Claims (2)
1.A synchronous defluorination and denitration method for a composite absorbent is characterized by comprising the following steps of: the composite absorbent composed of the hydrophobic ionic liquid film and the alkaline aqueous solution is used for treating the fluorine-containing nitrate tail gas, the hydrophobic ionic liquid film and the alkaline aqueous solution are fully mixed to form the composite absorbent, so that the fluorine-containing nitrate tail gas fully contacts with the composite absorbent, and synchronous purification and selective separation of NO and HF are realized;
The hydrophobic ionic liquid film is prepared by immersing a massive dry film body into the hydrophobic ionic liquid, standing, separating solid from liquid, drying and crushing;
The hydrophobic ionic liquid is one of tridecafluoro-1-octene-3-methylimidazole trifluoromethanesulfonyl imide lithium [ C 8F13MIM][Tf2 N ], methacryloyloxyethyl trimethyl ammonium tetrafluoroborate [ MATMA ] [ BF 4 ], 1-alkyl-3-methylimidazole tricyanomethyl amine [ RMIM ] [ TCM ];
The alkaline aqueous solution is one or more of NH 3·H2 O solution, ca (OH) 2 solution, naOH solution and Na 2CO3 solution with the concentration of 0.05-5 mol/L, and the membrane body is one or more of a polyether sulfone membrane, a cellulose acetate membrane, a polyvinylidene fluoride membrane, a nylon membrane and a polytetrafluoroethylene membrane;
The mass ratio of the ionic liquid film to the alkaline aqueous solution in the composite absorbent formed by the ionic liquid film and the alkaline aqueous solution is 1-1.5:3-4.
2. The method for synchronous defluorination and denitration of composite absorbent according to claim 1, which is characterized in that: the concentration of HF in the fluorine-containing nitrate tail gas is 500-1500 ppm, and the concentration of NO is 700-2500 ppm.
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