CN115475484A - Method and device for recovering VOCs (volatile organic compounds) in two-phase cycle - Google Patents
Method and device for recovering VOCs (volatile organic compounds) in two-phase cycle Download PDFInfo
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- CN115475484A CN115475484A CN202110660446.7A CN202110660446A CN115475484A CN 115475484 A CN115475484 A CN 115475484A CN 202110660446 A CN202110660446 A CN 202110660446A CN 115475484 A CN115475484 A CN 115475484A
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- 238000000034 method Methods 0.000 title claims abstract description 48
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
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- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- 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
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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
- B01D53/18—Absorbing units; Liquid distributors therefor
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- 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
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention relates to the technical field of VOCs recovery, in particular to a method and a device for recovering VOCs in a two-phase circulation manner. According to the method provided by the invention, the bubbles of the VOCs-containing feed gas flow upwards in the dilution process, VOCs capture function liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs capture function liquid drops flow in parallel for mass transfer, especially the initial diameter range of the bubbles, the diameter of the VOCs capture function liquid drops and the ascending flow velocity of the bubbles are limited, so that the mass transfer effects of the VOCs capture function liquid drops and the bubbles are effectively improved, the gas purification and capture phase recovery are realized, and meanwhile, the VOCs capture function liquid drops capturing VOCs are subjected to coalescence and phase separation and enter a regenerator to complete the regeneration and cyclic utilization of the concentrated capture phase. The method reduces the circulation quantity of the trapped phase and reduces the production cost while realizing the high-efficiency separation and recovery of VOCs.
Description
Technical Field
The invention relates to the technical field of VOCs recovery, in particular to a method and a device for recovering VOCs in a two-phase circulation manner.
Background
Volatile Organic Compounds (VOCs) are an increasingly important air pollutant. According to the definition of world health organization, various organic compounds with the boiling point of 50-260 ℃ at normal temperature are defined. In China, VOCs refer to organic compounds with saturated vapor pressure of more than 70Pa at normal temperature and boiling point of 260 ℃ or below at normal pressure or all organic compounds with vapor pressure of more than or equal to 10Pa and volatility at 20 ℃. Common volatile organic compounds include hydrocarbons, alcohols, ethers, ketones, esters, amines, acids, aldehydes, phenols and the like, generally have strong malodor and toxicity, and partially also have three-cause effects. These volatile organic compounds are typically derived from process off-gases, process off-gases and process by-products of coal chemical and petrochemical processes. On the other hand, the solvent is expensive, and especially the high-concentration VOC waste gas causes not only environmental pollution but also a great amount of economic loss if directly discharged.
The volatile organic matter treating technology includes: a recycling treatment method such as a compression-condensation method, an adsorption method, a membrane separation method, an absorption method, or the like; destructive treatment methods such as advanced oxidation, incineration, catalytic oxidation, plasma, etc. The condensation method mainly aims at the recovery of a high-concentration solvent, but the concentration of VOCs in non-condensable gas is still high, so that the non-condensable gas is difficult to discharge after reaching the standard; the adsorption method is particularly suitable for purifying tail gas with low concentration and large gas amount, and has potential safety hazard for serious heat release of VOCs with higher concentration; the membrane separation method is suitable for concentration from medium-concentration organic solvent and cannot realize deep purification; the absorption method is to adopt a solvent with a high boiling point to absorb volatile organic compounds, and then heat and regenerate the solvent saturated in absorption to regenerate the absorbent, and is an effective method aiming at recovering a solvent with medium and high concentration. However, conventional absorption processes for treating VOCs gases require the use of large absorbent cycles, wasting large amounts of electrical and thermal energy. On the other hand, water-soluble solvents such as alcohols, ketones, acids, ethers, etc. have limited solubility in hydrophobic absorbents such as silicone oil and diesel oil, and have poor absorption capacity.
Therefore, there is a need to develop a treatment process for VOCs that has good solubility in water-soluble and insoluble VOCs, less circulating amount of capture solvent, and low energy consumption.
Disclosure of Invention
The invention aims to solve the problems of large solution circulation amount, high energy consumption, high VOCs content in noncondensable gas and the like in the VOCs treatment process in the prior art, and provides a method and a device for recycling VOCs in a double circulation manner.
In order to achieve the above objects, a first aspect of the present invention provides a method for recovering VOCs with a two-phase cycle, comprising the steps of:
(1) Dispersing the trapping phase in the diluted phase to form VOCs trapping functional liquid drops; introducing the raw gas containing the VOCs into the dilute phase to form uniformly distributed bubbles containing the raw gas containing the VOCs; the bubbles flow upwards in the diluted phase, the VOCs capture function liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs capture function liquid drops perform cocurrent mass transfer, so that the VOCs in the bubbles are captured by the VOCs capture function liquid drops, coalescence and phase separation are performed, and a concentrated capture phase for capturing VOCs and a purified gas for removing VOCs are obtained;
(2) Regenerating the concentrated trapping phase to obtain a VOCs (volatile organic compounds) recovery gas and a regenerated trapping phase;
(3) Carrying out heat exchange on the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase;
wherein the residence time of the bubbles in the dilute phase is not less than 30s.
In a second aspect, the present invention provides an apparatus for recovering VOCs in a biphasic cycle, the apparatus comprising: the concentration recovery tower, the regenerator and the heat exchanger are connected in sequence; wherein, the concentration recovery tower comprises a feeding dispersion area, a mass transfer trapping area and a flaring separation area;
the feed dispersion zone comprises a gas distributor and a liquid distributor, wherein the gas distributor is used for introducing the raw gas containing the VOCs into the dilution phase of the mass transfer trapping zone to form uniformly distributed bubbles of the raw gas containing the VOCs; the liquid distributor is used for dispersing a trapping phase into a dilution phase of the mass transfer trapping area to form VOCs trapping functional liquid drops;
the mass transfer trapping area is used for the gas bubble to flow in the dilution phase in an ascending way, the surface of the gas bubble is attached with the VOCs trapping function liquid drop, and the VOCs in the gas bubble and the VOCs trapping function liquid drop are subjected to cocurrent mass transfer, so that the VOCs trapping function liquid drop captures the VOCs in the gas bubble;
the flaring separation area is used for carrying out coalescence and phase separation on VOCs trapping functional liquid drops for trapping VOCs to obtain a concentrated trapping phase for trapping VOCs and a purified gas for removing VOCs;
the regenerator is used for regenerating the concentrated trapping phase to obtain VOCs (volatile organic compounds) recovery gas and a regenerated trapping phase;
the heat exchanger is used for exchanging heat between the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase.
According to the technical scheme, in the method for recovering VOCs in a two-phase circulation manner, bubbles containing VOCs raw material gas flow upwards in dilution, VOCs capture function liquid drops are attached to the surfaces of the bubbles, VOCs and the VOCs capture function liquid drops in the bubbles flow in parallel for mass transfer, and particularly the mass transfer effect of the VOCs capture function liquid drops and the bubbles is effectively improved by limiting the initial diameter range of the bubbles, the diameter of the VOCs capture function liquid drops and the ascending flow velocity of the bubbles, so that gas purification and capture phase recovery are realized, and meanwhile, the VOCs capture function liquid drops capturing VOCs are subjected to coalescence and phase separation and enter a regenerator to complete regeneration and cyclic utilization of a concentrated capture phase.
Meanwhile, the method provided by the invention reduces the circulation quantity of the trapping phase and the production cost while realizing the efficient separation and recovery of VOCs, and is suitable for trapping and separating various polar and nonpolar VOCs.
The device provided by the invention adopts the concentration recovery tower containing the feeding dispersion area, the mass transfer trapping area and the flaring separation area, thereby simplifying the process flow and reducing the equipment investment consumption.
Drawings
FIG. 1 is a schematic diagram of a two-phase recycle VOCs recovery apparatus according to the present invention.
Description of the reference numerals
1. Raw gas 2 containing VOCs, trapping phase 3 and diluting phase
4. VOCs trapping functional liquid drop 5, VOCs trapping functional molecule 6 and hydrophobic end
7. Hydrophilic end 8, concentrated trapping phase 9 and purified gas
10. VOCs recycle gas 11, regeneration trapping phase 12 and regeneration trapping phase after heat exchange
13. Purified gas 14 after heat exchange, fresh trapping phase 15 and purified gas after separation
16. Supplemental trapping phase
I. Concentration recovery tower II, regenerator III and heat exchanger
IV, a separator I-1, a feed dispersing area I-2 and a mass transfer collecting area
I-3, flaring separation zone I-4, gas distributor I-5 and liquid distributor
I-6, a first wire mesh demister II-1, a second wire mesh demister II-2 and a heat exchange medium inlet
II-3, heat exchange medium outlet
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the terms "first" and "second" do not denote any order or importance, and do not denote any limitation to each material or operation, but merely distinguish each material or operation. For example, the "first" and "second" of the "first wire mesh demister" and the "second wire mesh demister" are merely used to distinguish that this is not the same wire mesh demister.
In the present invention, the "top" of the container referred to in the specification means a position of 0 to 10% of the container from the top to the bottom, without special cases; the "upper part" of the vessel refers to 10-30% of the vessel from top to bottom; the "lower part" of the container means 70-90% of the position of the container from top to bottom; the "bottom" of the container refers to 90-100% of the container from top to bottom.
In a first aspect, the present invention provides a method for recovering VOCs in a biphasic cycle, the method comprising the steps of:
(1) Dispersing the trapping phase in the diluted phase to form VOCs trapping functional liquid drops; introducing the raw gas containing VOCs into the diluted phase to form uniformly distributed bubbles containing the raw gas containing VOCs; the bubbles flow upwards in the diluted phase, the VOCs trapping functional liquid drops are attached to the surfaces of the bubbles, and parallel-flow mass transfer is carried out on VOCs in the bubbles and the VOCs trapping functional liquid drops, so that the VOCs in the bubbles are trapped by the VOCs trapping functional liquid drops, coalescence and phase separation are carried out, and a concentrated trapping phase for trapping VOCs and purified gas for removing VOCs are obtained;
(2) Regenerating the concentrated trapping phase to obtain a VOCs (volatile organic compounds) recovery gas and a regenerated trapping phase;
(3) Carrying out heat exchange on the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase;
wherein the residence time of the bubbles in the dilute phase is more than or equal to 30s.
The inventor of the present invention found out that: a solvent two-phase extraction system and gas-assisted mass transfer are introduced into the field of VOCs recovery, and a method for recovering VOCs in a two-phase circulation manner is provided, so that the defects of large solution circulation amount and high energy consumption of the traditional absorption mass transfer are effectively overcome, and the method has the advantages of large phase ratio (for example, 20-100), small solution circulation amount, low energy consumption, adjustable trapping phase property, strong adaptability and the like.
In the present invention, the co-current mass transfer of the gas bubbles and the captured functional liquid droplets is brought into equilibrium by defining the residence time of the gas bubbles in the dilute phase in step (1).
In the present invention, the VOCs in the feed gas may be oxygen-containing organic compounds, hydrocarbon-containing organic compounds, trimethylamine, ethyl acetate, benzene-containing compounds, tetrahydrofuran, or the like, unless otherwise specified; the raw material gas may contain a diluent gas in addition to the VOCs, wherein the diluent gas is selected from an inert gas and/or air, and the inert gas may be, for example, nitrogen, helium, argon, and the like.
In some embodiments of the present invention, preferably, the feed gas has a content of VOCs in the range of 0.1 to 100g/cm 3 Preferably 1 to 20g/cm 3 。
In the present invention, there is a wide range of choices for the source of the feed gas, as long as the feed gas has a content of VOCs that satisfies the above-mentioned limitations. Preferably, the raw material gas is selected from VOCs waste gas generated by a coal chemical MTO process, VOCs waste gas generated by a petrochemical device, VOCs waste gas generated by a liquid crystal screen packaging material production device, VOCs waste gas generated by a pharmaceutical device, VOCs waste gas generated by a printing device, VOCs waste gas generated by a water treatment device and the like.
In the invention, the mass transfer effect between the bubbles and the VOCs trapping functional liquid drops can be effectively improved by regulating and controlling the initial diameter range of the bubbles of the VOCs-containing feed gas. Preferably, the initial diameter of the bubbles is 0.1 to 2mm, preferably 0.1 to 1.5mm.
In the present invention, the initial diameter range of the bubbles depends on the pore size of the gas distributor without specific description.
In some embodiments of the invention, it is preferred that the ascending flow velocity of the bubbles is 0.2 to 0.6m/s, preferably 0.3 to 0.5m/s. In the invention, VOCs trapping functional liquid drops for trapping VOCs are enriched and separated by regulating the ascending flow velocity range of the bubbles.
In the invention, the dilute phase is used as a solvent for mass transfer, and effective contact between bubbles and VOCs capture function liquid drops in the dilute phase is promoted, so that the VOCs capture function liquid drops capture VOCs in the bubbles. Preferably, the dilute phase is an aqueous solution containing inorganic and/or organic acid salts.
In some embodiments of the present invention, preferably, the concentration of the inorganic salt and/or organic acid salt in the dilute phase is 0.1 to 20mol/L, preferably 1 to 10mol/L.
In the present invention, there is a wide range of selection of the kind of the dilute phase as long as the concentration of the inorganic salt and/or organic acid salt in the aqueous solution containing the inorganic salt and/or organic acid salt satisfies the above-mentioned limitation. In the invention, the inorganic salt and/or the organic acid salt are each independently a soluble salt, wherein the solubility means that the salt is easily soluble in water or is dissolved in water under the action of an auxiliary agent.
In some embodiments of the present invention, preferably, when the dilute phase is an aqueous solution containing an inorganic salt selected from at least one of nitrate, sulfate, hydrochloride, and phosphate; further preferably, the cation in the inorganic salt is at least one selected from the group consisting of lithium ion, potassium ion, sodium ion, magnesium ion and ammonium ion, for example, sodium sulfate, sodium chloride, ammonium chloride, magnesium nitrate, ammonium sulfate, lithium nitrate, ammonium phosphate, magnesium sulfate and the like.
In a real-time mode of the present invention, preferably, when the dilute phase is an aqueous solution containing an organic acid salt, the organic acid salt is at least one selected from citrate, oxalate and acetate; further preferably, the cation in the organic acid salt is at least one selected from potassium ion, sodium ion, magnesium ion and ammonium ion, for example, sodium citrate, sodium oxalate, ammonium acetate, potassium oxalate and the like.
In the present invention, the capture phase acts as an absorbent for capturing VOCs in the feed gas containing VOCs. Preferably, the capture phase is a solution containing capture functional molecules of VOCs.
In the present invention, the VOCs trapping functional molecule has a wide selection range. Preferably, the VOCs capture functional molecules are selected from at least one of polymers, organic sugars, ionic liquids, and surfactants.
In one embodiment of the present invention, preferably, when the VOCs-trapping functional molecule is a polymer, the trapping phase is an aqueous polymer solution, the concentration of the polymer in the aqueous polymer solution is 10 to 50%, and the weight average molecular weight of the polymer is 1500 to 20000g/mol.
In some embodiments of the present invention, preferably, the polymer is selected from at least one of polyethylene glycol, polyethylene oxide-propylene oxide block copolymer, polyoxyethylene-polyoxypropylene random copolymer, polyoxyethylene fatty acid esters, and polyoxyethylene fatty alcohol ether polymers.
In one embodiment of the present invention, preferably, when the VOCs capture functional molecules are organic sugars, the capture phase is an aqueous organic sugar solution, the concentration of the organic sugars in the aqueous organic sugar solution is 50-200g/L, and the organic sugars are at least one selected from glucose, maltose, sucrose, xylose, fructose and galactose.
In one embodiment of the present invention, preferably, when the VOCs capture functional molecules are ionic liquids, the capture phase is a hydrophilic ionic liquid and/or a hydrophobic ionic liquid. More preferably, the trapping phase is composed of at least one cation selected from imidazoles, pyridines, quaternary ammonium salts and quaternary phosphonium salts and PF 6 - And/or N (CF) 3 SO 2 ) 2 - A hydrophobic ionic liquid comprising the anion of (a), or a hydrophobic ionic liquid comprising at least one cation selected from the group consisting of imidazoles, pyridines, quaternary ammonium salts and quaternary phosphonium salts and PF 4 - 、Cl - And Br - At least one kind of anion.
In one embodiment of the present invention, preferably, when the VOCs capture functional molecule is a surfactant, the capture phase is an aqueous surfactant solution, and the surfactant content in the aqueous surfactant solution is 5 to 30wt%.
In the present invention, it is further preferable that the surfactant is at least one selected from the group consisting of an anionic surfactant, a cationic surfactant, a polyoxyethylene type surfactant and a polyol type surfactant.
In some embodiments of the present invention, preferably, the anionic surfactant is selected from at least one of stearic acid, oleic acid, lauric acid, sodium dodecylsulfate, sodium hexadecylsulfate, sodium octadecyl sulfate, sodium dioctyl succinate, and sodium dodecylbenzene sulfonate.
In some embodiments of the present invention, preferably, the polyoxyethylene-type surfactant is selected from at least one of alkylphenol ethoxylates (APEO), octylphenol polyoxyethylene ether, and higher fatty alcohol polyoxyethylene ether (AEO).
In some embodiments of the present invention, preferably, the polyol-type surfactant is selected from at least one of sorbitan ester, tween and alkyl alcohol amine. Wherein the sorbitan ester may be a sorbitan fatty acid ester (span).
In the present invention, the VOCs trapping functional droplets are self-assembled aggregates of the VOCs trapping functional molecules, unless otherwise specified.
In the invention, the VOCs trapping functional liquid drop is an amphiphilic organic molecule with a compatibilization effect on VOCs molecules, has a hydrophobic end and a hydrophilic end, forms a self-assembly agglomerate in a dilution phase, and continuously collides with bubbles dispersed into a VOCs-containing feed gas to contact with the mass transfer, so that the VOCs are continuously solubilized into micelles.
In some embodiments of the present invention, it is preferable that the diameter of the VOCs trapping functional droplets is 0.1 to 5mm, preferably 0.5 to 3mm.
In the present invention, the range of the diameters of the droplets of the VOCs trapping function depends on the pore size of the liquid distributor without specific description.
By adopting the method provided by the invention, the content of VOCs in the purified gas can be effectively reduced. Preferably, the content of VOCs in the purified gas is 0.1-1g/cm 3 Preferably 0.3 to 0.8g/cm 3 。
In the present invention, the condensed capture phase is an aggregate of droplets of the VOCs capture function that captures VOCs, unless otherwise specified.
In the present invention, the regeneration is intended to desorb the VOCs captured in the concentrated trap phase. Preferably, in step (2), the regeneration process comprises: and contacting the concentrated trapping phase with a heat exchange medium to desorb the VOCs captured in the concentrated trapping phase.
In some embodiments of the present invention, preferably, the desorption conditions comprise: the temperature is 90-180 ℃, preferably 120-150 ℃; the time is 0.5-20min, preferably 5-10min. Preferred conditions are used to facilitate desorption and/or release of the VOCs from the concentrated capture phase enriched in VOCs, thereby facilitating regeneration of the capture phase.
In the present invention, there is a wide range of choices for the type of heat exchange medium. Preferably, the heat exchange medium is selected from at least one of saturated steam, low pressure steam and hot water.
In some embodiments of the invention, preferably, the inlet temperature of the heat exchange medium is 120 to 220 ℃, preferably 140 to 180 ℃; the outlet temperature is 110 to 210 ℃ and preferably 130 to 170 ℃.
In the present invention, exchanging the regenerated capture phase against the purified gas is intended to reduce the temperature of the regenerated capture phase, thereby increasing the efficiency of the regenerated capture phase in capturing VOCs. Preferably, the ratio of the regenerated capture phase to the purge gas is from 1 to 30:1-100, preferably 1-50:1-80.
In some embodiments of the invention, preferably, the temperature of the regenerated capture phase after heat exchange is in the range of 30 to 60 ℃, preferably 35 to 50 ℃.
According to the invention, preferably, the step (3) also obtains heat-exchanged purified gas; further preferably, the method further comprises: and separating the purified gas after heat exchange, and removing residual regeneration trapping phase liquid drops of the purified gas after heat exchange.
According to the present invention, preferably, the method further comprises: and separating the purified gas after heat exchange from the fresh trapping phase, and returning the obtained supplementary trapping phase and mixing the supplementary trapping phase into the trapping phase.
According to a particularly preferred embodiment of the invention, the method comprises: (1) Dispersing the trapping phase in the diluted phase to form VOCs trapping functional liquid drops; introducing the raw gas containing VOCs into the diluted phase to form uniformly distributed bubbles containing the raw gas containing VOCs; the bubbles flow upwards in the diluted phase, the VOCs trapping functional liquid drops are attached to the surfaces of the bubbles, and parallel-flow mass transfer is carried out on VOCs in the bubbles and the VOCs trapping functional liquid drops, so that the VOCs in the bubbles are trapped by the VOCs trapping functional liquid drops, coalescence and phase separation are carried out, and a concentrated trapping phase for trapping VOCs and purified gas for removing VOCs are obtained;
(2) Regenerating the concentrated trapping phase to obtain a VOCs (volatile organic compounds) recovery gas and a regenerated trapping phase;
(3) Carrying out heat exchange on the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase;
wherein the retention time of the bubbles in the dilute phase is more than or equal to 30s;
in the step (1), the content of VOCs in the feed gas is 10-20g/cm 3 (ii) a The initial diameter of the bubbles is 0.5-1mm; the rising flow velocity of the bubbles is 0.3-0.4m/s; the diameter of the VOCs trapping functional liquid drop is 0.5-1.5mm; in the dilute phase, the concentration of inorganic salt is 2-5mol/L; the content of VOCs in the purified gas is 0.5-0.6g/cm 3 ；
In the step (2), the regeneration process comprises the following steps: contacting the concentrated trapping phase with a heat exchange medium to desorb the VOCs captured in the concentrated trapping phase, wherein the desorption temperature is 120-150 ℃, and the desorption time is 5-8min;
in the step (3), the volume ratio of the regeneration trapping phase to the purge gas is 1:50-60.
In a second aspect, the invention provides an apparatus for recovering VOCs in a biphasic cycle, the apparatus comprising: the concentration recovery tower, the regenerator and the heat exchanger are connected in sequence; wherein, the concentration recovery tower comprises a feeding dispersion area, a mass transfer trapping area and a flaring separation area;
the feeding dispersion area comprises a gas distributor and a liquid distributor, wherein the gas distributor is used for uniformly distributing raw gas containing VOCs (volatile organic compounds) to generate bubbles of the raw gas containing VOCs to enter the mass transfer trapping area, and the liquid distributor is used for uniformly dispersing a trapping phase to generate VOCs trapping functional liquid drops to enter the mass transfer trapping area;
the mass transfer trapping area is used for the gas bubble to flow upwards in the dilute phase, the surface of the gas bubble is attached with the VOCs trapping function liquid drop, and the VOCs in the gas bubble and the VOCs trapping function liquid drop are subjected to cocurrent mass transfer, so that the VOCs trapping function liquid drop captures the VOCs in the gas bubble;
the flaring separation area is used for carrying out coalescence and phase separation on VOCs trapping functional liquid drops for trapping VOCs in the bubble rising process to obtain a concentrated trapping phase and purified gas;
the regenerator is used for regenerating the concentrated trapping phase to obtain VOCs (volatile organic compounds) recovery gas and a regenerated trapping phase;
the heat exchanger is used for exchanging heat between the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase.
In the invention, the concentration and recovery tower is a gas-liquid three-phase mass transfer separation device, the concentration and recovery tower sequentially comprises a feed dispersion area, a mass transfer trapping area and a flaring separation area from bottom to top, wherein the feed dispersion area is also provided with a raw material gas inlet and a trapping phase inlet which are respectively used for introducing the raw material gas containing VOCs into a dilution phase of the mass transfer trapping area through the gas distributor to form uniformly distributed bubbles of the raw material gas containing VOCs, and dispersing the trapping phase into the dilution phase of the mass transfer trapping area through the liquid distributor to form VOCs trapping functional liquid drops. In the present invention, the arrangement of the feed gas inlet and the trapped phase inlet depends on the positions of the gas distributor and the liquid distributor, respectively.
According to the invention, preferably, the height ratio of the feed dispersion zone, the mass transfer trapping zone and the flaring dispersion zone is 1-4:8-15:1-4, preferably 2-3:10-13:2-3; the diameter ratio is 1:1:3-6, preferably 1:1:4-5.
According to the invention, preferably, the bottom of the flaring dispersion zone is provided with a concentrated trapped phase outlet, and the concentrated trapped phase outlet is connected with the lower part of the regenerator.
According to the invention, preferably, the top of the flared dispersion zone is provided with a first wire mesh demister for removing VOCs capture function liquid droplets entrained by the purge gas.
According to the invention, preferably, the top of the regenerator is provided with a second wire mesh demister for removing the regeneration trapping phase carried by the recovered gas of the VOCs; further preferably, the lower part of the regenerator is provided with a heat medium inlet and a heat medium outlet for contacting the concentrated capture phase with the heat medium and regenerating.
According to the present invention, preferably, the apparatus further comprises: and the separator is further preferably connected with an outlet of the heat exchanger and used for separating the heat-exchanged purified gas.
In some embodiments of the present invention, preferably, the outlet of the separator is further connected to the concentration and recovery tower, and is used for separating the heat-exchanged purified gas from the fresh capture phase, and returning and mixing the obtained supplement capture phase into the capture phase.
In accordance with a preferred embodiment of the present invention, a two-phase recycle VOCs recovery apparatus is schematically illustrated in FIG. 1, and comprises: concentrated recovery tower I, regenerator II and heat exchanger III that connect gradually, the device still includes: a separator IV; wherein the concentration recovery tower I comprises a feed dispersing area I-1, a mass transfer trapping area I-2 and a flaring separation area I-3;
the feed dispersing area I-1 comprises a gas distributor I-4 and a liquid distributor I-5, wherein the gas distributor I-4 is used for introducing the raw gas 1 containing the VOCs into the dilution phase 3 of the mass transfer trapping area I-2 to form uniformly distributed bubbles of the raw gas containing the VOCs; the liquid distributor I-5 is used for dispersing the trapping phase 2 into the dilution phase 3 of the mass transfer trapping area I-2 to form VOCs trapping functional liquid drops 4; the VOCs trapping functional liquid drops 4 are self-assembly aggregates of VOCs trapping functional molecules 5, and the VOCs trapping functional molecules 5 comprise a hydrophobic end 6 and a hydrophilic end 7;
the mass transfer trapping area I-2 is used for the gas bubbles to flow in the diluted phase 3 in an ascending way, the VOCs trapping function liquid drops 4 are attached to the surfaces of the gas bubbles, and the VOCs in the gas bubbles and the VOCs trapping function liquid drops 4 are subjected to cocurrent mass transfer, so that the VOCs trapping function liquid drops 4 trap the VOCs in the gas bubbles;
the flaring separation area I-3 is used for collecting and separating the VOCs trapping functional liquid drops 4 of the VOCs to obtain a concentrated trapping phase 8 for trapping the VOCs and a purified gas 9 for removing the VOCs; a concentrated trapping phase outlet is formed in the bottom of the flaring dispersing area I-3 and connected with the lower part of the regenerator II; a first wire mesh demister I-6 is arranged at the top of the flaring dispersion area I-3 and is used for removing VOCs trapping functional liquid drops 4 carried by the purified gas 9;
the regenerator II is used for regenerating the concentrated trapping phase 8 to obtain a VOCs (volatile organic compounds) recovery gas 10 and a regenerated trapping phase 11; the top of the regenerator II is provided with a second wire mesh demister II-1 for removing a regeneration trapping phase 11 carried by the VOCs recycled gas 10; the lower part of the regenerator II is provided with a heat exchange medium inlet II-2 and a heat exchange medium outlet II-3 which are used for contacting the concentrated trapping phase 8 with a heat exchange medium so as to desorb VOCs captured in the concentrated trapping phase 8;
the heat exchanger III is used for exchanging heat between the regeneration trapping phase 11 and the purified gas 9, returning the obtained regenerated trapping phase 12 after heat exchange to be mixed into the trapping phase 2, and obtaining purified gas 13 after heat exchange;
the separator IV is connected with the outlet of the heat exchanger III and is used for separating the heat-exchanged purified gas 13 to obtain separated purified gas 15;
the outlet of the separator IV is also connected to the feed dispersion zone I-1 of the concentration recovery column I for separating the heat exchanged purified gas 13 from the fresh capture phase 14 and returning and mixing the obtained make-up capture phase 16 into the capture phase 1.
The present invention will be described in detail below by way of examples.
Example 1
In a two-phase recycle VOCs recovery plant as shown in FIG. 1; wherein, the height ratio of the feeding dispersion zone, the mass transfer trapping zone and the flaring dispersion zone is 1;
(1) The capture phase (EOPO 2500 solution with a content of 40 wt%) was dispersed in a dilute phase (3 mol/L in concentration of (NH) 4 ) 2 SO 4 Aqueous solution) to form VOCs trapping functional liquid drops (the diameter is 0.1-0.5 mm); raw material gas containing VOCs (VOCs waste gas mainly containing oxygen organic matters generated by a coal chemical engineering MTO device, wherein the content of VOCs in the raw material gas is 80-100g/cm 3 ) Introducing into the diluted phase to form bubbles with initial diameter of 0.1-0.5mm (flow rate of 0.2 m/s); the bubbles (ascending flow velocity of 0.2 m/s) flow in the diluted phase in an ascending manner, the VOCs trapping function liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs trapping function liquid drops are subjected to cocurrent mass transfer, so that the VOCs trapping function is realizedThe liquid drops capture the VOCs in the bubbles and carry out coalescence and phase separation to obtain a concentrated capture phase for capturing the VOCs and the content of the VOCs is 0.1-0.5g/cm 3 The purified gas of (4);
wherein the residence time of the gas bubbles in the dilute phase is 34s;
(2) Contacting the concentrated trapping phase with hot water to desorb the VOCs captured in the concentrated trapping phase to obtain VOCs recovered gas and a regenerated trapping phase; wherein the desorption conditions comprise: the temperature is 90 ℃ and the time is 20min; the inlet temperature of the hot water is 120 ℃, and the outlet temperature of the hot water is 110 ℃;
(3) Carrying out heat exchange on the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase, wherein the temperature of the regenerated trapping phase after heat exchange is 30 ℃; the volume ratio of the regeneration trapping phase to the purge gas is 1.
Example 2
In a two-phase recycle VOCs recovery plant as shown in FIG. 1; wherein the height ratio of the feeding dispersion area to the mass transfer trapping area to the flaring dispersion area is 3.
(1) The trapped phase (20 wt% sucrose aqueous solution) was dispersed in a dilute phase (8 mol/L LiNO) 3 Aqueous solution) to form VOCs trapping functional liquid drops (the diameter is 2-3 mm); the raw material gas containing VOCs (VOCs waste gas which is generated by petrochemical MTO device and mainly contains hydrocarbon organic matters, and the content of VOCs in the raw material gas is 0.1-1g/cm 3 ) Introducing into the diluted phase to form bubbles with initial diameter of 1.5-2mm (flow rate of 0.5-0.6 m/s); the bubbles (with the upward flow velocity of 0.5-0.6 m/s) flow in the dilute phase in an upward manner, the VOCs capture function liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs capture function liquid drops carry out cocurrent mass transfer, so that the VOCs in the bubbles are captured by the VOCs capture function liquid drops, coalescence and phase separation are carried out, and a concentrated capture phase for capturing the VOCs and the content of the VOCs is 0.1-0.3g/cm 3 The purified gas of (4);
wherein the residence time of the gas bubbles in the dilute phase is 40s;
(2) Contacting the concentrated trapping phase with hot water to desorb the VOCs captured in the concentrated trapping phase to obtain VOCs recovered gas and a regenerated trapping phase; wherein the desorption conditions comprise: the temperature is 180 ℃ and the time is 0.5min; the inlet temperature of the hot water is 220 ℃, and the outlet temperature of the hot water is 210 ℃;
(3) Carrying out heat exchange on the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase, wherein the temperature of the regenerated trapping phase after heat exchange is 60 ℃; the volume ratio of the regeneration trapping phase to the purge gas is 1.
Example 3
In a two-phase recycle VOCs recovery plant as shown in FIG. 1; wherein, the height ratio of the feeding dispersion area, the mass transfer trapping area and the flaring dispersion area is 4.
(1) The collected phase (40 wt% 4-methylimidazolium hexafluoroborate aqueous solution) was dispersed in a dilute phase (0.1 mol/L (NH) 4 ) 3 PO 4 Aqueous solution) to form VOCs trapping functional liquid drops (the diameter is 1-2 mm); raw material gas containing VOCs (VOCs waste gas mainly containing trimethylamine and generated by liquid crystal screen production device, wherein the content of VOCs in the raw material gas is 50-80g/cm 3 ) Introducing into the diluted phase to form bubbles with initial diameter of 1-1.5mm (flow rate of 0.3-0.5 m/s); the bubbles (with the upward flow velocity of 0.3-0.5 m/s) flow in the diluted phase in an ascending way, the VOCs trapping functional liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs trapping functional liquid drops perform cocurrent flow mass transfer, so that the VOCs in the bubbles are trapped by the VOCs trapping functional liquid drops, and are subjected to coalescence and phase separation to obtain a concentrated trapping phase for trapping VOCs and a VOCs content of 0.5-0.8g/cm 3 The purified gas of (3);
wherein the residence time of the bubbles in the dilute phase is 50s;
(2) Contacting the concentrated trapping phase with hot water to desorb the VOCs captured in the concentrated trapping phase to obtain VOCs recovered gas and a regenerated trapping phase; wherein the desorption conditions comprise: the temperature is 150 ℃, and the time is 10min; the inlet temperature of the steam is 180 ℃, and the outlet temperature is 170 ℃;
(3) Carrying out heat exchange on the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase, wherein the temperature of the regenerated trapping phase after heat exchange is 45 ℃; the volume ratio of the regeneration trapping phase to the purge gas is 1.
Example 4
In a two-phase recycle VOCs recovery plant as shown in fig. 1; wherein the height ratio of the feeding dispersion area to the mass transfer trapping area to the flaring dispersion area is 3.
(1) Dispersing a trapping phase (sodium dodecyl sulfate aqueous solution with the content of 5 wt%) in the diluted phase (NaCl aqueous solution with the concentration of 10 mol/L) to form VOCs trapping functional liquid drops (the diameter is 0.5-2 mm); raw material gas containing VOCs (VOCs waste gas generated by pharmaceutical device and mainly using ethyl acetate, the content of VOCs in the raw material gas is 40-60g/cm 3 ) Introducing into the diluted phase to form bubbles with diameter of 1-1.5mm (flow rate of 0.4-0.5 m/s); the bubbles (with the upward flow velocity of 0.4-0.5 m/s) flow in the diluted phase in an ascending way, the VOCs trapping functional liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs trapping functional liquid drops perform cocurrent flow mass transfer, so that the VOCs in the bubbles are trapped by the VOCs trapping functional liquid drops, and are subjected to coalescence and phase separation to obtain a concentrated trapping phase for trapping VOCs and a VOCs content of 0.5-0.6g/cm 3 The purified gas of (4);
wherein the residence time of the bubbles in the dilute phase is 38s;
(2) Contacting the concentrated trapping phase with saturated steam to desorb the VOCs captured in the concentrated trapping phase to obtain VOCs recovered gas and a regenerated trapping phase; wherein the desorption conditions comprise: the temperature is 160 ℃, and the time is 8min; the inlet temperature of saturated steam is 140 ℃, and the outlet temperature of saturated steam is 130 ℃;
(3) Carrying out heat exchange on the regeneration trapping phase and purified gas, and returning the obtained regenerated trapping phase subjected to heat exchange and mixing the regenerated trapping phase into the trapping phase, wherein the temperature of the regenerated trapping phase subjected to heat exchange is 50 ℃; the volume ratio of the regeneration trapping phase to the purge gas is 1.
Example 5
In a two-phase recycle VOCs recovery plant as shown in fig. 1; wherein, the height ratio of the feeding dispersion zone, the mass transfer trapping zone and the flaring dispersion zone is 2.
(1) Dispersing a trapping phase (10 wt% Tween 80 aqueous solution) in the diluted phase (K with the concentration of 6 mol/L) 2 C 2 O 4 Aqueous solution) to form VOCs trapping functional liquid drops (the diameter is 3-4 mm); raw material gas containing VOCs (VOCs waste gas produced by printing device and mainly containing benzene series, and VOCs content in raw material gas is 50-80g/cm 3 ) Introducing into the diluted phase to form bubbles with diameter of 0.8-1.4mm (flow rate of 0.3-0.5 m/s); the bubbles (with the upward flow velocity of 0.3-0.5 m/s) flow in the dilute phase in an upward manner, the VOCs capture function liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs capture function liquid drops carry out cocurrent mass transfer, so that the VOCs in the bubbles are captured by the VOCs capture function liquid drops, coalescence and phase separation are carried out, and a concentrated capture phase for capturing the VOCs and the content of the VOCs is 0.6-0.7g/cm 3 The purified gas of (4);
wherein the residence time of the bubbles in the dilute phase is 35s;
(2) Contacting the concentrated trapping phase with a heat medium to desorb the VOCs captured in the concentrated trapping phase to obtain VOCs recovered gas and a regenerated trapping phase; wherein the desorption conditions comprise: the temperature is 160 ℃, and the time is 13min; the inlet temperature of the heat medium is 130 ℃, and the outlet temperature is 140 ℃;
(3) Carrying out heat exchange on the regeneration trapping phase and purified gas, and returning the obtained regenerated trapping phase subjected to heat exchange and mixing the regenerated trapping phase into the trapping phase, wherein the temperature of the regenerated trapping phase subjected to heat exchange is 40 ℃; the volume ratio of the regeneration trapping phase to the purge gas is 1.
Example 6
In a two-phase recycle VOCs recovery plant as shown in FIG. 1; wherein, the height ratio of the feeding dispersion zone, the mass transfer trapping zone and the flaring dispersion zone is 1.
(1) Dispersing a trapping phase (25 wt% oleic acid aqueous solution) in the diluted phase (3 mol/L concentration)Sodium citrate aqueous solution) to form VOCs trapping functional liquid drops (the diameter is 3-5 mm); raw material gas containing VOCs (VOCs waste gas mainly containing oxygen organic matters generated by a water treatment device, wherein the content of VOCs in the raw material gas is 80-94g/cm 3 ) Introducing into the diluted phase to form bubbles with diameter of 0.4-0.8mm (flow rate of 0.4-0.5 m/s); the bubbles (with the upward flow velocity of 0.4-0.5 m/s) flow in the dilute phase in an upward manner, the VOCs capture function liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs capture function liquid drops carry out cocurrent mass transfer, so that the VOCs in the bubbles are captured by the VOCs capture function liquid drops, coalescence and phase separation are carried out, and a concentrated capture phase for capturing the VOCs and the content of the VOCs is 0.6-0.7g/cm 3 The purified gas of (4);
wherein the residence time of the bubbles in the dilute phase is 37s;
(2) Contacting the concentrated trapping phase with a heat medium to desorb the VOCs captured in the concentrated trapping phase to obtain VOCs recovered gas and a regenerated trapping phase; wherein the desorption conditions comprise: the temperature is 120 ℃, and the time is 15min; the inlet temperature of the heat medium is 190 ℃ and the outlet temperature is 180 ℃;
(3) Carrying out heat exchange on the regeneration trapping phase and a purified gas, and returning the obtained regenerated trapping phase subjected to heat exchange and mixing the regenerated trapping phase into the trapping phase, wherein the temperature of the regenerated trapping phase subjected to heat exchange is 37 ℃; the volume ratio of the regeneration trapping phase to the clean gas is 1.
Example 7
In a two-phase recycle VOCs recovery plant as shown in FIG. 1; wherein the height ratio of the feeding dispersion area to the mass transfer trapping area to the flaring dispersion area is 2.
(1) The collected phase (25 wt% oleic acid aqueous solution) was dispersed in a dilute phase (7 mol/L MgSO. RTM 4 Aqueous solution) to form VOCs trapping functional liquid drops (the diameter is 3-5 mm); raw material gas containing VOCs (VOCs waste gas mainly containing tetrahydrofuran and generated by a petrochemical processing device, wherein the content of VOCs in the raw material gas is 30-40g/cm 3 ) Uniformly distributed in the dilute phase to form bubbles with the diameter of 1-1.5mm (the flow rate is 0.3-0.4 m/s); the bubbles (upflow stream)Speed of 0.3-0.4 m/s) rises and flows in the dilute phase, and performs parallel-flow mass transfer with the VOCs trapping functional liquid drop, so that the VOCs in the bubbles are trapped by the VOCs trapping functional liquid drop, coalescence and phase separation are performed, and a concentrated trapping phase for trapping VOCs and VOCs content of 0.6-0.8g/cm are obtained 3 The purified gas of (4);
wherein the residence time of the bubbles in the dilute phase is 36s;
(2) Contacting the concentrated trapping phase with hot water to desorb the VOCs captured in the concentrated trapping phase to obtain VOCs recovered gas and a regenerated trapping phase; wherein the desorption conditions comprise: the temperature is 165 ℃ and the time is 8min; the inlet temperature of the hot water is 190 ℃ and the outlet temperature is 180 ℃;
(3) Carrying out heat exchange on the regeneration trapping phase and purified gas, and returning the obtained regenerated trapping phase subjected to heat exchange and mixing the regenerated trapping phase into the trapping phase, wherein the temperature of the regenerated trapping phase subjected to heat exchange is 35 ℃; the volume ratio of the regeneration trapping phase to the purge gas is 1.
Comparative example 1
According to the plant shown in fig. 1, the concentration recovery column does not comprise a gas distributor, however.
According to the method of the embodiment 1, except that in the step (1), the raw material gas containing the VOCs is directly introduced into the dilution phase of the mass transfer trapping area to carry out cocurrent mass transfer with the VOCs trapping functional liquid drops, and the rest steps are the same, so that the content of the VOCs is 20g/cm 3 The purified gas of (3).
Comparative example 2
According to the apparatus shown in FIG. 1, except that the concentration recovery column does not contain a liquid distributor.
The procedure of example 1 was followed, except that in the step (1), the bubbles (upflow velocity of 0.3 to 0.4 m/s) were upflowed in the dilute phase and subjected to cocurrent mass transfer with the trap phase, and the remaining steps were the same, to obtain a content of VOCs of 40g/cm 3 The purified gas of (1).
Comparative example 3
Absorbing VOCs-containing gas by adopting diesel oil, and carrying out mass transfer in a parallel flow mode by adopting an absorption tower, wherein the required liquid is as follows: the gas ratio needs to reach 1:10 above, however, except that nonpolar hydrocarbons are absorbed, the absorption effect of polar oxygen-containing organic matters such as alcohol, ether, ketone and lipid is poor, and the overall removal rate of VOCs is only 60%. A large amount of absorption phase needs to be thermally regenerated, and the energy consumption is high. For such VOCs gases, the treatment apparatus of the present invention can be used to treat a liquid: the gas ratio is reduced to 1.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for bi-phase recycle recovery of VOCs, comprising the steps of:
(1) Dispersing the trapping phase in the diluted phase to form VOCs trapping functional liquid drops; introducing the raw gas containing VOCs into the diluted phase to form uniformly distributed bubbles containing the raw gas containing VOCs; the bubbles flow upwards in the diluted phase, the VOCs capture function liquid drops are attached to the surfaces of the bubbles, and the VOCs in the bubbles and the VOCs capture function liquid drops perform cocurrent mass transfer, so that the VOCs in the bubbles are captured by the VOCs capture function liquid drops, coalescence and phase separation are performed, and a concentrated capture phase for capturing VOCs and a purified gas for removing VOCs are obtained;
(2) Regenerating the concentrated trapping phase to obtain a VOCs (volatile organic compounds) recovery gas and a regenerated trapping phase;
(3) Carrying out heat exchange on the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase;
wherein the residence time of the bubbles in the dilute phase is not less than 30s.
2. The method of claim 1, wherein the feed gas has a VOCs content of 0.1-100g/cm 3 Preferably 1 to 20g/cm 3 ；
Preferably, the initial diameter of the bubbles is 0.1 to 2mm, preferably 0.1 to 1.5mm;
preferably, the ascending flow velocity of the bubbles is 0.2 to 0.6m/s, preferably 0.3 to 0.5m/s;
preferably, the dilute phase is an aqueous solution containing inorganic and/or organic acid salts;
preferably, the concentration of the inorganic salt and/or organic acid salt in the dilute phase is 0.1 to 20mol/L, preferably 1 to 10mol/L.
3. The method of claim 1 or 2, wherein the capture phase is a solution containing capture functional molecules of VOCs;
preferably, the VOCs capture functional molecules are selected from at least one of polymers, organic sugars, ionic liquids, and surfactants;
preferably, the diameter of the VOCs trapping functional liquid drop is 0.1-5mm, preferably 0.5-3mm;
preferably, the content of VOCs in the purified gas is 0.1-1g/cm 3 Preferably 0.3 to 0.8g/cm 3 。
4. The method according to any one of claims 1-3, wherein in step (2), the regenerating comprises: contacting the concentrated capture phase with a heat exchange medium to desorb VOCs captured in the concentrated capture phase;
preferably, the desorption conditions include: the temperature is 90-180 ℃, preferably 120-150 ℃; the time is 0.5-20min, preferably 5-10min;
preferably, the inlet temperature of the heat exchange medium is 120-220 ℃, preferably 140-180 ℃; the outlet temperature is 110 to 210 ℃ and preferably 130 to 170 ℃.
5. The method of any of claims 1-4, wherein the volumetric ratio of the regeneration catch phase to the purge gas is from 1 to 30:1-100, preferably 1-50:1-80;
preferably, the temperature of the regenerated capture phase after heat exchange is 30-60 ℃, preferably 35-50 ℃;
preferably, the purified gas after heat exchange is obtained in the step (3);
preferably, the method further comprises: separating the heat-exchanged purified gas to remove residual regeneration trapping phase liquid drops of the heat-exchanged purified gas;
preferably, the method further comprises: and separating the purified gas after heat exchange from the fresh trapping phase, and returning the obtained supplementary trapping phase and mixing the supplementary trapping phase into the trapping phase.
6. An apparatus for recovering VOCs in a biphasic cycle, the apparatus comprising: the concentration recovery tower, the regenerator and the heat exchanger are connected in sequence; wherein, the concentration recovery tower comprises a feeding dispersion area, a mass transfer trapping area and a flaring separation area;
the feeding dispersion area comprises a gas distributor and a liquid distributor, wherein the gas distributor is used for introducing the raw gas containing the VOCs into the dilute phase of the mass transfer trapping area to form uniformly distributed bubbles of the raw gas containing the VOCs; the liquid distributor is used for dispersing the trapping phase into the dilute phase of the mass transfer trapping area to form VOCs trapping functional liquid drops;
the mass transfer trapping area is used for the gas bubble to flow in the dilution phase in an ascending way, the surface of the gas bubble is attached with the VOCs trapping function liquid drop, and the VOCs in the gas bubble and the VOCs trapping function liquid drop are subjected to cocurrent mass transfer, so that the VOCs trapping function liquid drop captures the VOCs in the gas bubble;
the flaring separation area is used for performing coalescence and phase separation on VOCs trapping functional liquid drops for trapping VOCs to obtain a concentrated trapping phase for trapping VOCs and a purified gas for removing VOCs;
the regenerator is used for regenerating the concentrated trapping phase to obtain VOCs (volatile organic compounds) recovered gas and a regenerated trapping phase;
the heat exchanger is used for exchanging heat between the regeneration trapping phase and the purified gas, and returning the obtained regenerated trapping phase after heat exchange and mixing the regenerated trapping phase into the trapping phase.
7. The apparatus of claim 6 wherein the height ratio of the feed dispersion zone, mass transfer trap zone and flared dispersion zone is from 1 to 4:8-15:1-4, preferably 2-3:10-13:2-3; the diameter ratio is 1:1:3-6, preferably 1:1:4-5.
8. The apparatus of claim 6 or 7, wherein the bottom of the flared dispersion zone is provided with a concentrated trapped phase outlet, and the concentrated trapped phase outlet is connected to the lower portion of the regenerator;
preferably, a first wire mesh demister is arranged at the top of the flaring dispersion area and is used for removing VOCs trapping function liquid drops entrained by the purified gas.
9. The apparatus of any one of claims 6-8, wherein a second wire mesh demister is arranged at the top of the regenerator for removing the regenerated capture phase entrained by the recovered gas of VOCs;
preferably, the lower part of the regenerator is provided with a heat exchange medium inlet and a heat exchange medium outlet, and the heat exchange medium inlet and the heat exchange medium outlet are used for contacting the concentrated capture phase with the heat exchange medium, so that the VOCs captured in the concentrated capture phase are desorbed.
10. The apparatus of any one of claims 6-9, wherein the apparatus further comprises: a separator for separating the liquid from the gas to be treated,
preferably, the separator is connected to an outlet of the heat exchanger, and is used for separating the heat-exchanged purified gas;
preferably, the outlet of the separator is further connected to the feed dispersion zone of the concentration and recovery tower, and is used for separating the heat-exchanged purified gas from the fresh capture phase, and returning and mixing the obtained supplement capture phase into the capture phase.
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