CN110496500B - Process for treating VOC (volatile organic compounds) in water phase by utilizing continuous adsorption and desorption - Google Patents
Process for treating VOC (volatile organic compounds) in water phase by utilizing continuous adsorption and desorption Download PDFInfo
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- CN110496500B CN110496500B CN201910767158.4A CN201910767158A CN110496500B CN 110496500 B CN110496500 B CN 110496500B CN 201910767158 A CN201910767158 A CN 201910767158A CN 110496500 B CN110496500 B CN 110496500B
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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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
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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
- B01D53/1425—Regeneration of liquid 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
- 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
Abstract
The invention belongs to the technical field of waste gas treatment, and provides a process for treating VOC (volatile organic compounds) by continuous adsorption and desorption in a water phase, which comprises the following steps of: s1, allowing VOC gas to flow in from the bottom, enriching organic matters in the gas at the bottom of the resin layer, and S2, spraying working solution downwards from the upper part, and enriching at the upper part of the resin layer; s3, desorbing the enriched organic matters from the resin layer by the downwards sprayed working solution, and accumulating the organic matters in the working solution; and S4, adsorbing and desorbing the working solution with the accumulated organic matters by using a targeted fixed bed adsorption device to obtain overflowing liquid and desorption liquid, wherein the overflowing liquid is the working solution, the step S2 is returned for cyclic utilization, and the desorption liquid is the concentrated solution of the organic matters in the VOC. Through the technical scheme, the problems of complex process, high operation cost and incomplete removal of low-concentration VOC waste gas in the prior art are solved.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and relates to a process for treating VOC (volatile organic compounds) in a water phase by utilizing continuous adsorption and desorption.
Background
Volatile Organic Compound (VOC) waste gas is a common pollutant discharged from petrochemical, pharmaceutical, printing and other industries, and includes hydrocarbons, ketones, esters, phenols, aldehydes, amines, nitriles and the like, which have toxicity and cause pollution to the atmospheric environment, but has economic recovery value, so that the VOC waste gas is treated by a common recovery method. The recovery method is to separate VOC by physical methods, such as temperature, pressure, selective adsorbent, selective permeable membrane and the like, and mainly comprises activated carbon adsorption, pressure swing adsorption, condensation and membrane separation technologies. The activated carbon adsorption method is low in price, but the activated carbon adsorption period is short, adsorption and desorption are frequent, the adsorption process is easy to block, the adsorbent activated carbon is short in service life, and the ineffective activated carbon is listed as solid hazardous waste; the pressure swing adsorption method has high recovery efficiency and no pollutants, but has higher technical operation cost, and the adsorption needs pressurization and the desorption needs decompression, so the method is less applied to environmental protection; the condensing method has simple recovery technology, but the exhaust gas leaving the condenser still contains VOC with quite high concentration and can not meet the environmental emission standard; the membrane separation method has simple flow, high separation efficiency, high recovery rate and no secondary pollution, but has high equipment cost, high pretreatment cost, high membrane element manufacturing cost and the problems of blockage and pollution.
For high-concentration VOC waste gas, the invention patent application with application number 201610271006.1 discloses a VOCs waste gas treatment method, which comprises the steps of collecting, absorbing, desorbing and turning wheel concentrating high-concentration, low-medium gas quantity and normal-pressure VOCs waste gas discharged in the production process of the industries such as medicine and chemical industry, recovering to obtain VOCs organic solvent, and purifying to realize the standard discharge of the gas. In the invention, the residual gas of VOCs discharged from the top of the absorption tower does not reach the standard, and a rotating wheel concentration unit is required to perform adsorption treatment, so that the waste gas treatment process is complex.
For low-concentration VOC waste gas, a catalytic oxidation method, an electrocatalysis method and an ozone oxidation method are mostly adopted, and the problems of high investment, high operation cost and incomplete removal exist.
Disclosure of Invention
The invention provides a process for treating VOC by continuous adsorption and desorption in a water phase, which solves the problems of complex process, high operation cost and incomplete removal of low-concentration VOC waste gas in the prior art.
The technical scheme of the invention is realized as follows:
a process for treating VOCs in an aqueous phase using continuous adsorption and desorption, comprising the steps of:
s1, enabling VOC gas to flow into the resin layer from the bottom, and enriching organic matters in the gas at the bottom of the resin layer;
s2, spraying working solution downwards from the upper part, and enriching at the upper part of the resin layer, wherein the process and the process of enriching organic matters at the bottom of the resin layer are carried out simultaneously or at intervals;
s3, desorbing the enriched organic matters from the resin layer by the working solution enriched in the resin layer, and accumulating the organic matters in the working solution;
and S4, adsorbing and desorbing the working solution with the accumulated organic matters to obtain overflowing liquid and desorption liquid, wherein the overflowing liquid is the working solution, the step S2 is returned for cyclic utilization, and the desorption liquid is the organic matter concentrated solution.
As a further technical solution, the downward speed of the working fluid in the resin layer in the step S2 is greater than the speed of the organic matter in the VOC gas in the step S1 that is enriched at the bottom of the resin layer.
As a further technical scheme, the inflow speed of the VOC gas in the step S1 is 0.01-0.3 BV/H, and the downward spraying speed of the working solution in the step S2 is 0.1-3 BV/H.
As a further technical scheme, the temperature of the resin bottom layer in the step S1 is 20-35 ℃.
As a further technical scheme, the resin layer material is macroporous adsorption resin, and the macroporous adsorption resin is one of HT-47 type, CAD-49 type, HT-PA, HT-PB, HT-B, HT-312 type and HT-1600 type macroporous adsorption resin.
As a further technical scheme, the adsorption speed in the step S4 is 0.4-0.6 BV/H, the adsorption temperature is 20-35 ℃, the desorption speed is 0.4-0.6 BV/H, and the desorption temperature is 20-55 ℃.
As a further technical scheme, the working solution consists of the following components in parts by weight: 10-90 parts of water, 0-1 part of sodium dodecyl benzene sulfonate, 0.1-3 parts of high-molecular polyether, 1-30 parts of ethanol, 800.1-0.5 part of tween and 0.1-3 parts of emulsifier, wherein the emulsifier is sorbitol fatty acid ester, phospholipid or glycolipid emulsifier.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the organic VOC and harmful substances in the waste gas are forcibly absorbed by water by adopting a physical method, transferred to the water phase and converted into COD (chemical oxygen demand) for recycling, the treatment process is simple for low-concentration VOC waste gas, the operation cost is low, the treated gas is discharged after reaching the standard, and the problems of complexity, high operation cost and incomplete removal of low-concentration VOC waste gas in the prior art are effectively solved.
2. In the invention, low-concentration VOC gas enters from the bottom, VOC organic matters in the gas are adsorbed by the resin layer and then are enriched at the bottom of the resin layer, working liquid flows from top to bottom and then forms a liquid-phase film on the upper part of the resin layer, so that the organic matters can be effectively prevented from continuously diffusing to the upper part of the resin, the organic matters in the waste gas can be effectively separated from the gas, the treated gas reaches the standard and is discharged, because the downward flowing speed of the working liquid is greater than the upward diffusion speed of the organic matters in the resin, the organic matters are desorbed from the resin layer by the downward flowing working liquid, the concentration of the organic matters are accumulated in the working liquid, and then the organic matters are adsorbed and desorbed by the targeting fixed adsorption device, so that the working liquid can be recycled, the desorbed liquid is the organic matter concentrated liquid in the waste gas and can be further utilized, therefore, the organic matters in the waste gas are successfully transferred to the water phase for recycling, and the organic matters are effectively separated from the gas, realizing clean production.
3. According to the invention, the material of the resin layer is macroporous adsorption resin, for VOC waste gas, the resistance of the resin layer is about 500-1000 Pa, VOC in the waste gas can be effectively adsorbed, VOC is enriched at the bottom of the resin layer, and a liquid phase film formed by downwards sprayed working solution on the upper part of the resin layer is a necessary path for gas to upwards diffuse.
4. In the prior art, after the organic matters in the gas are adsorbed and enriched in the resin, in order to desorb the organic matters from the resin, the adsorption process must be stopped, so that the technical problem that continuous adsorption and desorption cannot be realized exists.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 a process for treating carbon disulphide-containing waste gas in an aqueous phase using continuous adsorption and desorption, comprising the steps of:
s1, allowing waste gas containing carbon disulfide to flow in from the bottom of an absorption tower, wherein the volume concentration of the carbon disulfide in the waste gas is 10000ppm before the waste gas flows in, enriching the carbon disulfide in the waste gas at the bottom of a resin layer in the absorption tower after the waste gas flows in, wherein the enriching speed of the carbon disulfide in the waste gas at the bottom of the resin layer is 0.01-0.3 BV/H, the temperature at the bottom of the resin layer is 20-35 ℃, and the material of the resin layer is HT-47 type macroporous adsorption resin;
s2, spraying the working solution downwards at a speed of 0.1-3 BV/H from the upper part of the absorption tower, and then enriching the working solution at the upper part of the resin layer to form a liquid phase film to prevent the carbon disulfide in the waste gas from continuously rising, wherein the process and the process of enriching the carbon disulfide at the bottom of the resin layer are carried out simultaneously, and the working solution consists of the following components in parts by weight: 10 parts of water, 0.1 part of high-molecular polyether, 1 part of ethanol, 800.1 parts of tween and 0.1 part of sorbitol fatty acid ester emulsifier;
s3, because the downward spraying speed of the working solution is greater than the upward diffusion speed of the carbon disulfide in the waste gas in the resin layer, the enriched carbon disulfide is desorbed from the bottom of the resin layer by the working solution, and the carbon disulfide is accumulated in the working solution;
s4, adsorbing and desorbing the working solution accumulating the carbon disulfide by using a targeted fixed bed adsorption device, wherein the adsorption speed is 0.4-0.6 BV/H, the adsorption temperature is 20-35 ℃, the desorption speed is 0.4-0.6 BV/H, the desorption temperature is 20-55 ℃, an overflowing liquid and a desorption liquid are obtained, the overflowing liquid is the working solution, the working solution returns to the step S2 for cyclic utilization, and the desorption liquid is a carbon disulfide concentrated solution.
In the process, the gas flowing out of the upper part of the absorption tower is detected, and carbon disulfide is not detected.
Example 2 a process for treating a mercaptan-containing off-gas in an aqueous phase using continuous adsorptive desorption, comprising the steps of:
s1, enabling waste gas containing mercaptan to flow into the bottom of an absorption tower, wherein the volume concentration of the mercaptan in the waste gas is 8000ppm before the waste gas flows into the absorption tower, enriching the mercaptan in the waste gas at the bottom of a resin layer in the absorption tower, wherein the enriching speed of the mercaptan in the waste gas at the bottom of the resin layer is 0.01-0.3 BV/H, the temperature at the bottom of the resin layer is 20-35 ℃, and the resin layer is made of HT-PA type macroporous adsorption resin;
s2, spraying working liquid downwards from the upper part of the absorption tower at the speed of 0.1-3 BV/H, and then enriching the working liquid on the upper part of the resin layer to form a liquid-phase film to prevent mercaptan in the waste gas from continuously rising; the process and the process of enriching mercaptan at the bottom of the resin layer are carried out simultaneously, and the working solution consists of the following components in parts by weight: 90 parts of water, 1 part of sodium dodecyl benzene sulfonate, 3 parts of high molecular polyether, 30 parts of ethanol, 800.5 parts of tween and 3 parts of phospholipid emulsifier;
s3, because the downward spraying speed of the working solution is higher than the upward diffusion speed of the mercaptan in the waste gas in the resin layer, the working solution desorbs the enriched mercaptan from the bottom of the resin layer, and the mercaptan is accumulated in the working solution;
s4, adsorbing and desorbing the working solution accumulating the mercaptan by using a targeted fixed bed adsorption device, wherein the adsorption speed is 0.4-0.6 BV/H, the adsorption temperature is 20-35 ℃, the desorption speed is 0.4-0.6 BV/H, the desorption temperature is 20-55 ℃, an overflowing liquid and a desorption liquid are obtained, the overflowing liquid is the working solution, the working solution returns to the step S2 for cyclic utilization, and the desorption liquid is a mercaptan concentrated solution.
In the above process, the gas flowing out of the upper part of the absorption column was detected and no mercaptan was detected.
Example 3 a process for treating a sulfide-containing waste gas in an aqueous phase using continuous adsorption and desorption, comprising the steps of:
s1, enabling waste gas containing thioether to flow into an absorption tower from the bottom of the absorption tower, wherein before flowing, the volume concentration of thioether in the waste gas is 10000ppm, after flowing, the thioether in the waste gas is enriched at the bottom of a resin layer in the absorption tower, the enrichment speed of the thioether in the waste gas at the bottom of the resin layer is 0.01-0.3 BV/H, the temperature at the bottom of the resin layer is 20-35 ℃, and the material of the resin layer is CAD-47 type macroporous adsorption resin;
s2, spraying working liquid downwards from the upper part of the absorption tower at the speed of 0.1-3 BV/H, and then enriching the working liquid on the upper part of the resin layer to form a liquid-phase film to prevent thioether in the waste gas from continuously rising, wherein the process and the process of enriching the thioether at the bottom of the resin layer are carried out simultaneously; the working solution consists of the following components in parts by weight: 30 parts of water, 0.3 part of sodium dodecyl benzene sulfonate, 1 part of high-molecular polyether, 10 parts of ethanol, 800.2 parts of tween and 1 part of glycolipid emulsifier;
s3, because the downward spraying speed of the working solution is higher than the upward diffusion speed of the thioether in the waste gas in the resin layer, the enriched thioether is desorbed from the bottom of the resin layer by the working solution, and the thioether is accumulated in the working solution;
s4, adsorbing and desorbing the thioether accumulated working solution by using a targeted fixed bed adsorption device at the adsorption speed of 0.4-0.6 BV/H, the adsorption temperature of 20-35 ℃, the desorption speed of 0.4-0.6 BV/H and the desorption temperature of 20-55 ℃ to obtain overflowing liquid and desorption liquid, wherein the overflowing liquid is the working solution, the working solution returns to the step S2 for cyclic utilization, and the desorption liquid is thioether concentrated solution.
In the above process, the gas flowing out of the upper part of the absorption column was detected, and no thioether was detected.
Embodiment 4 a process for treating butyl acetate-containing waste gas in an aqueous phase using continuous adsorption and desorption, comprising the steps of:
s1, allowing waste gas containing butyl acetate to flow from the bottom of an absorption tower, wherein the volume concentration of butyl acetate in the waste gas is 8000ppm before the waste gas flows in, after the waste gas flows in, the butyl acetate in the waste gas is enriched at the bottom of a resin layer in the absorption tower, the enrichment speed of the butyl acetate in the waste gas at the bottom of the resin layer is 0.01-0.3 BV/H, the temperature at the bottom of the resin layer is 20-35 ℃, and the material of the resin layer is HT-312 macroporous adsorption resin;
s2, spraying working liquid downwards from the upper part of the absorption tower at the speed of 0.1-3 BV/H, and then enriching the working liquid on the upper part of the resin layer to form a liquid-phase film to prevent butyl acetate in waste gas from continuously rising, wherein the process is carried out at intervals with the process of enriching thioether at the bottom of the resin layer; the working solution consists of the following components in parts by weight: 50 parts of water, 0.5 part of sodium dodecyl benzene sulfonate, 2 parts of high-molecular polyether, 15 parts of ethanol, 800.3 parts of tween and 1.5 parts of sorbitol fatty acid ester emulsifier;
s3, because the downward spraying speed of the working solution is greater than the upward diffusion speed of the butyl acetate in the waste gas in the resin layer, the working solution desorbs the enriched butyl acetate from the bottom of the resin layer, and the butyl acetate is accumulated in the working solution;
s4, adopting a targeted fixed bed adsorption device to carry out adsorption and desorption on the working solution accumulating the butyl acetate, wherein the adsorption speed is 0.4-0.6 BV/H, the adsorption temperature is 20-35 ℃, the desorption speed is 0.4-0.6 BV/H, the desorption temperature is 20-55 ℃, obtaining overflowing liquid and desorption liquid, the overflowing liquid is the working solution, returning to the step S2 for cyclic utilization, and the desorption liquid is butyl acetate concentrated solution.
In the process, the gas flowing out of the upper part of the absorption tower is detected, and butyl acetate is not detected.
In the processes of embodiments 1 to 4, the periodic forced regeneration and the super-strong regeneration are performed when the resin is polluted, the forced regeneration is performed by using a sodium hypochlorite solution with a concentration of 0.5%, the forced regeneration is performed 1 to 3 times every two weeks, the super-strong regeneration is performed by using a sodium hypochlorite solution with a concentration of 1 to 10%, after headspace, after washing with water according to the residual amount of sodium hypochlorite, the forced regeneration is performed by using hydrochloric acid with a concentration of 1%, the forced regeneration is performed 1 time every two months, the regenerated and restored resin is returned to the step S3 for recycling, and the remained wastewater is biochemically treated and then discharged up to the standard.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A process for treating VOCs in an aqueous phase using continuous adsorption and desorption, comprising the steps of:
s1, the VOC gas flows into the resin layer from the bottom, organic matters in the gas are enriched at the bottom of the resin layer,
s2, spraying the working solution downwards from the upper part, and enriching at the upper part of the resin layer, wherein the process is carried out simultaneously with the process of enriching organic matters at the bottom of the resin layer;
s3, desorbing the enriched organic matters from the resin layer by the working solution enriched in the resin layer, and accumulating the organic matters in the working solution;
s4, adsorbing and desorbing the working solution of the accumulated organic matters to obtain overflowing liquid and desorption liquid, wherein the overflowing liquid is the working solution, the step S2 is returned for recycling, and the desorption liquid is an organic matter concentrated solution;
the working solution consists of the following components in parts by weight: 10-90 parts of water, 0-1 part of sodium dodecyl benzene sulfonate, 0.1-3 parts of high-molecular polyether, 1-30 parts of ethanol, 800.1-0.5 part of tween and 0.1-3 parts of emulsifier, wherein the emulsifier is sorbitol fatty acid ester, phospholipid or glycolipid emulsifier;
the downward speed of the working solution in the resin layer in the step S2 is greater than the speed of the organic matters in the VOC gas in the step S1 which are enriched at the bottom of the resin layer;
the resin layer is made of macroporous adsorption resin.
2. The process of claim 1, wherein the concentration rate of the organic substances in the VOC gas in the bottom of the resin layer in step S1 is 0.01-0.3 BV/H, and the spraying rate of the working solution downward in step S2 is 0.1-3 BV/H.
3. A process for the treatment of VOCs in an aqueous phase using continuous adsorptive desorption according to claim 1,
in the step S1, the temperature of the resin bottom layer is 20-35 ℃.
4. The process of claim 1, wherein the adsorption rate in step S4 is 0.4-0.6 BV/H, the adsorption temperature is 20-35 ℃, the desorption rate is 0.4-0.6 BV/H, and the desorption temperature is 20-55 ℃.
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