CN114797381B - VOCs waste gas green treatment process capable of reducing carbon emission - Google Patents
VOCs waste gas green treatment process capable of reducing carbon emission Download PDFInfo
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Abstract
The invention discloses a green treatment process for VOCs waste gas with reduced carbon emission, which is used for carrying out active dynamic membrane absorption treatment on industrial VOCs waste gas, and carrying out steps of bad aqueous solution membrane stripping treatment, biological carbon fixation treatment, sludge treatment and the like to realize biological carbon solidification in most VOCs, reduce carbon dioxide emission, reduce the dangerous waste production amount of the treatment process and lower the dangerous waste treatment cost; the VOCs treatment system has low energy consumption, low operation cost and stable operation effect, and can stably realize ultra-low concentration emission for a long time.
Description
Technical Field
The invention belongs to the field of waste gas treatment, and particularly relates to a green VOCs treatment process for reducing carbon emission.
Background
Volatile Organic Compounds (VOCs) are various organic compounds with boiling points of 50-260 ℃ under normal pressure. Therefore, the compounds contained in VOCs are relatively wide ranging, and include alcohols, aldehydes, ketones, fatty acids, benzene and its derivatives, phenols and its derivatives, and the like. In the development of industries such as petrochemical industry, medical synthesis, plastic materials, building materials and the like, the social life is greatly improved, and the economic level is greatly improved. Therefore, the treatment of VOCs waste gas becomes a hot spot of concern for researchers and enterprises in scientific research institutions.
The current common methods for treating VOCs waste gas are a catalytic combustion method, a photocatalysis method, a biological method and the like. The catalyst is adopted for catalytic combustion, so that the preparation cost is high, the catalyst for the photocatalysis method is simple, the energy consumption is low, and the application range is wide. The disadvantages are: the photocatalyst is required to be attached to a carrier and irradiated by ultraviolet light, so that the requirements on the internal structure of equipment and the carrier are strict in order to avoid insufficient illumination; when the concentration of the organic component is low, the photocatalytic oxidation speed is slow, harmful intermediate products are generated, the catalyst is poisoned, and secondary pollution is caused. The biological method mainly comprises the steps of capturing and degrading VOCs into CO by microorganisms in a filtering tank, a trickling filter tower or a regeneration tank 2 、H 2 Small molecule processes such as O. The biological method has mild operation conditions and can be carried out at normal temperature and normal pressure; the removal rate is high. However, the above treatments all have a common problem that the conversion of VOCs into carbon dioxide and water does not reduce the emission of carbon dioxide.
Therefore, the invention provides the VOCs waste gas treatment process capable of reducing carbon emission, which can effectively remove VOCs and solidify carbon in the VOCs at the same time, thereby achieving the aims of energy conservation and emission reduction.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a green treatment process for VOCs waste gas with reduced carbon emission, which carries out active dynamic membrane absorption treatment on industrial VOCs waste gas, and carries out steps of bad aqueous solution stripping treatment, biological carbon fixation treatment, sludge treatment and the like to realize the biological solidification of carbon in most VOCs, thereby reducing carbon dioxide emission, reducing the production amount of hazardous waste in the treatment process and having low hazardous waste treatment cost; the VOCs treatment system has low energy consumption, low operation cost and stable operation effect, and can stably realize ultra-low concentration emission for a long time.
The above object of the present invention can be achieved by the following technical solutions:
a green treatment process for VOCs waste gas with reduced carbon emission mainly comprises the following steps:
1) The active dynamic membrane absorption treatment, namely, the waste gas containing VOCs is contacted with an active circulating water solution, so that the active circulating water solution is atomized into water drops in the waste gas to form an active dynamic membrane, and the VOCs in the waste gas are rapidly dissolved in the active circulating water solution;
2) Recovering the atomized water drops into an active circulating water solution, and recycling the active circulating water solution;
3) Removing the film from the active circulating water solution, and transferring the active circulating water solution to perform film removal treatment when the waste gas after the active circulating water solution is treated is close to exceeding standard, so as to obtain scum and high-concentration COD (chemical oxygen demand) waste water; the stripping treatment is to add an active agent and a stripping catalyst into an active circulating water solution to layer the active circulating water solution, wherein the upper layer is scum, the lower layer forms high-concentration COD wastewater, and the stripping treatment realizes that toxic organic matters are removed in the form of scum and the attenuation treatment of the high-concentration COD wastewater;
4) Treating scum obtained by the stripping treatment in a dangerous waste mode, and pretreating high-concentration COD wastewater obtained by the stripping treatment;
5) Biological carbon fixation treatment, namely biological carbon fixation is carried out on the pretreated high COD wastewater to obtain biochemical sludge and clear water, the obtained clear water is used as circulating water to be added with an active agent and then is supplemented into the step 1) to obtain an active circulating water solution, and organic sludge formed by biological solidification is used as municipal sludge for treatment.
The active circulating water solution is an aqueous solution added with an active medicament, wherein the dosage ratio of clear water to the active medicament is 100:10-1; the active agent is one or more of sulfolane, paraffin oil, epoxidized soybean oil and surfactant; the flow ratio of the waste gas to the active circulating water solution is 500-3000:1, a step of; the active circulating water solution containing the active agent can promote the quick dissolution of VOCs in the active circulating water solution, thereby achieving the purpose of removing VOCs in the waste gas.
Further, the waste gas and the active circulating water solution can be contacted in various modes, including a gas-liquid mixer, a dynamic membrane generator, a spray tower, a jet device and the like, wherein the dynamic membrane generator is a Venturi gas-liquid mixer or a cavitation spray head, the active dynamic membrane in the step 1), namely the water solution, is atomized into tiny water drops, the active agent is dispersed on the surfaces of the water drops to form the active dynamic membrane, the surfaces of the water drops have higher surface tension, and the uniform dispersion of the active agent on the surfaces of the water drops is promoted; the active dynamic membrane promotes VOCs to be quickly dissolved in water drops, so that the aim of efficiently removing the VOCs is fulfilled; the exhaust gas containing VOCs can reach the emission standard after being absorbed and purified by the active dynamic membrane.
In the step 2), atomized water drops are recovered, on the one hand, the water drops with active agents are prevented from being discharged to the air, on the other hand, the active agents in the water drops can be recovered, in the step 2, the recovery adopts a conventional recovery mode, including but not limited to a mode of communicating with a spray tower, a cyclone separator, a packed tower and the like, preferably a spray tower is adopted for recovery, the solution adopted by the spray tower is the active circulating water solution adopted in the step 1), and a spraying mode adopts a high-flow spraying mode, on the other hand, tiny liquid drops can be prevented from being formed, and the treated waste gas is discharged to the air; on the other hand, the active dynamic membrane generated in the step 1) can be better absorbed and recycled by a large-flow spraying mode, the active medicament is effectively recycled, and the waste gas treated by the active dynamic membrane can be further treated by a large-flow active circulating water solution spraying mode, so that the absorption effect of VOCs in the waste gas is improved.
Furthermore, the active circulating water solution is shared by the processes of the step 1) and the step 2), so that the cost of process materials can be saved, and the main components of the active circulating water solution can be kept stable; and (3) performing stripping treatment on the active circulating water solution until the absorption performance of VOCs (volatile organic compounds) in the active circulating water solution does not reach the exhaust emission standard.
The specific step of the stripping treatment in the step 3) is to add an active agent into an active circulating water solution, wherein the active agent can enable the active circulating water solution to be layered, scum is formed on the upper layer, high-concentration COD wastewater is formed on the lower layer, the active agent is one or more of hydrogen peroxide, ozone, oxygen, fenton reagent, sodium hypochlorite, chlorine dioxide, chlorine and the oxidant, a stripping catalyst is required to be added into the circulating water in the stripping treatment process, the stripping catalyst is one or more of water-soluble aluminum salt, magnesium salt, ferric salt and copper salt, the stripping catalyst can promote the stripping of the circulating water, foam scum is formed on the upper layer, and high-concentration COD wastewater is formed on the lower layer; the adding amount of the active agent is 1-20 kg per cubic circulating water, the adding amount of the stripping catalyst is 0.5-10 kg per cubic circulating water, the main principle of stripping the stripping catalyst and the active agent is that the stripping catalyst is used for enabling the stripping active agent to react with organic matters in circulating liquid to polymerize and form foam scum, thus realizing stripping of the circulating liquid, and the stripping process can separate high-concentration and high-toxicity matters to be used as hazardous waste treatment until the lower layer solution is clear and stops stripping. The high-toxic substances in the pollutants are classified and dangerous to treat through the demolding treatment step, so that the influence of the high-toxic substances on subsequent biological curing is avoided, and the subsequent biological curing is protected, therefore, the demolding treatment in the step is also an indispensable part in the whole process treatment step, and is an organic whole.
Further, after the active circulating water solution is subjected to the stripping treatment, the COD of the circulating solution is generally 20000-50000mg/L.
In the step 4), dangerous waste treatment is carried out on filter residues generated by demolding; pretreating high-concentration COD wastewater, wherein the pretreatment of the high-concentration COD wastewater is coagulation air floatation, the used coagulant can be one or more of polyaluminium chloride and ferrous chloride, and the used flocculant is polyacrylamide. After pretreatment of the high-concentration COD wastewater, the COD is usually 15000-30000mg/L.
In the step 5), specific microorganisms are selected as heterotrophic aerobic microorganisms and autotrophic aerobic microorganisms, the concentration of the microorganisms is 3000-8000 mg/L, active microorganisms are cultured in the biological carbon fixation process, old and dead sludge and sludge with low activity are timely removed, the microorganisms are ensured to absorb more organic matters dissolved in water for growth and propagation of the microorganisms, and meanwhile the autotrophic microorganisms absorb carbon dioxide generated by the heterotrophic microorganisms, so that the microbial carbon fixation is realized; the organic sludge formed by biological solidification is treated as municipal sludge, and clear water obtained by biological solidification is recycled to the step 1).
Further, the method for removing the aged and dead sludge and the sludge with poor activity comprises the following steps: and in the standing sedimentation stage, the suspended sludge is discharged and removed, and in the aeration stage, the sludge deposited at the bottom of the water tank is discharged and removed by adopting a technology. Thus, the microorganism with higher activity is ensured to be remained in the reaction system for carbon fixation, and the dissolved organic matters are converted into active sludge instead of being decomposed into carbon dioxide. After biological carbon fixation treatment, COD in water is required to be lower than 2000mg/L.
Further, in the above-mentioned biological solidification process, the biological solidification is stopped when the COD of the water quality is lower than 2000mg/L, and the heterotrophic aerobic microorganisms may be microorganisms of the genus Acinetobacter, pseudomonas, alcaligenes, flavobacterium and the like which take soluble organic matters as carbon sources, and the autotrophic aerobic microorganisms are microorganisms of the genus Bacillus nitrate, helicobacter and coccus which take soluble carbonate matters as carbon sources. The heterotrophic aerobic microorganisms and the autotrophic aerobic microorganisms can be regulated and controlled by controlling operation parameters, and can also be regulated and controlled by microorganism inoculation or biological microbial inoculum addition, and the ratio of the heterotrophic aerobic microorganisms to the autotrophic aerobic microorganisms is 100: preferably 10 to 1.
Further, the biochemical sludge obtained in step 5) may be treated as municipal sludge.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts biological carbon fixation technology to realize the basically zero emission of VOCs, does not adopt high energy consumption technologies such as combustion or plasma, and has good effects of energy conservation and emission reduction.
(2) The treatment process adopted by the invention has mild conditions, high safety and wide application range, is favorable for large-scale popularization and application in industry, and has high economic and commercial values.
(3) The invention combines the active dynamic membrane absorption process, the circulating water stripping process and the biological carbon fixation process, the active dynamic membrane absorption process ensures the efficient removal of VOCs, and obtains the high-concentration COD active circulating water solution, thereby providing preconditions for the subsequent stripping treatment and biological solidification treatment; the stripping treatment can effectively separate and remove high toxic substances in the high-concentration wastewater, only needs to treat a small amount of hazardous waste, saves the treatment cost, provides favorable conditions for subsequent biological solidification, and realizes the green treatment of VOCs waste gas treatment without other pollution in the process.
(4) The process method provided by the invention has the advantages of less hazardous waste production amount and low hazardous waste disposal cost; the VOCs treatment system has low energy consumption and low operation cost.
(5) The VOCs provided by the invention has the advantages of high treatment efficiency, stable operation effect, capability of stably realizing ultralow concentration emission for a long time, mild treatment process conditions of all process steps and high safety.
Drawings
FIG. 1 is a process flow diagram of the treatment process of the present invention.
FIG. 2 is a schematic diagram of an apparatus for the treatment process of the present invention.
The device is marked as a 1-active dynamic membrane generator, a 2-spray tower recovery device, a 3-membrane removing device, a 4-coagulation air floatation tank and a 5-microorganism carbon fixing device in the attached drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the present invention. In addition, the technical features described below in the various embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
A green treatment process for VOCs for reducing carbon emission mainly comprises the following steps:
1) The active dynamic membrane absorption treatment, namely mixing and contacting organic waste gas and an active circulating water solution in a Venturi type gas-liquid mixer (1), namely an active dynamic membrane generator (1), wherein the maximum air quantity of the organic waste gas is 30000 cubic/hour; the usage amount of the active circulating water solution is 8 cubic meters, the adding amount of the active agent is 20 kilograms per cubic meter, and the flow ratio of the organic waste gas to the active circulating water solution is 1500:1.
2) The recovery of tiny water drops formed in the active dynamic membrane generator is realized by adopting a connected spray tower recovery device (2), the spray solution adopted by the spray tower is the active circulating water solution adopted in the step 1), and the spray mode adopts a high-flow spray mode, so that on one hand, tiny water drops can be prevented from being formed, and the treated waste gas is discharged into the air; on the other hand, the active dynamic membrane generated in the step 1) can be better absorbed and recycled by a large-flow spraying mode, the active medicament is effectively recycled, and the waste gas treated by the active dynamic membrane can be further treated by a large-flow active circulating water solution spraying mode, so that the absorption effect of VOCs in the waste gas is improved; the processes of step 1) and step 2) share an active circulating aqueous solution.
3) After the adopted active circulating water solution is continuously treated for 90 days, the continuous monitoring result of a third party environmental protection monitoring unit shows that after 90 days of continuous uninterrupted operation, the waste gas purification efficiency can meet the discharge standard requirement, and the active circulating water solution after 90 days of continuous treatment is introduced into a stripping device (3) for stripping treatment, so that the average production amount of foam scum is 36 kg/month; dangerous treatment is carried out on scum, filtrate after the demoulding treatment is introduced into a coagulation air floatation tank (4) for coagulation air floatation pretreatment, and the COD of the water solution is ensured to be 15000-30000mg/L
4) Introducing the waste liquid subjected to coagulation air floatation pretreatment into a microbial carbon fixing device (5) for carbon fixing treatment, namely biologically fixing carbon to the pretreated high COD waste water to obtain biochemical sludge and clear water, wherein the average production amount of the microbial carbon fixing sludge is 170 kg/month; the obtained clean water is used as circulating water for recycling, the active agent is directly recycled to the organic waste gas purifying system after being added into the circulating water according to 20 kg/cube, and the waste gas purifying efficiency is not obviously reduced. In addition, the organic sludge formed by biological solidification is treated as municipal sludge.
The process described by the invention is successfully applied to organic waste gas pollution control engineering of a coating line of an automobile part production enterprise. The maximum design treatment air quantity of the organic waste gas is 30000 cubic/hour, and the actual air quantity of the fan is regulated through a fan frequency converter so as to meet the requirements of an automatic spraying line on air quantity and air speed. The usage amount of the system active circulating water solution is 8 cubic meters, the adding amount of the active agent is 20 kilograms per cubic meter, and the flow ratio of the organic waste gas to the active circulating water solution is 1500:1. the design saturation time of the active circulating water is 90 days, and the continuous monitoring result of the third-party environmental protection monitoring unit shows that the waste gas purification efficiency can meet the emission standard requirement after 90 days of continuous uninterrupted operation. The saturated active circulating liquid is clear and transparent in sense after being treated, has no smell, is directly reused in an organic waste gas purifying system after being added with active medicaments according to 20 kg/cube, and has no obvious reduction of waste gas purifying efficiency. The average production amount of foam scum in the organic waste gas pollution treatment engineering is 36 kg/month, and the average production amount of microorganism carbon fixation sludge is 170 kg/month.
Wherein, the concentration of the waste gas treated by the active dynamic membrane process is detected, the detection is entrusted to a third party, and the standard limit value of the waste gas is derived from the integrated emission standard of air pollution (GB 16297-1996). The detection results are shown in Table 1.
TABLE 1
The atmospheric pollutant limit value in the second table meets the maximum allowable emission concentration of surface coating in the third table of DB51/2377-2017 of the emission standard of atmospheric volatile organic compounds of fixed pollution sources of Sichuan province.
The active circulating water solution runs for more than 150 days continuously, and can ensure that the waste gas is discharged up to the standard after being treated.
The embodiments herein are not exhaustive of the values of points in the technical scope of the invention claimed, and new technical solutions formed by equivalent substitution of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the invention claimed, and all the parameters involved in the solutions of the invention are not mutually and non-replaceable unique combinations unless specifically stated.
It will be readily understood by those skilled in the art that the foregoing description is merely illustrative of the presently preferred embodiments of the invention and is not intended to limit the invention to the particular forms disclosed, but to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. The green treatment process for the VOCs waste gas for reducing carbon emission is characterized by comprising the following steps of:
1) The active dynamic membrane absorption treatment, the waste gas containing VOCs is contacted with the active circulating water solution, so that the active circulating water solution is atomized into water drops in the waste gas to form an active dynamic membrane, and the VOCs in the waste gas are rapidly dissolved in the active circulating water solution;
2) Recovering the atomized water drops into an active circulating water solution, and recycling the active circulating water solution;
3) The method comprises the steps of (1) performing film stripping treatment on an active circulating water solution, transferring the active circulating water solution to film stripping treatment when waste gas after the active circulating water solution is treated is close to exceeding standard, wherein the film stripping treatment is to add an active agent and a film stripping catalyst into the active circulating water solution to layer the active circulating water solution, wherein the upper layer is scum, and the lower layer forms high-concentration COD (chemical oxygen demand) waste water;
4) Treating scum obtained by the stripping treatment in a dangerous waste mode, and pretreating high-concentration COD wastewater obtained by the stripping treatment;
5) Biological carbon fixing treatment, namely biological carbon fixing is carried out on the pretreated high-concentration COD wastewater to obtain organic sludge and clear water, the obtained clear water is used as circulating water, added with an active agent and then supplemented into the step 1) to obtain an active circulating water solution, and the organic sludge formed by biological solidification is used as municipal sludge for treatment;
the biological carbon fixing treatment step cultures active microorganisms, timely removes old and dead sludge and sludge with poor activity, ensures that the microorganisms absorb more organic matters dissolved in water for growth and propagation of the microorganisms, and simultaneously, autotrophic microorganisms absorb carbon dioxide generated by heterotrophic microorganisms, thereby realizing the carbon fixing of the microorganisms;
the method for removing the aged and dead sludge and the sludge with poor activity comprises the following steps: a standing sedimentation stage, namely discharging and removing suspended sludge; in the aeration stage, timely discharging the sludge deposited at the bottom of the water tank;
the atomized water drops are recovered by a spray tower, a cyclone separator or a packed tower; the solution adopted by the spray tower is the active circulating water solution adopted in the step 1), and the spraying mode adopts a high-flow spraying mode;
the step 1) and the step 2) share the active circulating water solution, so that the cost of process materials can be saved, and the main components of the active circulating water solution can be kept stable; the active circulating water solution is subjected to stripping treatment until the absorption performance of VOCs (volatile organic compounds) of the active circulating water solution does not reach the exhaust emission standard;
the microorganisms selected by the biological carbon fixing process are heterotrophic aerobic microorganisms and autotrophic aerobic microorganisms, and the concentration of the microorganisms is 3000-8000 milligrams per liter.
2. The green treatment process for VOCs waste gas with reduced carbon emission according to claim 1, wherein the active circulating aqueous solution is an aqueous solution added with an active agent, and the dosage ratio of clear water to the active agent is 100:10-1; the active agent is one or more of sulfolane, paraffin oil, epoxidized soybean oil and surfactant.
3. The process for green treatment of VOCs off-gas with reduced carbon emissions according to claim 1 or 2, wherein the active agent is one or more of hydrogen peroxide, ozone, oxygen, fenton's reagent, sodium hypochlorite, chlorine dioxide, chlorine gas; the stripping catalyst is one or more of water-soluble aluminum salt, magnesium salt, ferric salt and copper salt; the addition amount of the active agent is 1-20 kg per cubic circulating water, and the addition amount of the stripping catalyst is 0.5-10 kg per cubic circulating water.
4. The green treatment process for the waste gas of VOCs for reducing carbon emission according to claim 1 or 2, wherein the scum is treated in a dangerous waste mode, the high-concentration COD waste water is subjected to coagulation air floatation treatment, the coagulant can be one or more of polyaluminium chloride and ferrous chloride, and the flocculant is polyacrylamide.
5. The process for green treatment of VOCs off-gas with reduced carbon emissions according to claim 1 or 2, wherein the heterotrophic aerobic microorganism is one or more of the genus acinetobacter, pseudomonas, alcaligenes, flavobacterium, and the autotrophic aerobic microorganism is one or more of the genus bacillus, helicobacter, and coccoid.
6. The process for green treatment of VOCs off-gas with reduced carbon emissions according to claim 1 or 2, wherein the ratio of heterotrophic aerobic microorganisms to autotrophic aerobic microorganisms is 100:10 to 1.
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