CN114887434A - VOCs treatment process for finished oil - Google Patents
VOCs treatment process for finished oil Download PDFInfo
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- CN114887434A CN114887434A CN202210481742.5A CN202210481742A CN114887434A CN 114887434 A CN114887434 A CN 114887434A CN 202210481742 A CN202210481742 A CN 202210481742A CN 114887434 A CN114887434 A CN 114887434A
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- waste gas
- activated carbon
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- vocs
- finished oil
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
- B01D50/60—Combinations of devices covered by groups B01D46/00 and B01D47/00
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a treatment process for VOCs in finished oil, which comprises the following steps: step 1, collecting waste gas from a finished oil transportation truck; step 2, arranging an atomizing head inside the prewashing tower, arranging a filler filtering layer below the atomizing head, and enabling the collected waste gas to pass through the lower part of the filler filtering layer and be in reverse contact with the spraying liquid for treatment to obtain the washed waste gas; step 3, conveying the washed waste gas to a membrane separation device through a fan for further separation and purification to obtain separated waste gas; step 4, conveying the separated waste gas to an active carbon treatment device, and further completing adsorption and purification treatment to obtain adsorbed waste gas; and 5, detecting VOCs (volatile organic chemicals) in the adsorbed waste gas, and discharging the waste gas after reaching the standard. The invention aims at the characteristic of high concentration of VOCs waste gas of the finished oil transportation truck loading, and selects the treatment process in a targeted manner to ensure that the treatment effect can reach the relevant requirements and emission standards after the waste gas passes through the treatment device.
Description
Technical Field
The invention relates to the field of waste gas treatment, in particular to a VOCs treatment process for finished oil.
Background
Generally, the exhaust gas exists in three forms, namely solid, liquid and gaseous, and more in gaseous form. In recent years, domestic advanced technology is vigorously developed and actively introduced, and the whole structure of the environmental protection industry is gradually improved. Especially, the treatment technology of waste gas and malodorous gas has more advanced development and wide application. At present, the VOCs treatment technology applied at home and abroad mainly comprises photocatalysis, ion method, absorption method, adsorption method, biodegradation method, combustion method, condensation method and the like.
The VOCs waste gas of the finished oil is a mixture consisting of hydrocarbons and non-hydrocarbons with different molecular sizes and chemical structures, and has the characteristics of low concentration and high gas content, and complex and variable components. Because the concentration of VOCs waste gas of the finished oil transportation truck is very high, the single treatment process cannot be efficiently and stably carried out so as to reach the relevant emission standard. The existing treatment effect on the waste gas of finished oil transportation and loading is not ideal, the most used process is an activated carbon adsorption process, the initial treatment effect of the process is barely up to the standard, but the efficiency is reduced after long-term operation, and all indexes can not stably reach the relevant national emission standards; meanwhile, the requirement of people on VOCs adsorption is higher and higher, and the traditional activated carbon is only suitable for adsorbing gas with low temperature, low humidity and low concentration, otherwise, the adsorption effect is greatly attenuated, the adsorption is easy to saturate, and the problem of frequent replacement is solved.
Disclosure of Invention
Aiming at the problem that the existing process for treating and adsorbing the waste gas of the finished oil transportation truck by using the activated carbon cannot meet the requirements of people in the prior art, the invention aims to provide a treatment process for VOCs of the finished oil.
The purpose of the invention is realized by adopting the following technical scheme:
a treatment process for VOCs in finished oil comprises the following steps:
step 1, carrying out closed treatment on a finished oil transportation truck, carrying out closed collection on generated waste gas, and sending the waste gas to a pre-washing tower to obtain collected waste gas;
step 2, arranging an atomizing head inside the prewashing tower, arranging a filler filtering layer below the atomizing head, and enabling the collected waste gas to pass through the lower part of the filler filtering layer and be in reverse contact with the spraying liquid for treatment to obtain the washed waste gas;
step 3, conveying the washed waste gas to a membrane separation device through a fan for further separation and purification to obtain separated waste gas;
step 4, conveying the separated waste gas to an active carbon treatment device, and further completing adsorption and purification treatment to obtain adsorbed waste gas;
and 5, detecting VOCs (volatile organic chemicals) in the adsorbed waste gas, and discharging the waste gas after reaching the standard.
Preferably, in the step 1, after the finished oil transportation truck is sealed, the waste gas is collected and sent to the prewashing tower under the action of the centrifugal fan.
Preferably, in step 1, the centrifugal fan comprises a suction port, a conveying air pipe and a motor.
Preferably, in the step 2, the filler filter layer is kept wet by spraying the spraying liquid in the atomizing head before use, the temperature of the spraying liquid is 20-55 ℃, and the spraying liquid is an organic solution.
Preferably, in the step 2, the organic solution includes heavy oil and/or engine oil.
More preferably, in the step 2, the organic solution is 46# refrigerator oil.
Preferably, in the step 2, the filler filtering layer is made of polypropylene hollow spheres with the diameter of 30-50 mm.
Preferably, in the step 3, a separation membrane is provided in the membrane separation device, and the separation membrane is a polymeric membrane for separation.
Preferably, in the step 3, the separation membrane is a microporous silicone rubber membrane, the thickness of the separation membrane is 10-100 μm, the porosity of the separation membrane is 30-80%, and the pore diameter of the separation membrane is 100-1000 nm.
Preferably, in step 3, the separation membrane uses hydrocarbon component as a permeation phase and air as a retention phase. The process of penetrating the membrane by the penetrating phase is that firstly the penetrating phase molecules are adsorbed, dissolved and attached on the membrane at the upstream side of the membrane, then permeate through the separation membrane under the action of the pressure difference and the concentration gradient driving force applied to the two sides of the separation membrane, and finally are desorbed from the downstream side of the membrane.
Preferably, in the step 3, the pressure of the washed waste gas passing through the separation membrane is 0.5-1 MPa, and the temperature is 25-35 ℃.
Preferably, in the step 4, an activated carbon filter layer is arranged in the activated carbon treatment device, the time for the separated waste gas to pass through the activated carbon filter layer is 10-30 min, an ultraviolet light source is further arranged in the activated carbon filter device, the wavelength is 325-385 nm, and the illumination intensity is 20-50 mW/cm 2 。
Preferably, in the step 4, the component in the activated carbon filter layer is modified activated carbon.
Preferably, the preparation method of the modified activated carbon comprises the following steps:
s1, activating the activated carbon particles by using a hot sulfuric acid solution, and sequentially washing, filtering and drying to obtain activated carbon;
s2, mixing strontium iodate and iodic acid, adding a mixed acid solution, and stirring until the strontium iodate and the iodic acid are completely dissolved to obtain a mixed liquid A;
s3, adding the activated carbon into the mixed liquid A, stirring and mixing uniformly, placing the mixture into a reaction kettle for reaction, and washing, filtering and drying the mixture in sequence to obtain a mixed solid B;
s4, mixing selenium powder into a sodium borohydride solution, dropwise adding a sodium molybdate solution, adding the mixed solid B, uniformly mixing, placing the mixture into a reaction kettle for reaction, and sequentially washing, filtering and drying to obtain the modified activated carbon.
More preferably, the preparation method of the modified activated carbon comprises the following steps:
s1, placing the activated carbon particles in a sulfuric acid solution, heating to 60-80 ℃, stirring for 2-4 hours, cooling to room temperature, aging for 8-12 hours, filtering out solids, washing with water to be neutral, and drying under reduced pressure to obtain activated carbon;
s2, weighing phosphoric acid, adding the phosphoric acid into hydrofluoric acid, and uniformly mixing to form a mixed acid solution; mixing strontium iodate powder and iodic acid powder together, adding the mixture into a mixed acid solution, and stirring at room temperature until all solids are dissolved to obtain a mixed liquid A;
s3, dispersing the activated carbon activator into the mixed liquid A, stirring for 0.5-1 h at room temperature, then pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a drying oven, heating to 200-240 ℃, carrying out heat preservation treatment for 36-60 h, taking out the reaction kettle, naturally cooling, filtering out a solid, washing to be neutral, and drying under reduced pressure to obtain a mixed solid B;
s4, weighing selenium powder, mixing with a sodium borohydride solution, and stirring uniformly at room temperature to form a mixed liquid C; mixing sodium molybdate with deionized water, and completely dissolving to form a sodium molybdate solution; firstly, dropwise adding a sodium molybdate solution into a continuously stirred mixed liquid C, then adding a mixed solid B, uniformly mixing at room temperature, pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven, heating to 180-220 ℃, carrying out heat preservation treatment for 24-48 h, taking out the reaction kettle, naturally cooling, filtering out a solid, washing to be neutral, and drying under reduced pressure to obtain the modified activated carbon.
Preferably, in the S1, the particle size of the activated carbon particles is 1.25-2.75 mm; the mass concentration of the sulfuric acid solution is 15-20%.
Preferably, in S1, the mass ratio of the activated carbon particles to the sulfuric acid solution is 1: 20-30.
Preferably, in the S2, in the mixed acid solution, the mass concentration of phosphoric acid is 85%, the mass concentration of hydrofluoric acid is 40%, and the mass ratio of phosphoric acid to hydrofluoric acid is 1: 0.2-0.4.
Preferably, in the S2, the mass ratio of the strontium iodate powder, the iodic acid powder and the mixed acid solution is 1.2-1.4: 1.76: 28.3-33.5.
Preferably, in S3, the mass ratio of the activated carbon activator to the mixed liquid A is 1: 12-15.
Preferably, in the S4, in the mixed liquid C, the mass fraction of the sodium borohydride solution is 5-10%, and the mass ratio of the selenium powder to the sodium borohydride solution is 1: 18.2-24.6; in the sodium molybdate solution, the mass ratio of sodium molybdate to deionized water is 1: 28.3-32.5; the mass ratio of the mixed solid B, the mixed liquid C and the sodium molybdate solution is 0.1-0.3: 1.2-1.6: 6-8.
The invention has the beneficial effects that:
1. the invention aims at the characteristic of high concentration of VOCs waste gas of the finished oil transportation truck loading, and selects the treatment process in a targeted manner to ensure that the treatment effect can reach the relevant requirements and emission standards after the waste gas passes through the treatment device.
2. The invention adopts pre-spraying absorption, membrane filtration separation and active carbon adsorption to carry out combined process purification treatment. The absorption solvent is adopted for pretreatment in the early stage, the interior of the spray tower is improved compared with the conventional design, in order to ensure that the waste gas is fully contacted with the liquid, the spray atomizing layer scientifically and reasonably arranges spray heads according to the internal structure of the spray tower, so that 'dead-angle-free' gas-liquid contact is achieved, and fine-particle oily molecules in the waste gas can be condensed and absorbed; in the middle period, unabsorbed waste gas enters a membrane filtration separation device, VOCs waste gas passing through the membrane filtration separation device is filtered and separated, and organic molecules can permeate through a membrane and be separated from the waste gas, so that the purpose of purifying peculiar smell is achieved; modified activated carbon is adopted in the later stage to strengthen the adsorption of VOCs, the modified activated carbon not only can absorb peculiar smell and adsorb harmful gas, but also has a degradation effect on Volatile Organic Compounds (VOC), so that the high removal efficiency of VOCs is ensured, and the effect of deep treatment is achieved.
3. The modified activated carbon is obtained by modifying strontium fluoiodate and then generating molybdenum diselenide in situ. Compared with unmodified activated carbon, the modified activated carbon prepared by the invention has excellent degradation capability, and the adsorption speed is additionally improved, so that the effect of one arrow and two carves is achieved.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a flow chart of the treatment process of VOCs in the finished oil of the present invention;
FIG. 2 is a schematic diagram of the equipment used in the finished oil VOCs remediation process of the present invention;
fig. 3 is an SEM image of the modified activated carbon prepared in example 1.
Reference numerals: the system comprises a prewashing tower-1, a first vacuum pump-2, a circulating absorption tank-3, a separation storage tank-4, a fan-5, a membrane separation device-6, a second vacuum pump-7, an active carbon treatment device-8, a desorption tank-9 and a chimney-10.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
Waste gas generated by the finished oil transportation truck is controlled in a fixed area by a sealed and collected air pipe, and is sent to each waste gas treatment unit for purification under the action of a centrifugal fan, so that the aim of environment-friendly emission is achieved. The specific analysis about the operation of each step is as follows:
1. pre-washing and absorbing:
the pre-absorption process collects and transports the exhaust gas to a multi-stage cross-flow wash tank where the gas is purified after passing horizontally through one or more packed beds. The filler is cleaned from the top, and the cleaning liquid is sprayed on the top of the filler and flows through the filler and then enters the circulating box. Organic solution (heavy oil and engine oil) is added into the circulating box to absorb VOCs molecules and the like. In the pre-washing step, organic solvent is selected as spraying liquid for pre-washing, the spraying liquid is uniformly sprayed into the filler through an atomizing head, and waste gas reversely contacts with the spraying liquid when penetrating through the filler layer, so that a certain treatment effect is achieved.
2. Gas membrane separation:
the basic principle of the membrane separation method is that the separation membrane made of special methods and materials has different permeability to different gas molecules, so that some gas molecules selectively permeate through the separation membrane and other gas molecules are prevented from permeating, and thus the separation of different components is realized. The separation membrane used in the invention is a polymer separation membrane, the hydrocarbon component is a permeable phase, and the air is a retention phase. The process of the permeation phase passing through the membrane is that the molecules of the permeation phase are firstly adsorbed, dissolved and attached on the membrane at the upstream side of the membrane, then permeate through the separation membrane under the action of the pressure difference and the concentration gradient driving force applied to the two sides of the separation membrane, and finally are desorbed from the downstream side of the membrane. In the step of membrane separation, when waste gas contacts the surface of the membrane material, organic matters can permeate the membrane, and enrichment and depletion are respectively achieved on the interception side and the permeation side of the membrane, so that the purpose of separation is achieved.
3. Activated carbon purification:
the activated carbon is a microcrystalline carbon material which is mainly made of carbon-containing materials, has black appearance, developed internal pore structure, large specific surface area and strong adsorption capacity. The difficulty of the existing adsorption treatment by using activated carbon is that the adsorption selectivity is poor, if gas moisture is too heavy or the temperature is too high or the concentration is large in the using process, the adsorption saturation can be caused very quickly, the adsorption effect is attenuated greatly, and the desorption is a laborious process which is easy to cause secondary pollution. In the step of treating the activated carbon, the activated carbon is modified, so that organic molecules, aromatic compounds, halogenated alkynes and the like can be firmly adsorbed on the surface or in gaps of the activated carbon, and importantly, the adsorbed organic substances can be degraded into pollution-free substances under the action of photocatalysis, and then desorption is carried out, so that the method is more environment-friendly and easier, and has great progress compared with the prior art.
Analysis of the modification process of the activated carbon according to the invention:
the active carbon selected by the invention is prepared by taking shells and sawdust as raw materials, and the specific surface area is 1000- 2 (g) total pore volume of 0.85-0.9cm 3 /g。
The modified active carbon is firstly subjected to heat treatment by a sulfuric acid solution, so that impurities in pores of the active carbon are removed, and the active carbon can be activated; then passing through strontium iodate (Sr (IO) 3 ) 2 ) With iodic acid (HIO) 3 ) Dissolving the strontium iodate under the action of mixed acid, carrying out solvothermal reaction on the activated carbon, and growing the strontium fluoiodate on the surface of the activated carbon to generate a strontium fluoiodate/activated carbon compound; then, reacting the selenium powder with sodium molybdate to generate molybdenum diselenide in situ on the surface of the strontium fluoiodate/active carbon compound, thereby finally obtaining the modified active carbon.
Molybdenum diselenide has a specific crystal structure and excellent thermodynamic properties, and thus is widely used in many fields such as photocatalysis, energy storage, solid lubrication, microelectronics, and photoelectricity. Molybdenum diselenide with photocatalysis is introduced into the modified activated carbon prepared by the invention, and VOCs adsorbed by the activated carbon can be catalytically degraded, so that pollution-free gas emission is formed. However, the molybdenum diselenide/active carbon compound prepared by directly loading molybdenum diselenide on active carbon is slow in photocatalytic efficiency and is found through researches, the active carbon is modified by strontium fluoiodate, and then molybdenum diselenide is generated in situ, so that the obtained active carbon compound has a better photocatalytic effect, and the adsorption performance is improved.
The starting materials, reagents or apparatuses used in the following examples are, unless otherwise specified, either commercially available from conventional sources or can be obtained by known methods.
The invention is further described with reference to the following examples.
Example 1
A treatment process for VOCs in finished oil comprises the following steps:
step 1, carrying out closed treatment on a finished oil transportation truck, collecting waste gas in the finished oil transportation truck under the action of a suction port of a centrifugal fan, a conveying air pipe and a motor, and sending the waste gas to a pre-washing tower to obtain collected waste gas;
step 2, arranging an atomizing head inside the prewashing tower 1, arranging a filler filter layer, namely a polypropylene hollow sphere with the diameter of 40mm, below the atomizing head, spraying the spray liquid in the atomizing head to keep the filler filter layer wet before use, wherein the temperature of the spray liquid is 35 ℃, the spray liquid is 46# refrigerator oil, and the collected waste gas passes through the lower part of the filler filter layer and is in reverse contact with the spray liquid to obtain the washed waste gas; collecting the washed spray liquid into a circulating absorption box 3 through a first vacuum pump 2, and then storing the spray liquid in a separation storage tank 4, wherein the separation storage tank 4 is communicated with the inside of a pre-washing tower 1;
step 3, the washed waste gas is sent to a membrane separation device 6 through a fan 5 for further separation and purification, a separation membrane is arranged in the membrane separation device 6, the separation membrane takes hydrocarbon components as a permeation phase and takes air as a retention phase, permeation phase molecules are firstly adsorbed, dissolved and attached to the membrane at the upstream side of the membrane in the process that the permeation phase passes through the membrane, then permeate through the separation membrane under the action of pressure difference and concentration gradient driving force applied to the two sides of the separation membrane, and are finally desorbed from the downstream side of the membrane, the desorbed organic phase is conveyed into a separation storage tank 4 under the action of a second vacuum pump 7, and the rest gas is the separated waste gas; the separation membrane is a microporous silicon rubber membrane, the thickness is 50 mu m, the porosity is 65%, the pore diameter is 500-600nm, the pressure of the washed waste gas passing through the separation membrane is 0.8MPa, and the temperature is 30 ℃;
step 4, conveying the separated waste gas to an active carbon treatment device 8, wherein an active carbon filter layer is arranged in the active carbon treatment device 8, the time of the separated waste gas passing through the active carbon filter layer is 20min, an ultraviolet light source is further arranged in the active carbon filter device, the wavelength is 335nm, and the illumination intensity is 35mW/cm 2 Further completing the adsorption and purification treatment to obtain the exhaust gas after adsorption;
and 5, detecting VOCs (volatile organic compounds) in the adsorbed waste gas, discharging the waste gas through a chimney 10 after the waste gas reaches the standard, and performing vacuum desorption treatment on the desorption box 9 after the activated carbon treatment device 8 is used for a period of time.
Wherein, the components in the active carbon filter layer are modified active carbon, and the preparation method of the modified active carbon comprises the following steps:
s1, placing activated carbon particles with the particle size of 2.15mm into a sulfuric acid solution with the mass concentration of 20%, wherein the mass ratio of the activated carbon particles to the sulfuric acid solution is 1:25, heating to 70 ℃, stirring for 3 hours, cooling to room temperature, aging for 10 hours, filtering out solids, washing with water to be neutral, and drying under reduced pressure to obtain activated carbon;
s2, weighing 85% phosphoric acid by mass concentration, adding the phosphoric acid into 40% hydrofluoric acid by mass concentration, wherein the mass ratio of the phosphoric acid to the hydrofluoric acid is 1:0.3, and uniformly mixing to form a mixed acid solution; mixing strontium iodate powder and iodic acid powder together, adding the mixture into a mixed acid solution, wherein the mass ratio of the strontium iodate powder to the iodic acid powder to the mixed acid solution is 1.3:1.76:31.2, stirring the mixture at room temperature until all solids are dissolved, and obtaining a mixed liquid A;
s3, dispersing an activated carbon activator into the mixed liquid A, stirring the activated carbon activator and the mixed liquid A at the room temperature for 0.5h, pouring the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven, heating to 220 ℃, carrying out heat preservation treatment for 48h, taking out the reaction kettle, naturally cooling, filtering out a solid, washing the solid to be neutral, and drying the solid under reduced pressure to obtain a mixed solid B, wherein the mass ratio of the activated carbon activator to the mixed liquid A is 1: 14;
s4, weighing selenium powder and 10% of sodium borohydride solution by mass, mixing the selenium powder and the sodium borohydride solution in a mass ratio of 1:21.5, and stirring uniformly at room temperature to form a mixed liquid C; mixing sodium molybdate with deionized water, wherein the mass ratio of the sodium molybdate to the deionized water is 1:30.4, and completely dissolving to form a sodium molybdate solution; firstly, dropwise adding a sodium molybdate solution into a continuously stirred mixed liquid C, then adding a mixed solid B, uniformly mixing the mixed solid B, the mixed liquid C and the sodium molybdate solution at a mass ratio of 0.2:1.4:7 at room temperature, pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, heating to 200 ℃, carrying out heat preservation treatment for 36 hours, taking out the reaction kettle, naturally cooling, filtering out a solid, washing with water to be neutral, and drying under reduced pressure to obtain the modified activated carbon.
Example 2
A treatment process for VOCs in finished oil comprises the following steps:
step 1, carrying out closed treatment on a finished oil transportation truck, collecting waste gas in the finished oil transportation truck under the action of a suction port of a centrifugal fan, a conveying air pipe and a motor, and sending the waste gas to a pre-washing tower to obtain collected waste gas;
step 2, arranging an atomizing head inside the prewashing tower 1, arranging a filler filtering layer below the atomizing head, namely a polypropylene hollow sphere with the diameter of 30mm, spraying the spraying liquid in the atomizing head to keep the filler filtering layer wet before use, wherein the temperature of the spraying liquid is 20 ℃, the spraying liquid is 180 ℃ heavy oil, and the collected waste gas passes through the lower part of the filler filtering layer and is in reverse contact with the spraying liquid to obtain the washed waste gas; collecting the washed spray liquid into a circulating absorption box 3 through a first vacuum pump 2, and then storing the spray liquid in a separation storage tank 4, wherein the separation storage tank 4 is communicated with the inside of a pre-washing tower 1;
step 3, the washed waste gas is sent to a membrane separation device 6 through a fan 5 for further separation and purification, a separation membrane is arranged in the membrane separation device 6, hydrocarbon components are used as a permeation phase of the separation membrane, air is used as a retention phase, permeation phase molecules are firstly adsorbed, dissolved and attached to the membrane at the upstream side of the membrane in the process that the permeation phase passes through the membrane, then the permeation phase molecules permeate the separation membrane under the action of pressure difference and concentration gradient driving force applied to the two sides of the separation membrane, and finally the desorption is carried out from the downstream side of the membrane, the desorbed organic phase is conveyed to a separation storage tank 4 under the action of a second vacuum pump 7, and the rest gas is the separated waste gas; the separation membrane is a microporous silicon rubber membrane, the thickness of the separation membrane is 10-100 mu m, the porosity is 30-80%, the pore diameter is 100-1000 nm, the pressure of the washed waste gas passing through the separation membrane is 0.5-1 MPa, and the temperature is 25-35 ℃;
step 4, conveying the separated waste gas to an active carbon treatment device 8, wherein an active carbon filter layer is arranged in the active carbon treatment device 8, the time of the separated waste gas passing through the active carbon filter layer is 10min, an ultraviolet light source is further arranged in the active carbon filter device, the wavelength is 325nm, and the illumination intensity is 20mW/cm 2 Further completing the adsorption and purification treatment to obtain the exhaust gas after adsorption;
and 5, detecting VOCs (volatile organic compounds) in the adsorbed waste gas, discharging the waste gas through a chimney 10 after the waste gas reaches the standard, and performing vacuum desorption treatment on the desorption box 9 after the activated carbon treatment device 8 is used for a period of time.
Wherein, the components in the active carbon filter layer are modified active carbon, and the preparation method of the modified active carbon comprises the following steps:
s1, placing activated carbon particles with the particle size of 1.25mm into a sulfuric acid solution with the mass concentration of 15%, wherein the mass ratio of the activated carbon particles to the sulfuric acid solution is 1:20, heating to 60 ℃, stirring for 2 hours, cooling to room temperature, aging for 8 hours, filtering out solids, washing with water to be neutral, and drying under reduced pressure to obtain activated carbon;
s2, weighing 85% phosphoric acid by mass concentration, adding the phosphoric acid into 40% hydrofluoric acid by mass concentration, wherein the mass ratio of the phosphoric acid to the hydrofluoric acid is 1:0.2, and uniformly mixing to form mixed acid solution; mixing strontium iodate powder and iodic acid powder together, adding the mixture into a mixed acid solution, wherein the mass ratio of the strontium iodate powder to the iodic acid powder to the mixed acid solution is 1.2:1.76:28.3, stirring the mixture at room temperature until all solids are dissolved, and obtaining a mixed liquid A;
s3, dispersing an activated carbon activator into the mixed liquid A, stirring the activated carbon activator and the mixed liquid A at the room temperature for 0.5h, pouring the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven, heating to 200 ℃, carrying out heat preservation treatment for 36h, taking out the reaction kettle, naturally cooling, filtering out a solid, washing the solid to be neutral, and drying the solid under reduced pressure to obtain a mixed solid B, wherein the mass ratio of the activated carbon activator to the mixed liquid A is 1: 12;
s4, weighing selenium powder and 5% of sodium borohydride solution by mass, mixing the selenium powder and the sodium borohydride solution in a mass ratio of 1:18.2, and stirring uniformly at room temperature to form a mixed liquid C; mixing sodium molybdate with deionized water, wherein the mass ratio of the sodium molybdate to the deionized water is 1:28.3, and completely dissolving to form a sodium molybdate solution; firstly, dropwise adding a sodium molybdate solution into a continuously stirred mixed liquid C, then adding a mixed solid B, uniformly mixing the mixed solid B, the mixed liquid C and the sodium molybdate solution at a mass ratio of 0.1:1.2:6 at room temperature, pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, heating to 180-220 ℃, carrying out heat preservation treatment for 24 hours, taking out the reaction kettle, naturally cooling, filtering out a solid, washing to be neutral, and drying under reduced pressure to obtain the modified activated carbon.
Example 3
A treatment process for VOCs in finished oil comprises the following steps:
step 1, carrying out closed treatment on a finished oil transportation truck, collecting waste gas in the finished oil transportation truck under the action of a suction port of a centrifugal fan, a conveying air pipe and a motor, and sending the waste gas to a pre-washing tower to obtain collected waste gas;
step 2, arranging an atomizing head inside the pre-washing tower 1, arranging a filler filter layer below the atomizing head, namely a polypropylene hollow sphere with the diameter of 30-50 mm, spraying spray liquid in the atomizing head to keep the filler filter layer wet before use, wherein the temperature of the spray liquid is 55 ℃, the spray liquid is 46# refrigerator oil, and the collected waste gas passes through the lower part of the filler filter layer and is in reverse contact with the spray liquid to obtain washed waste gas; collecting the washed spray liquid into a circulating absorption box 3 through a first vacuum pump 2, and then storing the spray liquid in a separation storage tank 4, wherein the separation storage tank 4 is communicated with the inside of a pre-washing tower 1;
step 3, the washed waste gas is sent to a membrane separation device 6 through a fan 5 for further separation and purification, a separation membrane is arranged in the membrane separation device 6, hydrocarbon components are used as a permeation phase of the separation membrane, air is used as a retention phase, permeation phase molecules are firstly adsorbed, dissolved and attached to the membrane at the upstream side of the membrane in the process that the permeation phase passes through the membrane, then the permeation phase molecules permeate the separation membrane under the action of pressure difference and concentration gradient driving force applied to the two sides of the separation membrane, and finally the desorption is carried out from the downstream side of the membrane, the desorbed organic phase is conveyed to a separation storage tank 4 under the action of a second vacuum pump 7, and the rest gas is the separated waste gas; the separation membrane is a microporous silicon rubber membrane, the thickness of the separation membrane is 10-100 mu m, the porosity is 30-80%, the pore diameter is 100-1000 nm, the pressure of the washed waste gas passing through the separation membrane is 0.5-1 MPa, and the temperature is 25-35 ℃;
step 4, conveying the separated waste gas to an active carbon treatment device 8, wherein an active carbon filter layer is arranged in the active carbon treatment device 8, the time of the separated waste gas passing through the active carbon filter layer is 30min, an ultraviolet light source is further arranged in the active carbon filter device, the wavelength is 385nm, and the illumination intensity is 50mW/cm 2 Further completing the adsorption and purification treatment to obtain the exhaust gas after adsorption;
and 5, detecting VOCs (volatile organic compounds) in the adsorbed waste gas, discharging the waste gas through a chimney 10 after the waste gas reaches the standard, and performing vacuum desorption treatment on the desorption box 9 after the activated carbon treatment device 8 is used for a period of time.
Wherein, the components in the active carbon filter layer are modified active carbon, and the preparation method of the modified active carbon comprises the following steps:
s1, placing activated carbon particles with the particle size of 2.75mm into a sulfuric acid solution with the mass concentration of 20%, wherein the mass ratio of the activated carbon particles to the sulfuric acid solution is 1:30, heating to 80 ℃, stirring for 4 hours, cooling to room temperature, aging for 12 hours, filtering out solids, washing with water to be neutral, and drying under reduced pressure to obtain activated carbon;
s2, weighing 85% phosphoric acid by mass concentration, adding the phosphoric acid into 40% hydrofluoric acid by mass concentration, wherein the mass ratio of the phosphoric acid to the hydrofluoric acid is 1:0.4, and uniformly mixing to form mixed acid solution; mixing strontium iodate powder and iodic acid powder together, adding the mixture into a mixed acid solution, wherein the mass ratio of the strontium iodate powder to the iodic acid powder to the mixed acid solution is 1.4:1.76:33.5, stirring the mixture at room temperature until all solids are dissolved, and obtaining a mixed liquid A;
s3, dispersing an activated carbon activator into the mixed liquid A, stirring the activated carbon activator and the mixed liquid A for 1:15 in mass ratio at room temperature, pouring the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a drying oven, heating to 240 ℃, carrying out heat preservation treatment for 60 hours, taking out the reaction kettle, naturally cooling, filtering out a solid, washing to be neutral, and drying under reduced pressure to obtain a mixed solid B;
s4, weighing selenium powder and mixing with 10% sodium borohydride solution by mass, wherein the mass ratio of the selenium powder to the sodium borohydride solution is 1:24.6, and stirring uniformly at room temperature to form a mixed liquid C; mixing sodium molybdate with deionized water, wherein the mass ratio of the sodium molybdate to the deionized water is 1:32.5, and completely dissolving to form a sodium molybdate solution; firstly, dropwise adding a sodium molybdate solution into a continuously stirred mixed liquid C, then adding a mixed solid B, uniformly mixing the mixed solid B, the mixed liquid C and the sodium molybdate solution at a mass ratio of 0.3:1.6:8 at room temperature, pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, heating to 220 ℃, carrying out heat preservation treatment for 48 hours, taking out the reaction kettle, naturally cooling, filtering out a solid, washing with water to be neutral, and drying under reduced pressure to obtain the modified activated carbon.
Comparative example 1
A modified activated carbon, compared to example 1, distinguished by the fact that the in situ formation of molybdenum diselenide was not continued after the formation of the strontium fluoiodate-activated carbon complex.
The preparation method of the modified activated carbon comprises the following steps:
s1, placing activated carbon particles with the particle size of 2.15mm in a sulfuric acid solution with the mass concentration of 20%, wherein the mass ratio of the activated carbon particles to the sulfuric acid solution is 1:25, heating to 70 ℃, stirring for 3 hours, cooling to room temperature, aging for 10 hours, filtering out solids, washing with water to be neutral, and drying under reduced pressure to obtain activated carbon;
s2, weighing 85% phosphoric acid by mass concentration, adding the phosphoric acid into 40% hydrofluoric acid by mass concentration, wherein the mass ratio of the phosphoric acid to the hydrofluoric acid is 1:0.3, and uniformly mixing to form mixed acid solution; mixing strontium iodate powder and iodic acid powder together, adding the mixture into a mixed acid solution, and stirring at room temperature until all solids are dissolved to obtain a mixed liquid A, wherein the mass ratio of the strontium iodate powder to the iodic acid powder to the mixed acid solution is 1.3:1.76: 31.2;
s3, dispersing the activated carbon activator into the mixed liquid A, stirring the activated carbon activator and the mixed liquid A at the room temperature for 0.5h, pouring the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven, heating to 220 ℃, carrying out heat preservation treatment for 48h, taking out the reaction kettle, naturally cooling, filtering out the solid, washing to be neutral, and drying under reduced pressure to obtain a mixed solid B.
Comparative example 2
A modified activated carbon, compared to example 1, the difference is that molybdenum diselenide is generated in situ directly on the surface of the activated carbon.
The preparation method of the modified activated carbon comprises the following steps:
s1, placing activated carbon particles with the particle size of 2.15mm into a sulfuric acid solution with the mass concentration of 20%, wherein the mass ratio of the activated carbon particles to the sulfuric acid solution is 1:25, heating to 70 ℃, stirring for 3 hours, cooling to room temperature, aging for 10 hours, filtering out solids, washing with water to be neutral, and drying under reduced pressure to obtain activated carbon;
s2, weighing selenium powder and 10% of sodium borohydride solution by mass, mixing the selenium powder and the sodium borohydride solution in a mass ratio of 1:21.5, and stirring uniformly at room temperature to form a mixed liquid C; mixing sodium molybdate with deionized water, wherein the mass ratio of the sodium molybdate to the deionized water is 1:30.4, and completely dissolving to form a sodium molybdate solution; firstly, dropwise adding a sodium molybdate solution into the continuously stirred mixed liquid C, then adding an active carbon activator, uniformly mixing the active carbon activator, the mixed liquid C and the sodium molybdate solution at the mass ratio of 0.2:1.4:7 at room temperature, pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven, heating to 200 ℃, carrying out heat preservation treatment for 36 hours, taking out the reaction kettle, naturally cooling, filtering out a solid, washing to be neutral, and drying under reduced pressure to obtain the modified active carbon.
Comparative example 3
Compared with example 1, only the activated carbon raw material is the same, and the rest is not treated at all, and is used as a blank control.
In order to illustrate the present invention more clearly, the activated carbon prepared in example 1 of the present invention and in comparative examples 1 to 3 was tested for performance by the following procedure:
1.00g of the dried activated carbon (or modified activated carbon) prepared in example 1 and comparative examples 1 to 3 was charged into a 4L closed container, and then mixed VOCs gas including benzene, chloroform and formaldehyde was simultaneously introduced so that the initial concentrations of benzene and chloroform were 100mg/m 3 Initial concentration of Formaldehyde is 10mg/m 3 Then irradiating at room temperature with ultraviolet light source with wavelength of 335nm and illumination intensity of 35mW/cm 2 After 20min of treatment, the final concentrations of benzene, chloroform and formaldehyde in the gas in the closed container were measured at 5min, 10min and 20min, respectively, and the removal rates of benzene, chloroform and formaldehyde were obtained by calculation using the formula (removal rate ═ initial concentration-final concentration)/initial concentration × 100%), respectively, with the results shown in table 1 below:
TABLE 1 purification Performance of different activated carbons
As can be seen from Table 1, the wavelength of the ultraviolet light source was 335nm, and the light intensity was 35mW/cm 2 Under the conditions, the method has better removal effect on benzene, trichloromethane and formaldehyde in the embodiment 1, and the removal rate of the benzene reaches up to 20min96.2 percent, the removal rate of trichloromethane is as high as 98.9 percent, and the removal rate of formaldehyde is as high as 94.6 percent. Compared with the comparative example 2, the example 1 has more obvious enhancement on the removal of the trichloromethane, which shows that the removal effect on halogenated hydrocarbon organic matters of the trichloromethane is better and the pertinence is stronger; as can be seen from the comparison between comparative example 1 and comparative example 3, the removal rate of VOCs gas is enhanced in comparative example 1 after the strontium fluoroiodate is compounded, and the possible reason is that the adsorption or degradation of the activated carbon is improved under the irradiation of ultraviolet rays.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A treatment process for VOCs in finished oil is characterized by comprising the following steps:
step 1, carrying out closed treatment on a finished oil transportation truck, carrying out closed collection on generated waste gas, and sending the waste gas to a pre-washing tower to obtain collected waste gas;
step 2, arranging an atomizing head inside the prewashing tower, arranging a filler filtering layer below the atomizing head, and enabling the collected waste gas to pass through the lower part of the filler filtering layer and be in reverse contact with the spraying liquid for treatment to obtain the washed waste gas;
step 3, conveying the washed waste gas to a membrane separation device through a fan for further separation and purification to obtain separated waste gas;
step 4, conveying the separated waste gas to an active carbon treatment device, and further completing adsorption and purification treatment to obtain adsorbed waste gas;
and 5, detecting VOCs (volatile organic compounds) of the adsorbed waste gas, and discharging the waste gas after reaching the standard.
2. The process for treating finished oil VOCs according to claim 1, wherein in step 1, after the finished oil transportation truck is closed, the waste gas is collected and sent to the prewashing tower under the action of a centrifugal fan.
3. The process for treating finished oil VOCs according to claim 1, wherein in step 2, the filler filter layer is kept wet by spraying a spray liquid in an atomizing head before use, the temperature of the spray liquid is 20-55 ℃, and the spray liquid is an organic solution.
4. The treatment process for VOCs in finished oil of claim 1, wherein in step 2, the filler filter layer is made of hollow polypropylene spheres with a diameter of 30-50 mm.
5. The treatment process for VOCs in product oil of claim 1, wherein in step 3, a separation membrane is disposed in the membrane separation device, and the separation membrane is a polymeric separation membrane.
6. The treatment process for VOCs in finished oil according to claim 1, wherein in step 3, the pressure of the washed waste gas passing through the separation membrane is 0.5-1 MPa, and the temperature is 25-35 ℃.
7. The process for treating VOCs in finished oil of claim 1, wherein in step 4, an activated carbon filter layer is arranged in the activated carbon treatment device, the time for the separated waste gas to pass through the activated carbon filter layer is 10-30 min, an ultraviolet light source is further arranged in the activated carbon filter device, the wavelength is 325-385 nm, and the illumination intensity is 20-50 mW/cm 2 。
8. The process of claim 1, wherein in step 4, the component in the activated carbon filter layer is modified activated carbon.
9. The treatment process for VOCs in finished oil according to claim 8, wherein the preparation method of the modified activated carbon comprises:
s1, activating the activated carbon particles by using a hot sulfuric acid solution, and sequentially washing, filtering and drying to obtain activated carbon;
s2, mixing strontium iodate and iodic acid, adding mixed acid solution, and stirring until the strontium iodate and the iodic acid are completely dissolved to obtain mixed liquid A;
s3, adding the activated carbon into the mixed liquid A, stirring and mixing uniformly, placing the mixture into a reaction kettle for reaction, and washing, filtering and drying the mixture in sequence to obtain a mixed solid B;
s4, mixing selenium powder into a sodium borohydride solution, dropwise adding a sodium molybdate solution, adding the mixed solid B, uniformly mixing, placing the mixture into a reaction kettle for reaction, and sequentially washing, filtering and drying to obtain the modified activated carbon.
10. The treatment process for VOCs in finished oil according to claim 8, wherein the preparation method of the modified activated carbon comprises:
s1, placing the activated carbon particles in a sulfuric acid solution, heating to 60-80 ℃, stirring for 2-4 hours, cooling to room temperature, aging for 8-12 hours, filtering out solids, washing with water to be neutral, and drying under reduced pressure to obtain activated carbon;
s2, weighing phosphoric acid, adding the phosphoric acid into hydrofluoric acid, and uniformly mixing to form a mixed acid solution; mixing strontium iodate powder and iodic acid powder together, adding the mixture into a mixed acid solution, and stirring at room temperature until all solids are dissolved to obtain a mixed liquid A;
s3, dispersing the activated carbon activator into the mixed liquid A, stirring for 0.5-1 h at room temperature, then pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a drying oven, heating to 200-240 ℃, carrying out heat preservation treatment for 36-60 h, taking out the reaction kettle, naturally cooling, filtering out a solid, washing to be neutral, and drying under reduced pressure to obtain a mixed solid B;
s4, weighing selenium powder, mixing with a sodium borohydride solution, and stirring uniformly at room temperature to form a mixed liquid C; mixing sodium molybdate with deionized water, and completely dissolving to form a sodium molybdate solution; firstly, dropwise adding a sodium molybdate solution into a continuously stirred mixed liquid C, then adding a mixed solid B, uniformly mixing at room temperature, pouring into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven, heating to 180-220 ℃, carrying out heat preservation treatment for 24-48 h, taking out the reaction kettle, naturally cooling, filtering out a solid, washing to be neutral, and drying under reduced pressure to obtain the modified activated carbon.
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