CN112295381A - Method for efficiently removing VOCs gas by adopting micro-nano bubbles - Google Patents
Method for efficiently removing VOCs gas by adopting micro-nano bubbles Download PDFInfo
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Classifications
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention provides a method for efficiently removing VOCs (volatile organic compounds) gas by adopting micro-nano bubbles, belonging to the technical field of waste gas treatment. The waste gas treatment method of the present invention comprises the steps of: (1) producing micro-nano bubbles by using a micro-nano bubble generating device; (2) introducing the micro-nano bubbles obtained in the step (1) into alkaline electrolytic water; (3) and (3) treating the VOCs gas by using the product obtained in the step (2). The treatment method provided by the invention can quickly and efficiently remove the VOCs gas, and the removal rate of the VOCs gas with complex components can reach 99%.
Description
Technical Field
The invention belongs to the technical field of environmental protection, relates to a waste gas treatment method, and particularly relates to a method for efficiently removing VOCs (volatile organic compounds) gas by adopting micro-nano bubbles.
Background
VOCs are a general term for organic substances that are easily volatilized at normal temperature, and formaldehyde, toluene, xylene, and the like are commonly used. VOCs are the most important precursors before PM2.5 is formed, fine particle pollution gradually becomes serious, and the treatment of the VOCs becomes a great factor for atmospheric pollution treatment in various placesAnd (4) point. Besides generating ozone pollution, VOCs also form secondary organic aerosol (25-35%), and VOCs become a decisive precursor of photochemical smog in cities in China. After the department such as the environmental protection department of China issues the 'guidance opinion on promoting the air quality of the area improved by the joint defense joint control work of atmospheric pollution', it is marked that the pollution of Volatile Organic Compounds (VOCs) in China is controlled after sulfur dioxide, nitrogen dioxide and PM10, and the key point of the environmental protection work is formally stepped. In recent two years, the national ministry of ecological environment and environmental protection agency of Shandong province have issued "standards for the unorganized emission control of volatile organic compounds" (GB 37822-2019) and "emission standards of volatile organic compounds part 6: organic chemical industry (DB 37/2801.6-2018). The standard clearly stipulates that the performance standard of the VOCs at the organic waste gas discharge port in the organic chemical industry is 120mg/m from 1 month and 1 day of 20203Changed to 60mg/m3. Therefore, the problem of excessive discharge of VOCs gas is solved, and the technical problem that domestic production enterprises need to overcome is solved.
In the low-temperature industry, the industries involved in the discharge of the VOCs are numerous, for example, the traditional spraying industry uses a large amount of raw and auxiliary nitrolacquer materials in the product spraying process, the raw and auxiliary nitrolacquer materials contain a large amount of organic solvents, and particularly aromatic hydrocarbons contained in high-volatility solvents such as xylene, toluene, benzene and the like are toxic and flammable and are easy to volatilize into the environment, so that a large amount of VOCs are discharged into the atmosphere, the atmosphere environment is polluted, and the human health is harmed. VOCs pollutants are various in types, components are complex, different types of compounds are different in properties, so that a VOCs treatment technical system is also complex, VOCs in most industries are discharged in a mixture mode, and therefore a treatment effect is often difficult to achieve by adopting a single treatment technology, and the economic cost is also low.
The micro-bubble generator (capable of generating water particles containing a large amount of micro-bubbles) and the axial flow fan for floating the water particles are used for mixing the water particle flow with the spraying aerial fog, enabling the VOC or organic resin coating to be attached to the water particle groups, and enabling the VOC or organic coating to lose activity through the destruction of the micro-bubbles. The ability of micro-bubbles to decompose volatile organic compounds has been verified, as in the 2008-180727 patent. Adopt the circulating fluid that the little nano-bubble purifying column of circulating fluid purification retrieval and utilization device handled and purified the more VOCs pollutant of containing of little nano-bubble purifying column and microorganism purifying column production like patent CN 205073862U, automatic supply and reuse, the restriction condition that monomer little nano-bubble purifying column and microorganism purifying column processing system produced waste liquid secondary pollution has greatly been optimized, make little nano-bubble purifying column and microorganism purifying column combine to handle VOCs waste gas and can extensively use, but in the concrete use, also VOC discharges problem not up to standard. CN 105056726A discloses a VOC's micro-nano bubble processing system of ozone, including exhaust treatment device, water spray circulation filter equipment, micro-nano bubble generating device and ozone generating device. But the patent uses the ozone generating device to limit the popularization and application of the patent. CN1428185A discloses a treatment apparatus and a treatment method for organic waste gas containing VOC, which integrate ozone oxidation technology and traditional wet washing technology, and utilize oxidant (especially hydrogen peroxide) to treat the VOC waste gas, the treatment method needs to provide a large amount of hydrogen peroxide, the treatment cost is high, and the inhalation of hydrogen peroxide vapor or mist can damage the respiratory tract of human body, the eye directly contacting with liquid can cause irreversible damage or even blindness, and the risk coefficient is large. In addition, this treatment method sometimes requires repeated treatment of the VOC-containing gas, which increases the treatment cost and lowers the treatment efficiency.
At present, the method for treating VOCs by adopting micro-nano bubbles mostly has the problems of higher treatment cost, more complex process operation, lower treatment efficiency and lower removal rate of VOCs with complex components. Therefore, there is a need in the art to develop a method for efficiently removing VOCs using micro-nano bubbles.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for efficiently removing VOCs gas by adopting micro-nano bubbles so as to rapidly and efficiently remove the VOCs gas and have higher removal rate of VOCs gas with complex components.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for efficiently removing VOCs gas by adopting micro-nano bubbles comprises the following steps:
(1) producing micro-nano bubbles by using a micro-nano bubble generating device;
(2) introducing the micro-nano bubbles obtained in the step (1) into alkaline electrolytic water;
(3) and (3) treating the VOCs gas by using the product obtained in the step (2).
The micro-nano bubbles have the following properties:
(1) large specific surface area: with a constant total volume (V constant), the total surface area of the bubbles is inversely proportional to the diameter of the individual bubbles. The specific surface area of the 10 μm bubbles is theoretically 100 times that of the 1mm bubbles at a certain volume. The contact area of air and water is increased by 100 times and the reaction speed is increased by 100 times.
(2) Self-pressurizing dissolution: for bubbles with spherical interfaces, surface tension can compress the gas within the bubble, thereby dissolving more of the gas within the bubble into the water. According to the young-laplace equation, Δ P is 2 σ/r, Δ P represents a value of pressure rise, σ represents surface tension, and r represents a bubble radius. Micro-bubbles 10 μm in diameter will be subjected to a pressure of 0.3 atmospheres, while bubbles 1 μm in diameter will be subjected to pressures up to 3 atmospheres. The dissolution of the nanometer micro bubbles in water is a process that the bubbles gradually decrease, the dissolution speed of gas can be increased by the rising of pressure, and the reduction speed of the bubbles becomes faster and faster along with the increase of the specific surface area, so that the nanometer micro bubbles are finally dissolved in the water, and theoretically, the pressure borne by the bubbles is infinite when the bubbles disappear.
(3) Surface charging: the gas-liquid interface formed by the bubbles in the water has easily accepted H+And OH-And generally cations are easier to leave the gas-liquid interface than anions, so that the interface is often negatively charged. The already charged surface generally tends to adsorb counterions, especially high-valence counterions, in the medium, forming a stable electric double layer. The potential difference generated by the surface charge of the microbubbles is usually characterized by zeta potential, when the nano-microbubbles shrink in water, the charged ions are rapidly concentrated and enriched on a very narrow bubble interface,very high values of zeta potential can develop at the interface by the time the bubble collapses.
(4) A large number of free radicals are generated: at the moment of micro-bubble breakage, high-concentration ions accumulated on the interface release accumulated chemical energy at a moment due to the violent change of disappearance of the gas-liquid interface, and at the moment, a large amount of hydroxyl radicals can be generated through excitation. The hydroxyl free radical has ultrahigh oxidation-reduction potential, and the generated super-strong oxidation can degrade paint mist which is captured by people after mixed reaction and pollutants which are difficult to oxidize and decompose under normal organic conditions, such as phenol and the like, so that the purification effect on gas is realized.
(5) The mass transfer efficiency is high: gas-liquid mass transfer is the rate-limiting step in many chemical and biochemical processes. Research shows that the gas-liquid mass transfer rate and efficiency are inversely proportional to the diameter of the bubbles, and the diameters of the microbubbles are extremely small, so that the micro-bubble. When the bubble diameter is small, the influence of the surface tension at the microbubble interface on the bubble characteristics appears more conspicuous. The surface tension generates compression action on the internal gas, so that the micro-bubbles continuously shrink in the rising process and show self-pressurization effect. Theoretically, as the diameter of the bubble is infinitely reduced, the specific surface area of the bubble interface is also infinitely increased, and finally, the internal air pressure can be increased to be infinite due to the self-pressurization effect. Therefore, in the volume contraction process of the micro-bubbles, as the specific surface area and the internal gas pressure are continuously increased, more gas passes through the bubble interface to be dissolved into the mixed water vapor, the effect of the surface tension is more and more obvious along with the reduction of the diameters of the bubbles, and finally the internal pressure reaches a certain limit value to cause the bubble interface to break and disappear. Therefore, the self-pressurization characteristic of the micro-bubbles in the contraction process can continuously enhance the mass transfer efficiency at the gas-liquid interface, and the characteristic enables the micro-bubbles to continue the mass transfer process of the gas and keep the high-efficiency mass transfer efficiency even when the gas content in the water body reaches the supersaturation condition.
(6) The gas dissolution rate is high: the nanometer micro-bubbles have the characteristics of slow rising speed and self-pressurization dissolution, so that the nanometer micro-bubbles are gradually reduced into nanometer level in the slow rising process, and finally annihilation and dissolution are carried out in water, thereby greatly improving the solubility of gas (air, oxygen, ozone, carbon dioxide and the like) in water. For ordinary gas bubbles, the solubility of the gas is often influenced by ambient pressure and the limit exists for saturated solubility. Under standard circumstances, the solubility of gases is difficult to reach above the saturation solubility. And the pressure inside the nano micro bubbles is higher than the ambient pressure, so that the gas supersaturated dissolution condition calculated by taking the atmospheric pressure as an assumed condition is broken.
According to the invention, by combining the micro-nano bubble removal technology, a large number of experiments and searches find that when water in the traditional micro-nano bubble removal technology is replaced by alkaline electrolyzed water in the step (2), a double electric layer on the surface of the micro-bubbles has a higher zeta potential value, more hydroxyl radicals are generated instantly when the micro-bubbles break, the removal effect of VOCs gas is obviously improved, the removal rate is up to more than 99%, and the removal rate of VOCs gas with complex components can still be kept at a high level.
Further, the diameter of the micro-nano bubbles in the step (1) is 50 nm-10 μm.
Further, the alkaline electrolyzed water in the step (2) is electrolyzed water with alkaline pH.
Further, the pH value of the alkaline electrolyzed water is 12-13.5.
Further, the alkaline electrolyzed water is electrolyzed water obtained by adding potassium carbonate as an electrolyte to water and performing electrolysis.
Further, the addition amount of the potassium carbonate is less than or equal to 1 percent by weight.
Further, the electrolysis is performed by repeatedly circulating electrolysis using a water-flowing type electrolysis device to generate alkaline electrolyzed water.
Further, the oxidation-reduction potential ORP of the alkaline electrolyzed water is-1200 mV to-900 mV.
Further, the VOCs gas in step (3) includes any volatile organic compound of hydrocarbons, ketones, esters, alcohols, phenols, aldehydes, amines, and cyanides.
Further, the VOCs gases include those generated by spraying, painting, printing, chemical and paint manufacturing industries, and municipal/industrial waste treatment plants, sewage plants, food processing plants, breweries, and slaughterhouses.
The invention has the following beneficial effects:
(1) the micro-nano bubble processing method provided by the invention can quickly and efficiently remove VOCs gas, and has the advantages of simple processing technology and high safety;
(2) the method has the advantage that the removal rate of VOCs gas with complex components is up to more than 99%.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
A method for efficiently removing VOCs gas by adopting micro-nano bubbles comprises the following steps:
(1) producing micro-nano bubbles by using a micro-nano bubble generating device, wherein the diameter of the micro-nano bubbles is 50 nm-10 mu m;
(2) introducing the micro-nano bubbles obtained in the step (1) into alkaline electrolytic water; the pH value of the alkaline electrolyzed water is 12-13.5, the alkaline electrolyzed water is obtained by adding potassium carbonate with the weight part not higher than 1% as electrolyte into domestic water and repeatedly circulating electrolysis by using running water type electrolysis equipment, and the oxidation-reduction potential ORP of the alkaline electrolyzed water is-1200 mV to-900 mV; .
(3) And (3) treating the VOCs gas by using the product obtained in the step (2).
The VOCs gas comprises any volatile organic compound of hydrocarbons, ketones, esters, alcohols, phenols, aldehydes, amines and cyanides.
Application example 1
The treatment method of example 1 was used for treating a composition containingVOCs gas containing formaldehyde, toluene and xylene (each gas concentration is 150, 148 and 152, respectively, unit: mg/m)3) The removal rates of the three were found to be 98.5%, 99.1%, and 99.2%, respectively.
Application example 2
The treatment method of example 1 was used for treating VOCs gases containing xylene, toluene, benzene and ethyl acetate (gas concentrations of 166, 160, 162 and 150, respectively, in mg/m)3) The removal rates of the four were found to be 99.0%, 98.9%, 99.3% and 99.5%, respectively.
Application example 3
The treatment method of example 1 was used to treat VOCs gases containing toluene, benzene, ethyl acetate and pyridine (gas concentrations: 155, 163, 172, 180, respectively, in mg/m)3) The removal rates of the four were found to be 99.0%, 99.1%, 99.2% and 99.3%, respectively.
Comparative example 1
The alkaline electrolyzed water from example 1, from which step (2) was omitted, was used to treat the VOCs gas in application example 1, and the removal rates were found to be 80.1%, 82.3%, and 81.8%, respectively.
Comparative example 2
The alkaline electrolyzed water of step (2) in example 2 was replaced with hydrogen peroxide for treating the VOCs gas in application example 2, and the removal rates were found to be 78.1%, 85.3%, 82.6%, and 79.5%, respectively.
Comparative example 3
The alkaline electrolyzed water of step (2) in example 2 was replaced with ozone for treating the VOCs gas in application example 3, and the removal rates were found to be 87.1%, 86.3%, 89.6%, and 90.4%, respectively.
Claims (10)
1. A method for efficiently removing VOCs gas by adopting micro-nano bubbles is characterized by comprising the following steps:
(1) producing micro-nano bubbles by using a micro-nano bubble generating device;
(2) introducing the micro-nano bubbles obtained in the step (1) into alkaline electrolytic water;
(3) and (3) treating the VOCs gas by using the product obtained in the step (2).
2. The method according to claim 1, wherein the micro-nano bubbles in step (1) have a diameter of 50nm to 10 μm.
3. The method according to claim 2, wherein the alkaline electrolyzed water in step (2) is electrolyzed water having an alkaline pH.
4. The method according to claim 3, wherein the pH of the alkaline electrolyzed water is 12 to 13.5.
5. The method according to claim 3 or 4, wherein the alkaline electrolyzed water is electrolyzed water obtained by adding potassium carbonate as an electrolyte to water and performing electrolysis.
6. The method of claim 5, wherein the potassium carbonate is added in an amount of 1% by weight or less.
7. The method according to claim 5, wherein the electrolysis is performed by repeated circulation electrolysis using a flow-type electrolysis apparatus to generate alkaline electrolyzed water.
8. The method according to claim 7, wherein the oxidation-reduction potential ORP of the alkaline electrolyzed water is from-1200 mV to-900 mV.
9. The method of claim 1, wherein the VOCs gas in step (3) comprises any volatile organic compounds selected from the group consisting of hydrocarbons, ketones, esters, alcohols, phenols, aldehydes, amines, and cyanides.
10. The method of claim 1 or 9, wherein the VOCs gases comprise VOCs gases generated by spray painting, printing, chemical and paint manufacturing industries, and municipal/industrial waste treatment plants, sewage plants, food processing plants, breweries, and slaughterhouses.
Priority Applications (1)
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