CN115138187B - Device and process for treating siloxane in VOCs (volatile organic compounds) by low-temperature plasma - Google Patents

Device and process for treating siloxane in VOCs (volatile organic compounds) by low-temperature plasma Download PDF

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Publication number
CN115138187B
CN115138187B CN202210688157.2A CN202210688157A CN115138187B CN 115138187 B CN115138187 B CN 115138187B CN 202210688157 A CN202210688157 A CN 202210688157A CN 115138187 B CN115138187 B CN 115138187B
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washing tank
water washing
vocs
plasma
alkaline solution
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CN115138187A (en
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代超
叶翔
廖蔚峰
齐洪广
邓良德
戴荣富
夏云龙
彭军
赵凯
周丽岗
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Shenzhen Jiejing Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/32Separation 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 electrical effects other than those provided for in group B01D61/00
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D50/00Combinations of methods or devices for separating particles from gases or vapours
    • B01D50/60Combinations of devices covered by groups B01D46/00 and B01D47/00
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/80Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/818Employing electrical discharges or the generation of a plasma
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention discloses a device and a process for treating siloxane in VOCs by low-temperature plasma, wherein a low-temperature plasma treatment method is adopted to break C-Si bonds of siloxane to form nano-scale silicon dioxide, so that the siloxane is removed from the VOCs; the macromolecular organic compound in the VOCs after the plasma treatment is decomposed into micromolecular organic compounds under the action of electric energy, so that the load of the terminals for VOCs treatment is reduced, and the overall removal rate of the VOCs is improved; the nano silicon dioxide collected from the ash bucket and the washing liquid is a byproduct with high value, and the whole process achieves the effect of waste utilization.

Description

Device and process for treating siloxane in VOCs (volatile organic compounds) by low-temperature plasma
Technical Field
The invention relates to the field of environmental protection, in particular to a device and a process for treating siloxane in VOCs by using plasma.
Background
Volatile Organic Compounds (VOCs)s) is a common waste in the tail gas of modern industry and has great harm to human health and environment. A series of technologies are provided for removing VOCs at home and abroad, wherein the rotary wheel concentration and RTO (regenerative incinerator) process is widely applied in practical industry. However, such processes suffer from difficulties in handling siloxane-containing VOCs, particularly common in the lithium battery production, semiconductor processing, silicone rubber processing, and like industries. The siloxane in VOCs is easily oxidized into glassy SiO at high temperature during combustion 2 Thereby blocking the heat accumulator of RTO, causing the equipment surface to agglomerate, the heat accumulator pore canal to block, causing the bed pressure to rise, making VOCs treatment efficiency decline, serious person causes equipment damage and shutdown. When a certain lithium battery manufacturer adopts a runner concentration and RTO process TO treat VOCs, the problem of RTO heat accumulator blockage occurs soon, and the silicon blockage problem cannot be effectively solved, so that the runner and TO (direct-fired incinerator) process can be selected TO replace the problem, but TO has lower furnace temperature and more fuel consumption compared with RTO, and the problems of VOCs treatment efficiency reduction and fuel cost increase are brought. Thus, removal of the siloxane contained in VOCs prior to terminal treatment is an effective solution to the problem of silicon blockage.
The plasma is the fourth state of matter, a gas in ionized form consisting of free electrons and ions. The low-temperature plasma technology can be performed at normal temperature, has low energy consumption, can degrade macromolecular compounds, and can be used for treating gaseous pollutants. Under the high-voltage discharge state, C-Si bond of siloxane is broken under the collision of high-energy electrons to form more stable nano-state SiO 2 The solid and other macromolecular organic compounds in VOCs can be decomposed into micromolecular organic compounds, so that the micromolecular organic compounds can be effectively removed in terminal removing equipment.
CN108283870B discloses a plasma waste gas comprehensive treatment device, which generates a large amount of static charges by using high pressure to generate plasma, so as to adsorb solid particles in waste gas and remove a certain amount of VOCs. But its pertinence to VOCs is not strong, and its area is great moreover, can't solve the silicon of VOCs processing terminal and block up the problem.
In summary, the current research has little attention to the siloxane in the VOCs, the prior art has no effective removal effect on the siloxane, and the silicon in the siloxane is also a resource, so that a process capable of effectively removing the siloxane in the VOCs and realizing the resource utilization of the silicon is necessary.
Disclosure of Invention
The invention aims to remove siloxane in VOCs and provides a device and a process for treating siloxane in VOCs by low-temperature plasma.
The device for treating siloxane in VOCs by low-temperature plasma comprises a plasma treatment device and a water washing tank which are sequentially connected, wherein the plasma treatment device comprises a plasma treatment device inlet (1), a plasma polar plate (2), an insulating medium (3), a plasma power supply (4), a blowing fan (5), a filter screen (6), an ash bucket (7) and an ash bucket solid outlet (8); the plasma pole plates (2) are tightly attached to the insulating medium (3) and are horizontally arranged along the main flow direction; the upper polar plate is connected with the positive electrode of the plasma power supply (4), and the lower polar plate is connected with the negative electrode of the plasma power supply (4); the purging fan (5) is connected with the plasma treatment device through a pipeline, and the outlet of the pipeline is close to the lower polar plate; the filter screen (6) is arranged right below the lower polar plate and covers the ash bucket (7); the water washing tank comprises a water washing tank gas inlet (9), a foaming column (10), a water pump (11), a water tank (12), a water washing tank liquid outlet (13) and a water washing tank gas outlet (14); the foaming column (10) is connected with the tail end of the gas inlet (9) of the water washing tank, and is completely immersed into washing liquid which is weak alkaline solution; the water pump (11) is connected with the water tank (12) and the water washing tank through a pipeline.
The invention discloses a process for treating siloxane in VOCs by low-temperature plasma, which comprises the following steps:
the organic waste gas enters the plasma treatment device through the inlet (1) of the plasma treatment device, high voltage is provided by the plasma power supply (4) to generate a high-strength electric field, the C-Si bond of siloxane in VOCs is broken under the action of electric energy to generate nano silicon dioxide and micromolecular organic matters, and other macromolecule organic matters in the VOCs are decomposed into micromolecular organic matters under the action of electric energy, so that the removal of the follow-up device is facilitated, and the purpose of improving the removal efficiency of the follow-up organic matters while removing the siloxane is achieved; the purging fan (5) periodically purges the lower polar plate, blows the generated nano silicon dioxide away from the lower polar plate, and simultaneously provides a small amount of air into the plasma treatment device to generate oxygen free radicals, so that the conversion of the nano silicon dioxide is facilitated; part of the nano silicon dioxide is carried by air flow and enters the water washing tank through the water washing tank inlet (9), the other part of the nano silicon dioxide is filtered by the filter screen (6) to remove large-size solid substances and then falls into the ash bucket (7), and when a certain amount of solid is accumulated in the ash bucket, the ash bucket solid outlet (8) is opened to clean the solid substances generated in the plasma treatment device; the foaming column (10) is immersed in the weak alkaline solution, a large amount of bubbles are generated by the gas passing through the foaming column (10), and the intensified gas is in gas-liquid contact with the weak alkaline solution, so that nano silicon dioxide carried by the gas flow is better dispersed in the weak alkaline solution, and meanwhile, acid gas which possibly comprises HF and HCl is absorbed, and the gas leaves the water washing tank through the gas outlet (14) of the water washing tank after washing; when the nano silicon dioxide in the water washing tank reaches a certain amount, part of old weak alkaline solution is discharged through a liquid outlet (13) of the water washing tank, and meanwhile, a water pump (11) is started, fresh weak alkaline solution is replenished into the water washing tank from a water tank (12), and the total amount of weak alkaline solution in the water washing tank is maintained.
The insulating medium is made of glass, quartz or ceramic.
The inlet VOCs temperature of the plasma treatment device is in the range of 150-300 ℃, preferably 220 ℃.
The plasma operating voltage is 0-30kV, preferably 25kV.
The washing liquid is a weak alkaline solution, and the alkaline substance is at least one of sodium carbonate, sodium bicarbonate, calcium hydroxide and disodium hydrogen phosphate, preferably 5% sodium carbonate solution.
The temperature of the weakly alkaline solution in the water washing tank is in the range of 40-60 ℃, preferably 55 ℃.
The invention adopts a low-temperature plasma treatment method to break C-Si bond of siloxane to form nano-scale silicon dioxide, thereby removing siloxane from VOCs and solving the problem of silicon blockage of RTO heat accumulator by siloxane in the VOCs; the macromolecular organic compound in the VOCs after the plasma treatment is decomposed into micromolecular organic compounds under the action of electric energy, so that the load of the terminals for VOCs treatment is reduced, and the overall removal rate of the VOCs is improved; the nano silicon dioxide collected from the ash bucket and the weak alkaline solution is a byproduct with high value, and the whole process achieves the effect of waste utilization.
The invention has the beneficial effects that: 1. by adopting a low-temperature plasma treatment method, siloxane in VOCs is effectively removed, and the problem of blockage of siloxane in VOCs to a heat accumulator of RTO equipment is solved.
2. The product nano silicon dioxide obtained by removing siloxane is a byproduct with high value, and improves the economy of the device and the process.
3. The plasma treatment enables macromolecular organic compounds in the VOCs to be decomposed into micromolecular organic compounds, and the removal efficiency of the VOCs treatment terminal is improved.
Drawings
FIG. 1 is a schematic view of a process apparatus for treating siloxane in VOCs with a low temperature plasma in accordance with the present invention.
Detailed Description
Taking a lithium power plant organic waste gas treatment system as an example, 10000m is produced from a zeolite runner outlet per hour 3 220 ℃ hot flue gas of (2) wherein the VOC content is about 400mg/m 3 The siloxane content was about 80mg/m 3 Referring to fig. 1, hot flue gas enters a plasma treatment device through an inlet (1) of the plasma treatment device, a plasma power supply (4) is connected with a plasma polar plate (2), the output voltage is set to 25kV, a discharge phenomenon is generated between insulating media (3), siloxane in VOCs is broken down by C-Si bonds under the action of electric energy, nano silicon dioxide and small molecular organic matters are generated, and other large molecular organic matters in the VOCs are decomposed into small molecular organic matters under the action of electric energy; a blowing fan (5) blows air into the device, blows generated nano silicon dioxide away from the lower polar plate, and simultaneously provides a small amount of air into the plasma treatment deviceOxygen free radicals are generated, which is beneficial to the conversion of nano silicon dioxide; part of the nano silicon dioxide is carried by air flow and enters the water washing tank through a gas inlet (9) of the water washing tank, the other part of the nano silicon dioxide is filtered by a filter screen (6) and falls into an ash bucket (7), and after a certain amount of solid is accumulated in the ash bucket, a solid outlet (8) of the ash bucket is opened to clean the solid generated in the plasma treatment device; the foaming column (10) is immersed in the weak alkaline solution, a large amount of bubbles are generated by the gas passing through the foaming column (10), and the intensified gas is in gas-liquid contact with the weak alkaline solution, so that nano silicon dioxide carried by the gas flow is better dispersed in the weak alkaline solution, and meanwhile, acid gases such as HF, HCl and the like which are possibly generated are absorbed, and the gas leaves the water washing tank through the gas outlet (14) of the water washing tank after washing; when the nano silicon dioxide in the water washing tank reaches a certain amount, part of old weak alkaline solution is discharged through a liquid outlet (13) of the water washing tank, and meanwhile, a water pump (11) is started, fresh weak alkaline solution is replenished into the water washing tank from a water tank (12), and the total amount of weak alkaline solution in the water washing tank is maintained. Collecting a smoke sample from a gas inlet (9) and a gas outlet (14) of the water washing tank, measuring the siloxane content in the smoke by using a mass spectrometer, wherein the siloxane concentration of the gas inlet and outlet of the water washing tank is 6.4mg/m respectively 3 2.1mg/m 3 According to measurement and calculation, the process device provided by the invention has the advantages that the removal rate of siloxane in VOCs is 97.4%, the siloxane removal capability is very remarkable, the treated flue gas completely meets the RTO combustion requirement, and the problem of silicon blockage does not occur.
After the device is operated for 6 hours, nano silicon dioxide crystals are separated from the ash bucket and the weak alkaline solution, so that the effect of waste utilization is achieved.
The above description of the embodiments is provided to facilitate a person skilled in the art to understand and apply the present invention, but is not intended to limit the present invention, and those skilled in the art should not make any improvement or modification to the method of the present invention without inventive effort.

Claims (10)

1. An organic waste gas treatment process is characterized in that: the process device for treating siloxane in VOCs by utilizing low-temperature plasma comprises a plasma treatment device and a water washing tank which are sequentially connected, wherein the plasma treatment device comprises a plasma treatment device inlet (1), a plasma polar plate (2), an insulating medium (3), a plasma power supply (4), a purging fan (5), a filter screen (6), an ash bucket (7) and an ash bucket solid outlet (8); the plasma pole plates (2) are tightly attached to the insulating medium (3) and are horizontally arranged along the main flow direction; the upper polar plate is connected with the positive electrode of the plasma power supply (4), and the lower polar plate is connected with the negative electrode of the plasma power supply (4); the purging fan (5) is connected with the plasma treatment device through a pipeline, and the outlet of the pipeline is close to the lower polar plate; the filter screen (6) is arranged right below the lower polar plate and covers the ash bucket (7); the water washing tank comprises a water washing tank gas inlet (9), a foaming column (10), a water pump (11), a water tank (12), a water washing tank liquid outlet (13) and a water washing tank gas outlet (14); the foaming column (10) is connected with the tail end of the gas inlet (9) of the water washing tank, and is completely immersed into washing liquid which is weak alkaline solution; the water pump (11) is connected with the water tank (12) and the water washing tank through a pipeline;
the organic waste gas enters the plasma treatment device through the inlet (1) of the plasma treatment device, high voltage is provided by the plasma power supply (4) to generate a high-strength electric field, the C-Si bond of siloxane in VOCs is broken under the action of electric energy to generate nano silicon dioxide and micromolecular organic matters, and other macromolecule organic matters in the VOCs are decomposed into micromolecular organic matters under the action of electric energy, so that the removal of the follow-up device is facilitated, and the purpose of improving the removal efficiency of the follow-up organic matters while removing the siloxane is achieved; the purging fan (5) periodically purges the lower polar plate, blows the generated nano silicon dioxide away from the lower polar plate, and simultaneously provides a small amount of air into the plasma treatment device to generate oxygen free radicals, so that the conversion of the nano silicon dioxide is facilitated; part of the nano silicon dioxide is carried by air flow and enters the water washing tank through a gas inlet (9) of the water washing tank, the other part of the nano silicon dioxide is filtered by a filter screen (6) and falls into an ash bucket (7), and after a certain amount of solid is accumulated in the ash bucket, a solid outlet (8) of the ash bucket is opened to clean the solid generated in the plasma treatment device; the foaming column (10) is immersed in the weak alkaline solution, a large amount of bubbles are generated by the gas passing through the foaming column (10), and the intensified gas is in gas-liquid contact with the weak alkaline solution, so that nano silicon dioxide carried by the gas flow is better dispersed in the weak alkaline solution, and meanwhile, acid gas which possibly comprises HF and HCl is absorbed, and the gas leaves the water washing tank through the gas outlet (14) of the water washing tank after washing; when the nano silicon dioxide in the water washing tank reaches a certain amount, part of old weak alkaline solution is discharged through a liquid outlet (13) of the water washing tank, and meanwhile, a water pump (11) is started, fresh weak alkaline solution is replenished into the water washing tank from a water tank (12), and the total amount of weak alkaline solution in the water washing tank is maintained.
2. The organic waste gas treatment process according to claim 1, wherein the insulating medium is glass, quartz or ceramic.
3. The organic waste gas treatment process according to claim 1, wherein the inlet VOCs temperature of the plasma treatment device is in the range of 150-300 ℃.
4. The organic waste gas treatment process according to claim 3, wherein the inlet VOCs temperature of the plasma treatment device is 220 ℃.
5. The organic waste gas treatment process according to claim 1, wherein the plasma operating voltage is 0-30kV.
6. The organic waste gas treatment process according to claim 5, wherein the plasma operating voltage is 25kV.
7. The process according to claim 1, wherein the alkaline substance to which the weakly alkaline solution acts is at least one of sodium carbonate, sodium bicarbonate, calcium hydroxide, and disodium hydrogen phosphate.
8. The organic waste gas treatment process according to claim 7, wherein the weakly alkaline solution is 5% sodium carbonate solution and the active alkaline substance is sodium carbonate.
9. The organic waste gas treatment process according to claim 1, wherein the temperature of the weakly alkaline solution in the water washing tank is in the range of 40-60 ℃.
10. The organic waste gas treatment process according to claim 1, wherein the temperature of the weakly alkaline solution in the water washing tank is 55 ℃.
CN202210688157.2A 2022-06-16 2022-06-16 Device and process for treating siloxane in VOCs (volatile organic compounds) by low-temperature plasma Active CN115138187B (en)

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CN108962596A (en) * 2018-07-18 2018-12-07 清华大学 High temperature capacitors method for manufacturing thin film based on atmos low-temperature plasma deposition
CN110655333A (en) * 2019-10-24 2020-01-07 宿州速果信息科技有限公司 Frosted treatment process for glass surface

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JP2000119993A (en) * 1998-10-12 2000-04-25 Toppan Printing Co Ltd Functional paper and its production
CN104159659A (en) * 2011-11-02 2014-11-19 荷兰能源建设基金中心 Supported polysilsesquioxane membrane and production thereof
JP2017064602A (en) * 2015-09-29 2017-04-06 ニッタ株式会社 Siloxane compound removal facility
CN108962596A (en) * 2018-07-18 2018-12-07 清华大学 High temperature capacitors method for manufacturing thin film based on atmos low-temperature plasma deposition
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