CN101450275B - Treatment method of odor gas containing sulfur and dust - Google Patents

Treatment method of odor gas containing sulfur and dust Download PDF

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CN101450275B
CN101450275B CN 200710158782 CN200710158782A CN101450275B CN 101450275 B CN101450275 B CN 101450275B CN 200710158782 CN200710158782 CN 200710158782 CN 200710158782 A CN200710158782 A CN 200710158782A CN 101450275 B CN101450275 B CN 101450275B
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waste gas
washing
dust
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CN101450275A (en
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郭兵兵
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a method for processing foul waste gas contained sulfur and dust. The waste gas is processed dedusting using liquid absorption, water solution contained additive is used as absorption washing liquid, the additive comprises a washing agent, the washing agent has washing organism, is one or some of the surface active agent, washing agent, emulsifying agent and dispersing agent, the absorption washing liquid also can comprise alkaline matter or oxidizing agent. Waste gas is deprived hazardous substance such as sulphide, hydrocarbon further after being absorption and washing. The method can deprive various contamination in foul waste gas contained sulfur and dust effectively, has advantages of high purifying rate and long device running period. The method can be used for purifying various foul waste gas contained sulfur and dust, especially in catalyst production process.

Description

The processing method of the foul waste gas of a kind of sulfur-bearing and dust
Technical field
The present invention relates to the processing method of the foul waste gas of harmful constituents such as method, particularly sulfur-bearing that the foul waste gas of a kind of sulfur-bearing and dust handles, dust, hydro carbons volatile matter.
Background technology
In the oil refining enterprise; Catalyst is indispensable core product; In producing the catalyst process; Because catalyst needs processes such as heating, roasting, thereby Catalyst Production equipment will produce the complex waste gas that various components such as containing dust, sulfide (hydrogen sulfide and sulfur-containing organic compound), VOCs (organic volatile), ammonia mix inevitably.The long-term activity of worker possibly cause diseases such as respiratory system, digestive system, reproductive system in the environment that is polluted by these materials, also possibly cause body disease and carcinogenic; When seriously polluted, also can make the people produce dizziness, larynx painful, feel sick, acute poisoning symptom such as vomiting.
These waste gas components are complicated, not only cause the odor pollution of surrounding enviroment, also worker health threatened.Therefore must administer this type waste gas.This type waste gas characteristics are that exhausted air quantity is little, the intermittent generation, and Dust Capacity is big, and component is complicated.
Traditional exhaust gas treatment method such as absorption method, burning method, Production by Catalytic Combustion Process, condensation method, absorption process etc. can not be administered this type waste gas well.The used adsorbent of existing absorption method directly adsorbs this type of waste gas makes adsorbent bed obstruction very soon easily, thereby treating apparatus can not be moved.Because this type of waste gas intermittently produces, thereby there is high, the less economical shortcoming of energy consumption in burning method.Though the Production by Catalytic Combustion Process energy consumption reduces, waste gas component is complicated, and also there is the beds blocking problem simultaneously in the easy poison deactivation of catalyst.Condensation method and absorption process only can be removed the part component in this type of waste gas.
CN01127539.1 has introduced a kind of method that purifies hydrogen sulfide, and CN1133568A has introduced the method that a kind of absorption process is removed hydrogen sulfide.CN91110451.8 has introduced the method for recovering solvents in a kind of hydro carbons process.These methods all only can be removed hydrogen sulfide or hydro carbons.Foul waste gas improvement for sulfur-bearing and dust does not still have better method.
" petrochemical industry environmental protection " 2005 28 the 4th phases of volume have been introduced the improvement method that adopts absorption process purification of sulphur-containing sewage jar waste gas.This method adopts the secondary absorption process to handle acid water pot waste gas, and absorbent is an alkaline solution.The tail gas that several sour water jars and alkaline residue jar are extracted through jet pump earlier with alkali lye blended absorbent in venturi mixer; In alkali liquid tank, carry out gas-liquid separation; Absorb processing through one-level alkali lye absorption tower and secondary deodorant absorption tower then, be pooled to the laggard smoke stack emission of deodorant jar gas-liquid separation at last.But this technology only can transform the sulfide oxidation that absorbs, but does not remove the ability of hydro carbons.
" design of sulphur phosphorus and powder technology " the 6th phase in 2004 has been introduced the waste gas that adopts solid absorbent adsorption cleaning sour water jar.This method adopts the swage adsorbent that this waste gas is handled, and has obtained certain effect.But this method only purifies hydrogen sulfide, and other pollutant does not purify, and also there is safety problem in adsorbent.
Existing absorption method is all used the single hop bed, adopts active carbon or NACF usually.Patent CN03254728.5CN03254729.3, CN200410023944.7, CN02805902.6 and CN00118594.2 have all proposed by active carbon hydro carbons to be adsorbed, and carry out steam desorb condensing and recycling or vacuum desorption solvent then and absorb the method that reclaims.Patent CN03254728.5 CN03254729.3 has proposed the device that a kind of absorption method oil gas reclaims respectively, adopts active carbon as adsorbent, and the hydro carbons behind the vacuum desorption absorbs as liquefied gas or diesel oil.With active carbon or NACF is adsorbent, and its advantage is that adsorbance is bigger, and adsorption efficiency is higher, and discharging tail gas reaches the environmental protection index requirement easily.
But above-mentioned method is handled this type of waste gas of the present invention and uneconomical; In the sulfur-bearing involved in the present invention and the foul waste gas of dust, the VOCs amount is less, and needing further after the recovery, processing just has value; For the value that VOCs embodied that is reclaimed, and uneconomical.
In addition, for the sulfide in this type of waste gas, adopt traditional sulfur recovery technology more uneconomical, the sulfide concentration that the present invention relates to is less than 1% (volume ratio), and traditional sulfur recovery technology concentration of hydrogen sulfide is generally more than 10% (volume ratio).
Summary of the invention
Deficiency to above-mentioned prior art; The present invention proposes the purification method of the foul waste gas of a kind of sulfur-bearing and dust; The occasion of sulfide, ammonia and hydrocarbon gas that the present invention can be applicable to produce in the various production processes is specially adapted to the foul waste gas that the Catalyst Production device produces.It is simple that the present invention has flow process, no safety issue, the advantage that the adsorbent life-span is long.
The processing method of sulfur-bearing of the present invention and dust foul waste gas comprises following content: waste gas adopts the liquid-absorbent dust removal process, and the liquid-absorbent dust removal process can remove harmful miscellaneous material through solid absorbent then.Wherein the liquid-absorbent dust removal process is an absorption and washing liquid with the aqueous solution that contains additive, and additive comprises cleaning agent, and additive can also comprise alkaline matter or oxidant.Cleaning agent is the material with cleaning organic matter function, specifically can use in surfactant, washing agent, emulsifying agent, the dispersant etc. one or more.The cleaning agent consumption is 0.1%~50% of an absorption and washing liquid by weight, is preferably 2%~20%.
Absorption and washing can adopt various suitable equipment, as being packed tower washing facility, whirlwind washing facility, self-excitation spray washing equipment, plate type washing equipment, Venturi scrubbing equipment, hypergravity absorption equipment, mechanical induction spray washing equipment, catheter type absorption and washing equipment etc.The air speed of waste gas in absorption and washing equipment is 100h -1~20000h -1, preferred 200~5000h -1, liquid-gas ratio is 0.2~50L/m 3, preferred 0.5~20L/m 3, 1.0~15L/m most preferably 3
Composition according to waste gas in the absorption and washing liquid can add other additive types; For example contain hydrogen sulfide in the waste gas more for a long time; Can add alkaline matter and absorb,, can when adding alkaline matter, add oxidant if organic sulfur compound content is more in the waste gas.Above-mentioned additive can make the sulfide part in the absorption and washing dust removal process in the waste gas remove, and reduces the load of follow-up desulfuration adsorbent.
The kind of solid absorbent can be selected according to the kind of objectionable impurities in the waste gas, can adopt desulfuration adsorbent to purify like sulfur-containing compound, and volatile organic matters such as hydro carbons can adopt and take off the hydrocarbon adsorbent purification.Desulfuration adsorbent with take off hydrocarbon adsorbent and can use the conventional adsorbent in this area, can be active carbon type desulfurizing agent, metal oxide type desulfurizing agent, alkali type desulfurizing agent etc. like desulfuration adsorbent.Taking off hydrocarbon adsorbent can be materials such as silica gel, aluminium oxide, molecular sieve, zeolite, active carbon.Desulfuration adsorbent with take off hydrocarbon adsorbent and can be seated in the absorber, also can be seated in respectively in the different adsorption device.Waste gas is earlier through desulfuration adsorbent, then through taking off hydrocarbon adsorbent; Can pass through desulfuration adsorbent then earlier through taking off hydrocarbon adsorbent; Also can and take off hydrocarbon adsorbent and mix use desulfuration adsorbent.Desulfuration adsorbent with take off the flow of the consumption of hydrocarbon adsorbent, the concentration of sulfide and hydro carbons in the waste gas, and the factors such as operation cycle that designed are definite according to waste gas.
In the foul waste gas of hydrocarbon-containifirst and dust; The less dust of particle generally is difficult for removing with common cleaning dust mode; The dust that does not remove has certain influence to follow-up waste gas treatment process, particularly to adopting the fixed bed waste gas treatment process to have bigger influence, because these dust deposits are in ADSORPTION IN A FIXED BED agent or catalyst; Can cause bed to stop up, shorten service cycle.Common cleaning dust method can not the possible reason of this type of effective elimination dust be that dust granules is less; Has bigger outer surface; These dust granules are easy to adsorb the weak organic matter of hydro carbons isopolarity in the waste gas, dust granules is become have hydrophobic particle.Since the hydrophobicity of particle, and absorption and washing solution is the aqueous solution, under surface tension effects, hydrophobic particle is difficult for being washed down in the entering wash solution, and major part is got back in the gas phase again behind the gas-liquid two-phase surface collision.The inventive method is destroyed the hydrophobicity on dust granules surface through in cleaning solution, adding cleaning agent, reduces to absorb the washing lotion surface tension, can dust granules be washed smoothly to absorb in the cleaning solution.In absorption and washing liquid, add additives such as alkaline matter and oxidant, can absorbing waste gas in part sulfide, reduce the load of subsequent treatment process, prolong service cycle.If sulfide concentration is lower in the waste gas, after cleaning dust, can directly discharge.
Through the present invention, can eliminate the odor pollution of sulfur compound, hydro carbons and dust, after handling through the present invention, purified gas can reach national relevant emission standards, and purification efficiency is high, and the device periphery of loss stench can be eliminated odor pollution fully.
Description of drawings
Fig. 1 is that waste gas purification of the present invention is handled a kind of idiographic flow sketch map.
The specific embodiment
This process using absorption and washing-two section absorbing process purifies the foul waste gas of sulfur-bearing and dust.After sulfur-containing foul waste gas purifies through technology of the present invention, but the sulfide zero-emission improves environmental ambient air greatly.Device applicable to the foul waste gas of various generation sulfur-bearings and dust.The field is reclaimed in the purification that is particularly suitable for the sulfur-containing foul waste gas of Catalyst Production device generation.
If contain bigger dust of particle or drop in the waste gas, can before the absorption and washing operation, flow tank be set, adopt modes such as electric precipitation, gravitational settling dedusting, inertial dust collection, cyclone dust removal to remove part big dust particle or drop.
At the absorption and washing equipment port of export, the foam removal facility is set.The foam removal facility can be selected the conventional foam removal facility in this area for use.Like mesh-like foam removal equipment, non-mesh-like foam removal equipment, foam removal gas distributor etc.
Below cleaning agent can be selected in several types of materials one or more, sodium alkyl benzene sulfonate, poly alkyl alcohol ethene, ethyoxyl ether sodium sulfate, NPE, alkanolamide, quaternary amines salt cationic surfactant, ethylene glycol stearate, silicate, phosphate, boric acid, polyhydroxy fatty acid amide, polycarboxylate, polyethylene glycol polymer, alkyl ester sulfonate, higher aliphatic, higher aliphatic polyethers, nitrogen-containing polyether, fatty acid ester, organopolysiloxane class, ethanol, acetate, acetaldehyde, acetone, dishwashing detergent liquid, clothes washing liquid, soap and toothpaste etc.
Alkaline matter generally is selected from alkaline solutions such as NaOH, NaOH, sodium carbonate, sodium acid carbonate, potassium hydroxide, potash, saleratus.The alkaline matter consumption is 0.5%~50% (weight), preferred 1%~30%.
Oxidant comprises one or more among clorox, hydrogen peroxide solution, chlorine dioxide, sulfonated phthalocyanine cobalt, molysite, the potassium permanganate etc., and consumption is 0~30% (weight), and is preferred 0.5%~20%, most preferably 1%~10%.
The concrete concentration of cleaning agent, alkaline matter and oxidant can be recycled condition such as time by liquid-gas ratio, the absorption and washing liquid that those skilled in the art absorb operation according to the concentration of harmful substance in the waste gas, washing and confirms in the absorption and washing liquid.
Waste gas is through after the absorption and washing, and particle in the waste gas and amino originally remove fully, can remove partial vulcanization thing and part hydrocarbons simultaneously.Salt after particle and the absorption is regularly discharged otherwise processed through being deposited in the absorption equipment bottom.In the method for gas purification of the present invention, absorption and washing liquid can be recycled, and regenerates after the inefficacy or harmless treatment.
Waste gas after the absorption foam removal gets into two sections adsorption towers, and adsorption tower adopts two-layer filling, and the adsorbent of hydro carbons is taken off in the upper strata filling, lower floor's filling desulfuration adsorbent.Taking off hydrocarbon adsorbent and desulfurizing agent also can be seated in respectively in two adsorption towers.The amount of adsorbent or desulfurizing agent is formed according to waste gas and is decided.It is 100~5000h that waste gas gets into adsorption tower cumulative volume air speed -1Switch to another or another group tower and adsorb when adsorbents adsorb is full, the adsorbent after saturated carries out Regeneration Treatment, adopts at least two or two groups of adsorbent equipment handover operations among the present invention.Waste gas is through behind two sections or two adsorption towers, and hydro carbons and sulfide all are removed, and the purified gas of adsorption tower outlet directly is discharged in the environment by blower fan suction chimney.
The adsorbent that removes hydro carbons that relates among the present invention comprises the material modified of silica gel, aluminium oxide, molecular sieve, zeolite, active carbon and above-mentioned substance, preferred molecular sieve, active carbon.Active carbon comprises plant material charcoal, ature of coal charcoal, malthenes charcoal, bone black, blood charcoal etc., preferred coal mass active carbon and malthenes active carbon, most preferably coal mass active carbon.Adsorbent can be selected the commodity adsorbent, also can prepare by the existing knowledge in this area.Concrete shape comprises powdery, indefinite form particle, sphere, fibrous, textile-like etc., average grain diameter 1~10mm, preferred 2~6mm, most preferably 3~5mm.The specific area scope of adsorbent is at 200~3000m 2/ g, preferred 400~3000m 2/ g considers most preferably 500~1500m of cost performance 2/ g average pore size 0.3~15nm, preferred 0.5~8nm, most preferably 1.0~3.0nm.Pore volume 0.2~2.0cm 3/ g, preferred 0.3~1.5cm 3/ g, most preferably 0.4~0.8cm 3/ g.
The desulfuration adsorbent that the present invention relates to comprises active carbon, metal mold desulfurizing agent, alkali type desulfurizing agent.Active carbon comprises plant material charcoal, ature of coal charcoal, malthenes charcoal, bone black, blood charcoal etc., preferred coal mass active carbon and malthenes active carbon, most preferably coal mass active carbon.The metal mold desulfurizing agent comprises oxide desulfurizing agent and the above-mentioned various combination of oxides type desulfurizing agent of iron (Fe), zinc (Zn), magnesium (Mg), manganese (Mn), aluminium (Al), calcium (Ca), vanadium (V), chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), molybdenum (Mo), silver (Ag), tungsten (W), with the desulfurizing agent of one or more metal salt solutions dipping modifications of above-mentioned process.Specifically comprise the desulfurizing agent under iron oxide type desulfurizing agent, zinc oxide type desulfurizing agent and all temps.The concrete selection of desulfurizing agent can be according to exhaust gas conditions such as the component of actual waste gas, temperature and is decided.
The adsorption method that relates among the present invention can be fixed bed, thermopnore and revolving bed, all simple fixed bed of preferred embodiment and operation.The quantity of adsorption tower is 1~10, preferred 1~6, and optimum 2~4.
When waste gas component is fairly simple, as only containing sulfide waste gas and dust, then can not add absorbed portion, only need bulky grain dedusting-washing process to get final product, if dust concentration is lower, then only use washing process.
In the running; As long as the sulfide of the control adsorption tower outlet particularly concentration of hydrogen sulfide reaches relevant national standard; Main standard has " odorant pollutant discharge standard " (GB 14554-93), " discharge standard of air pollutants " (GB 16297-1996).
The practical implementation method is as shown in Figure 1; After foul waste gas goes out from process units 1 loss, get into expansion chamber 3, in the waste gas after the particle sedimentation; Get into absorption equipment; Absorption equipment is a bubbling absorption column 2 in the present embodiment, the invention is not restricted to the mode of bubbling absorption column, also can be the tower washing facility of filler, whirlwind washing facility, self-excitation spray washing equipment, plate type washing equipment, Venturi scrubbing equipment, mechanical induction spray washing equipment, hypergravity absorption equipment etc.After the absorption of absorption and washing liquid, the particle in the waste gas is the bottom that the dust solids is deposited to absorption tower 2, discharges at last; Get into two sections adsorption towers 9 through the waste gas after the washing; The hydrocarbon active carbon is taken off in the filling of adsorption tower upper strata, and lower floor is a desulfurizing agent, through after the two layers of adsorbents; Pollutant in the waste gas all is removed, but all zero-emissions of hydro carbons and sulfur-containing compound.Waste gas after the purification is discharged through blower fan 11.
Further specify the implementation process and the effect of the inventive method below through embodiment.
Embodiment 1
Present embodiment adopts wet scrubbing-two section absorption method to handle the foul gas of sulfur-bearing dust and hydro carbons, wherein sulfide concentration 300mg/m 3, total hydrocarbon concentration is 0.2% (volume ratio), dust concentration is 3000mg/m 3, EGT normal temperature.Additive is a sodium alkyl benzene sulfonate, and the alkyl benzene sulphonate na concn is 2wt%.The air speed of waste gas in absorption and washing equipment is 4000h -1, liquid-gas ratio is 15L/m 3Adsorption tower lower floor adsorbent is the swage desulfurizing agent, specific area 713m 2/ g, pore volume 0.39ml/g, average pore size 2.2nm.The upper strata is the solvent recovery active carbon, its specific area 1013m 2/ g, pore volume 0.49ml/g, average pore size 1.3nm.After this PROCESS FOR TREATMENT, the exit gas total hydrocarbon concentration is less than 120 μ L/L, and sulfide concentration is lower than 1 μ L/L.Desulfurizing agent and active carbon volume ratio are 1: 2 in the adsorption tower, and waste gas is 800h through the adsorption tower air speed -1Be 1 year service cycle (adsorbent and desulfurizing agent replacement cycle).Toxic emission concentration is far below discharging standards.
Comparative example 1
This comparative example adopts process and the condition identical with embodiment 1, adopts traditional cyclone dust removal, adopts the water that does not contain additive to carry out wet dust removal then, carries out the purification of desulfurizing agent and adsorbent then.Under the treatment conditions identical with embodiment 1, adsorbent and desulfurizing agent replacement cycle are 2 weeks (be mainly dust deposit and cause pressure drop to raise, need to stop work and handle, the visible wet dust removal effect of additive of not using is relatively poor), and service cycle is very short.
Embodiment 2
In certain industrial plants loss waste gas, exhausted air quantity is 500m 3/ h, normal temperature, hydrogen sulfide 100mg/m 3, organic sulfur compound 50mg/m 3, dust concentration 4000mg/m 3Adopt flow tank-bubbling absorption column that waste gas is purified.Absorption and washing liquid consists of the 5wt% clorox, 1wt% NaOH, 5wt% NPE, 5wt% sodium alkyl benzene sulfonate.The air speed of waste gas in bubbling absorption column is 2000h -1, liquid-gas ratio is 5L/m 3After the purification of this technology, dust is removed fully, and hydrogen sulfide waste gas is purified fully, and organic sulfur compound exports less than 1mg/m 3
Comparative example 2
Exhaust gas conditions is the same, adopts the dedusting of wet type venturi scrubber, and deduster dust removal efficiency has only about 60%.Adopt the packed tower scrubbing tower to purify sulfide, the absorption and washing fluid component is a 10wt% NaOH.In the purified gas, hydrogen sulfide is removed fully, but the organic sulfur compound clearance has only 30%, and along with the prolongation of the duration of runs, dust deposit appears in packed tower, the phenomenon that the operation pressure drop raises.

Claims (13)

1. the processing method of the foul waste gas of sulfur-bearing and dust; Waste gas adopts the liquid-absorbent dust removal process; The aqueous solution to contain additive is absorption and washing liquid, and additive comprises cleaning agent, and cleaning agent is the material with cleaning organic matter function; Be in surfactant and the washing agent one or more, the cleaning agent consumption is 2%~50% of absorption and washing liquid by weight; Waste gas removes harmful miscellaneous material through solid absorbent after adopting the liquid-absorbent dust removal process, and solid absorbent comprises desulfuration adsorbent and/or takes off hydrocarbon adsorbent; The foul waste gas of sulfur-bearing and dust is the foul waste gas of sulfur-bearing, dust and hydro carbons, and the weak organic matter of hydro carbons polarity in the dust granules absorption waste gas becomes dust granules and has hydrophobic particle.
2. according to the described method of claim 1, it is characterized in that the cleaning agent consumption is 2%~20% in the absorption and washing liquid.
3. according to the described method of claim 1, it is characterized in that the additive in the absorption and washing liquid comprises alkaline matter or oxidant.
4. according to the described method of claim 3; It is characterized in that alkaline matter is selected from one or more in NaOH, sodium carbonate, sodium acid carbonate, potassium hydroxide, potash and the saleratus, the alkaline matter consumption is to account for 0.5%~50% of absorption and washing liquid weight.
5. according to the described method of claim 4, it is characterized in that the alkaline matter consumption is to account for 1%~30% of absorption and washing liquid weight.
6. according to the described method of claim 3, it is characterized in that oxidant is selected from one or more in clorox, hydrogen peroxide solution, chlorine dioxide, sulfonated phthalocyanine cobalt, molysite and the potassium permanganate, consumption is to account for 0.5%~20% of absorption and washing liquid weight.
7. according to the described method of claim 6, it is characterized in that the oxidant consumption is to account for 1%~10% of absorption and washing liquid weight.
8. according to the described method of claim 1; It is characterized in that absorption and washing adopts packed tower washing facility, whirlwind washing facility, self-excitation spray washing equipment, plate type washing equipment, Venturi scrubbing equipment, hypergravity absorption equipment, mechanical induction spray washing equipment or catheter type absorption and washing equipment, the air speed of waste gas in absorption and washing equipment is 100h -1~20000h -1, liquid-gas ratio is 0.2~50L/m 3
9. according to the described method of claim 1, it is characterized in that described desulfuration adsorbent is active carbon type desulfurizing agent, metal oxide type desulfurizing agent or alkali type desulfurizing agent, the described hydrocarbon adsorbent that takes off is silica gel, aluminium oxide, molecular sieve, zeolite or active carbon.
10. according to the described method of claim 1, it is characterized in that waste gas is earlier through desulfuration adsorbent, then through taking off hydrocarbon adsorbent.
11., it is characterized in that waste gas is 100~5000h through the cumulative volume air speed of solid absorbent according to the described method of claim 1 -1
12., it is characterized in that the foam removal facility being set at the absorption and washing equipment port of export according to the described method of claim 8.
13. according to the described method of claim 1, it is characterized in that before the absorption and washing operation, flow tank being set, adopt electric precipitation, gravitational settling dedusting, inertial dust collection or cyclone dust removal mode to remove big dust particle or drop.
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