CN108671740B - A kind of application of the biological active filling material comprising Meng Shi pseudomonad in purification of sulphur-containing exhaust gas - Google Patents

A kind of application of the biological active filling material comprising Meng Shi pseudomonad in purification of sulphur-containing exhaust gas Download PDF

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CN108671740B
CN108671740B CN201810455521.4A CN201810455521A CN108671740B CN 108671740 B CN108671740 B CN 108671740B CN 201810455521 A CN201810455521 A CN 201810455521A CN 108671740 B CN108671740 B CN 108671740B
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filler
microbial activity
sulphur
meng shi
exhaust gas
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CN108671740A (en
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任仁
朱利军
柴春燕
张徐祥
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Nanjing Jiangdao Environmental Science And Technology Research Institute Co ltd
Dajiang Environment Co ltd
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Dajiang Environment 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01DSEPARATION
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    • B01D53/34Chemical or biological purification of waste gases
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    • 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
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    • 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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Abstract

The invention belongs to field of environmental improvement, and in particular to a kind of application of the microbial activity filler in purification of sulphur-containing exhaust gas containing Meng Shi pseudomonad.The Meng Shi pseudomonad is specially Meng Shi pseudomonad (Pseudomonas monteilii) LW-1, deposit number is CGMCC No.13748, the microbial activity filler is adsorbed on filler by Meng Shi pseudomonad bacteria suspension, and filler is seated in wire side hollow sphere and is prepared, the filler be used to handle the generation of agricultural chemicals waste water reservoir containing the organic sulphur waste gas, gas flow 100-5000m3/ h, residence time 1.0-5.0min, 35-55 DEG C of temperature, malathion, parathion, parathion-methyl total concentration be 20-200mg/m3, malathion, parathion, parathion-methyl degradation efficiency can achieve 90% or more.

Description

A kind of biological active filling material comprising Meng Shi pseudomonad is in purification of sulphur-containing exhaust gas Using
Technical field:
The invention belongs to field of environmental improvement, and in particular to one kind includes Meng Shi pseudomonad (Pseudomonas Monteilii) application of the biological active filling material of LW-1 in removing sulphur-containing exhaust gas.
Background technique:
Waste water in pesticide producing contains a large amount of organosulfur pesticide and organo-chlorine pesticide intermediate, complicated component, concentration High, strong toxicity.The product or in which mesosome of part organosulfur pesticide and organo-chlorine pesticide such as parathion, malathion, methyl pair Sulphur phosphorus, trichloroacetaldehyde, phosphorus trichloride etc., have a volatility, and most of organic sulfur and organo-chlorine pesticide have it is pungent Peculiar smell.
Parathion (C10H14NO5It PS) is colourless oil liquid, solubility is 24mg/L (25 DEG C) in water.It is slightly soluble in petroleum ether And kerosene, there can be garlic odour with most immiscible organic solvents.It is promptly hydrolyzed in alkaline medium;In neutral or slightly acidic solution In it is relatively stable;It is all unstable to ultraviolet light and air.There are mutagenicity and animal teratogenesis to microorganism.Belong to hypertoxic type, tool There are acute toxicity, irritation, mutagenicity.Human lymphocyte Sister chromatid exohange is influenced when 200 μ g/L;10μmol/L When influence human fibroblasts unscheduled DNA synthesis;When 10 μm of ol/L, rat lymphocyte DNA damage, IARC are made in 16 hours Carcinogenicity is evaluated as G3 grades;The minimum toxic dose of rat oral (TDLo): 360 μ g/kg (pregnant 2~22d/ postpartum 15d) influence new Raw mouse is biochemical and is metabolized;The minimum toxic dose of subcutaneous rat (TDLo): 9800 μ g/kg (pregnant 7~13d), lethal tire.Parathion energy Enter human body by alimentary canal, respiratory tract and complete skin and mucous membrane.Parathion in environment can also be sent out by food chain Raw biological concentration.
Malathion (C10H19O6PS2) it is colourless or pale yellow oily liquid, there is garlic smell.Chance open fire, high fever is flammable;With Strong oxidizer reacts;Phosphorus, sulfur oxide gas are generated by thermal decomposition;It is toxic to animal, it is irritating to eyes, skin Property;Active in 5.0 or less pH, pH7.0 or more is easy hydrolysis failure.Female mice acute oral LD50 is 1751.5mg/kg, male Rat acute LD50 is 1634.5mg/kg, and the percutaneous LD50 of rat acute is 4000~6150mg/kg.Poisoning symptom is head Bitterly, dizziness, nausea, inability, hidrosis, vomiting, salivation, eye-blurred, myosis, spasm, stupor, flesh fibrillation, pulmonary edema etc.. Generally morbidity is very fast after contact in a short time (oral, sucking, skin, mucous membrane) a large amount of organophosphorus pesticides.Malathion poisoning is dived The volt phase is longer.It absorbs through skin, falls ill in 12h, poisoning symptom shows as appetite stimulator, Nausea and vomiting, abdominal pain, hidrosis, thing Object is fuzzy, myosis, respiratory secretions increase, bronchial spasm expiratory dyspnea, pulmonary edema;Sample Symptoms are muscle bundle shake It quivers, muscle spasmus, myoparalysis;Central nervous system symptom shows as headache, dizzy, insomnia drowsiness, out of strength, irritated, twitch living, dusk Fan, brain edema.The state of an illness is heavier when oral ingestion, and gastrointestinal symptom becomes apparent from.Some cases can have cardiac muscle, liver, renal damage.
Parathion-methyl (C8H10NO5PS): colorless crystalline powder, industrial goods are brown or yellow liquid or solid, are met bright Fire, high fever is flammable, by poisonous gas such as thermal decomposition release phosphorus, sulfur oxides, can decompose rapidly in lye.To big white mouse urgency Property LD50 of passing through mouth be 14~24mg/kg, to rabbit acute percutaneous LD50 be 300~400mg/kg, belong to high toxic pesticide.Methyl is to sulphur Phosphorus tool is tagged and stomach poison function, can inhibit the vigor of cholinesterase in pest nervous system and lethal, and insecticidal spectrum is wide, is often processed into Missible oil or pulvis (see the formulations of pesticide) use, and are mainly used for prevention and treatment various agricultural pest.It is prominent with certain cause to microorganism Denaturation, such as 667 μ g/ ware of salmonella typhimurium;Escherichia coli: 10mmol/L.Gaseous state, mist state, aerosol state or powdery It is easily absorbed for respiratory tract, liquid can be through eye mucous membrane, skin or gastrointestinal tract.Into after in vivo, distribution to each device of whole body rapidly Official's tissue, and be firmly combined with histone.
Organo-chlorine pesticide is one of current most popular insecticide, is occupied an important position in pesticide market.So And in organo-chlorine pesticide production and agricultural chemicals waste water treatment process, there is volatile Pesticidal products or intermediate, waved from liquid phase Hair, spills into air, forms air pollution.
Volatile pesticide and intermediate include: metrifonate, DDVP, phosphorus trichloride, dichlobenil, herbicide, thimet, Phoxim, biphenyl, BFPO, alkane and alkane substitute class intermediate, aromatic intermediate etc. (choosing organochlorine), these substances Most of have a pungent smell, some substances such as diethyl phosphite, trichloroacetaldehyde, belong to carcinogenicity, mutagenicity and The cause property substance of the three of teratogenesis.
It is these organic sulfurs with peculiar smell, organic because being aerated, pushing the mechanical disturbances such as water flow in wastewater treatment process Chlorine is spilt into air from water, forms odor pollution.If not being subject to processing appropriate, the organochlorine in air is spilt into, Serious pollution environment, is detrimental to health.
Biotechnology cleans because it has many advantages, such as at low cost, easy to operate, technology, is without secondary pollution, is effective at present Handle one of the important method containing organic compounds.The principle of biologic treating technique is to utilize the biological oxidation of microorganism will Organic sulfur conversion is the process of the harmless or low harmful substances such as sulfate, carbon dioxide, water, as follows:
Malathion → carbon dioxide+sulfate+water;
Parathion-methyl → p-nitrophenol+organic sulfate → sulfate+phosphate+carbon dioxide+water;
Parathion → p-nitrophenol+organic sulfate → sulfate+phosphate+carbon dioxide+water.
The principle of biologic treating technique is to convert carbon dioxide, salt for organochlorine using the biological oxidation of microorganism Hydrochlorate and water etc. be harmless or the process (formula 1) of low harmful substance.
C2HCl3O+O2→CO2+H2O+HCl (formula 1)
Existing research shows that the facultative chemoheterotrophy bacterium in natural environment belongs to pseudomonad (Pseudomonas Sp.) X2 (201310551914.2), Sphingobacterium (Sphingobacterium griseoflavus) SCU-B140 (201510715812.9), Acidithiobacillus ferrooxidans strain GF (Acidithiobacillus ferrooxidans), thermophilic iron hook end The mixed culture of spirillum (Leptospirillum ferriphilum) and Ferroplasma acidiphilum (201310745138.X) etc. has degradation to organosulfur pesticide.But not yet discovery is for handling organic sulfur and organic The Meng Shi pseudomonad (Pseudomonas monteilii) of chlorine, and use Meng Shi pseudomonad processing sulfur-bearing, contain chlorine pollution The method of object.
Summary of the invention:
In order to solve, volatility organic sulfur treatment effeciency in the prior art is low, microorganism is uneven in mixed carrier area load It is even, starting is slow, the problem of filler collapses is used for a long time, the present invention provides one plant of Meng Shi pseudomonad (Pseudomonas Monteilii), and by the bacterial strain removing is applied to containing in the organic sulphur waste gas.
The Meng Shi pseudomonad, specially Meng Shi pseudomonad (Pseudomonas monteilii) LW-1, be from It is tamed and dociled in agricultural chemicals waste water containing the organochlorines such as the organic sulfurs such as parathion-methyl, malathion, parathion and phosphorus trichloride, trichloroacetaldehyde Change, isolated separation bacterium.The bacterial strain is preserved in China Committee for Culture Collection of Microorganisms on March 10th, 2017 Common micro-organisms center, deposit number CGMCCNo.13748, preservation address: Yard 1, BeiChen xi Road, Chaoyang District, Beijing City 3, Institute of Microorganism, Academia Sinica, postcode 100101.
The bacterial strain feature is as follows:
Meng Shi pseudomonad (Pseudomonas monteilii) LW-1: cell is in the shape of a rod, peritrichous, gram dye Color is negative, and Starch Hydrolysis, VP, indole reaction are feminine gender, and gelatin liquefaction, glucose response are the positive.Bacterium colony is white, round, Surface is smooth, moistens sticky, flat protrusion.In the natural environment, competitiveness is strong, wide adaptation range, can utilize carbon extensively Hydrate, amino acid, organic acid be carbon source, pH wide adaptation range (pH 3.0-7.0), under high temperature (50 DEG C -60 DEG C) part all It can grow, optimum growth temperature is 30-55 DEG C, pH 4.0-6.5.
The present invention also provides a kind of microbial activity filler, the microbial activity filler is by Meng Shi pseudomonad LW-1 Bacteria suspension is adsorbed on filler, and filler is seated in wire side hollow sphere and is prepared, can preferably treatment and purification containing organic The exhaust gas of sulphur.
The filler is one of polyurethane foamed blocks, haydite, volcanic rock or molecular sieve or a variety of;
The packing density is 20-80kg/m3, porosity 50-97%, partial size 10-100mm;
The mass ratio of the microbial bacteria suspension and filler is 1-12: 1;
Meng Shi pseudomonad LW-1 cell concentration 1.0 × 10 in the microbial activity filler5-9.0×108CFU/ g(filler)
The wire side hollow sphere material is polyethylene, polyvinyl chloride or polypropylene;
The hollow bulb diameter 6cm of the wire side, is made of two hemisphere, and each hemisphere surface is porous, the aperture in each hole 2-8mm;
There is a circle reinforcing ring in the middle part of the wire side hollow sphere, reinforcing ring is equipped with lock, convenient for unlatching and closure two Hemisphere.
Specific preparation process is as follows for the filler:
(1) preparation of Meng Shi pseudomonad LW-1 bacteria suspension
1. being carried out liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activation by 10-25% inoculum concentration Expand fermented and cultured step by step;
Fermentation culture conditions are as follows: in 35-45 DEG C, ventilation quantity 10-100L/min, dissolved oxygen > 2.0mg/L, tank presses 0.03- Under the conditions of 0.10Mpa, incubation time 45-55h;
The composition of the liquid fermentation medium are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.2-7.0,115 DEG C go out Bacterium 20min is cooled to room temperature after sterilizing and adds 4.5mg/L parathion;
2. after fermented and cultured, fermentation liquid being placed in refrigerated centrifuge in 4 DEG C, 2000-8000rpm, 10- is centrifuged 20min discards supernatant liquid, and precipitating is diluted with sterile nutrient solution, and acquisition cell concentration is 0.30-0.95g/L Meng Shi pseudomonad LW-1 bacteria suspension;
The composition of the sterile nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgCl20.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.8-7.2,121 DEG C go out Bacterium 20min;
(2) preparation of microbial activity filler:
1. the filler of packet or grain shape is filled into wire side hollow sphere, the mass ratio of filler and wire side hollow sphere For 0.9-3:1;
2. being sprayed the Meng Shi pseudomonad LW-1 bacteria suspension of step (1) preparation by the hole of wire side hollow sphere to packet Or the surface of the filler of grain shape;
It is mixed 3. the wire side hollow sphere that load has filler is put into rotate in impeller;
4. again to the wire side hollow sphere surface spraying Meng Shi pseudomonad LW-1 bacteria suspension that filler is housed;
It repeats step 1. -4. 2-3 time, equal appendix on filler is made in hollow ball surface and hole to have bacterium cell, acquisition Meng Shi Pseudomonad LW-1 cell concentration reaches 1.0 × 105-9.0×108CFU/g(filler)Microbial activity filler, 4 DEG C of preservations are standby With.
The method containing the organic sulphur waste gas, specific steps are handled using mentioned microorganism active filler the present invention also provides a kind of It is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonad LW-1 to be placed in a container above-mentioned appendix, be passed through containing pair The gas of sulphur phosphorus activates microbial activity filler using parathion as phosphorus source, sulphur source;Activation time is 2-15 days;
The concentration of parathion in the gas containing parathion being passed through is 50-200mg/m3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacation Monad LW-1 purifies the organic sulfur in exhaust gas, and microbial activity packing volume is 0.1-1000m3, the total concentration of organic sulfur is 20-200mg/m3, gas flow rate 0.05-10000m3/ h, residence time 1.5-10.0min, purification temperature are 30-65 DEG C;It is fixed Phase maintains the activity of microbial activity filler to microbial activity filler surface spraying nutrient solution, and spray frequency is 1-3 days sprays 1 Secondary, each spray rate is 1.0-200L/min, and each spray time is 10-90min;
The composition of the nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, pH value 6.2-7.0.
The utility model has the advantages that
1. Meng Shi pseudomonad (Pseudomonas monteilii) LW-1 degradation organic sulfur with higher of the invention Efficiency, up to 90-100%;And the laundering period of dominant bacteria is short, and inoculation can quickly start degradation reaction in 1 week, applies It purifies in the exhaust gas bioreactor containing organic sulfur, the starting period can be shortened.
2. using the effect of a variety of mechanics such as sedimentation, attachment and centrifugation, by the Meng Shi pseudomonad (Pseudomonas that degrades Monteilii) LW-1 appendix forms microbial activity filler, bacterium cell on the light porous material of wire side hollow ball inside It can not only be uniformly adhered to filler surface, and be able to enter in the hole inside filler, the bacterium of microbial activity filler is made Cell appendix amount is high, is not easy to be lost from bioreactor.
3. Meng Shi pseudomonad (Pseudomonas monteilii) LW-1 has, distribution is wide, quantity is more, nutritional need is simple Feature single, breeding is fast, competition colonization power is strong.The pseudomonad inhibits other microorganisms, containing biting iron by secretion antibiotic Element, the siderophore that can be secreted have a clear superiority in the competition of iron.
4. Meng Shi pseudomonad (Pseudomonas monteilii) LW-1 is chemoorganotrophy type, there is catalase, It can utilize and decomposing volatile organic sulfur/organochlorine.
5. Meng Shi pseudomonad (Pseudomonas monteilii) LW-1 has antiviral activity, to TMV (Tobacco mosaic Virus), the viruses such as PVY (marmor upsilon) have inhibiting effect, use is safer.
6. the rough surface, porous of the carrier material for microbial activity filler is suitable for bacterium cell and adheres to;Specific surface area Greatly, be conducive to the volatility such as bacterium cell and parathion, trichloroacetaldehyde organic sulfur, organochlorine contacts;Load the wire side of light filler Hollow sphere hole is more, and good permeability, resistance is small, and mass-transfer efficiency is high;Microbial activity filler weight is light, intensity is high, the pressure loss It is small;It is high temperature resistant, corrosion-resistant;Not perishable deformation, can be used for a long time and adapt to the physical condition of Various Complex.
Detailed description of the invention:
Fig. 1 Meng Shi pseudomonad (Pseudomonas monteilii) LW-1 phylogenetic tree.
Specific embodiment:
In order to which the objects, technical solutions and advantages of this patent are more clearly understood, below in conjunction with specific embodiment, to this Patent is further elaborated.It should be appreciated that specific embodiment described herein is only to explain this patent, and do not have to It is of the invention in limiting.
Strain idenfication:
DNA is extracted: being mentioned using Full-automatic magnetic beads instrument for extracting nucleic acid Smart LabAssist-16 and respective environment sample DNA Take purification kit (Taiwan dot nanometer technical concern Co., Ltd) screen respectively acquisition bacterial strain DNA extract with it is pure Change, bacterial universal primers F16S-27 and R16S-1492 is selected to carry out PCR amplification, primer sequence is respectively as follows:
F16S-27(5`-AGAGTTTGATCCTGGCTCAG-3`)
R16S-1492(5`-CGGTTACCTTGTTACGACTTC-3`)
PCR reaction condition setting are as follows: 94 DEG C of initial denaturation 5min;Subsequent 94 DEG C of denaturation 30s, 56 DEG C of annealing 30s, 72 DEG C of extensions 90s recycles 25 periods;Then 72 DEG C of extension 10min;Last 4 DEG C of holdings 10min.By being purified to PCR product, after quality inspection PCR purified product is connected on PMD-18T carrier, is then transformed into bacillus coli DH 5 alpha competent cell.After converting 50 μ L of competent cell be coated on the LB culture medium containing isopropylthiogalactoside, X-gal and ammonia benzyl.37 DEG C of constant temperature Incubator is incubated overnight, and carries out LB liquid medium culture from each plate picking 25 white single bacterium spots.After culture 2 hours, Culture solution is subjected to sequencing analysis.The sequence measured uses DNAMAN software to carry out similitude merger first, and similitude is greater than 97% sequence merger is an operating unit, and the representative sequence chosen in each operating unit utilizes BLAST and GenBank number Homology analysis is carried out according to the 16SrDNA gene order in library, 1400bp or more length is chosen and is compared (Clustelx1.83), Phylogenetic Analysis (MEGA3.1) is carried out using ortho position connection (Neighbour Joining) method, system Development tree is as shown in Figure 1.It is compared by DNA sequence dna, which is Meng Shi pseudomonad (Pseudomonas monteilii), It is named as Meng Shi pseudomonad (Pseudomonas monteilii) LW-1.
Embodiment 1: a kind of microbe stuffing of the removing containing the organic sulphur waste gas and its preparation
A kind of microbial activity filler is to be adsorbed in polyurethane foamed blocks filler by Meng Shi pseudomonad LW-1 bacteria suspension On, and filler is seated in wire side hollow sphere and is prepared;
Packing density is 20kg/m3, porosity 90%, partial size 10mm;The mass ratio of microbial bacteria suspension and filler It is 1: 1;Meng Shi pseudomonad LW-1 cell concentration 1.0 × 10 in microbial activity filler5CFU/g(filler)
The wire side hollow sphere material is polyethylene;The hollow bulb diameter 6cm of wire side, is made of, Mei Geban two hemisphere Ball surface is porous, the aperture 2mm in each hole;There is a circle reinforcing ring in the middle part of wire side hollow sphere, reinforcing ring is equipped with lock, convenient for opening Open and be closed two hemisphere.
Specific preparation process is as follows for the filler:
(1) preparation of Meng Shi pseudomonad LW-1 bacteria suspension
1. being carried out liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activation step by step by 10% inoculum concentration Expand fermented and cultured;
Fermentation culture conditions are as follows: in 35 DEG C, ventilation quantity 10L/min, dissolved oxygen > 2.0mg/L, tank presses 0.03-0.10Mpa item Under part, incubation time 55h;
Slant medium composition are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, agar 20g, pH value 6.2-7.0,115 DEG C of sterilizings 20min;
The composition of the liquid fermentation medium are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.2-7.0,115 DEG C go out Bacterium 20min is cooled to room temperature after sterilizing and adds 4.5mg/L parathion;
2. after fermented and cultured, fermentation liquid being placed in refrigerated centrifuge in 4 DEG C, 2000rpm, 10min is centrifuged, discards Supernatant, precipitating are diluted with sterile nutrient solution, and acquisition cell concentration is 0.30g/L Meng Shi pseudomonad LW-1 bacteria suspension;
The composition of the sterile nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgCl20.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.8-7.2,121 DEG C go out Bacterium 20min;
(2) preparation of microbial activity filler:
1. packet filler is filled into wire side hollow sphere, the mass ratio of filler and wire side hollow sphere is 0.9:1;
2. being sprayed the Meng Shi pseudomonad LW-1 bacteria suspension of step (1) preparation by the hole of wire side hollow sphere to packet The surface of the filler of shape;
It is mixed 3. the wire side hollow sphere that load has filler is put into rotate in impeller;
4. again to the wire side hollow sphere surface spraying Meng Shi pseudomonad LW-1 bacteria suspension that filler is housed;
1. -4. 2 time it repeats step, makes in hollow ball surface and hole that equal appendix has bacterium cell on filler, obtain Meng Shi vacation Monad LW-1 cell concentration reaches 1.0 × 105CFU/g(filler)Microbial activity filler, 4 DEG C save backup.
Embodiment 2: a kind of microbe stuffing of the removing containing the organic sulphur waste gas and its preparation
A kind of microbial activity filler is to be adsorbed on ceramics filling by Meng Shi pseudomonad LW-1 bacteria suspension, and will fill out Material, which is seated in wire side hollow sphere, to be prepared;Packing density is 80kg/m3, porosity 50%, partial size 100mm;Micro- life The mass ratio of object bacteria suspension and filler is 12: 1;Meng Shi pseudomonad LW-1 cell concentration 9.0 in microbial activity filler × 108CFU/g(filler)
The wire side hollow sphere material is polyvinyl chloride;The hollow bulb diameter 6cm of wire side, is made of, each two hemisphere Hemisphere surface is porous, the aperture 8mm in each hole;There is a circle reinforcing ring in the middle part of wire side hollow sphere, reinforcing ring is equipped with lock, is convenient for Open and be closed two hemisphere.
Specific preparation process is as follows for the filler:
(1) preparation of Meng Shi pseudomonad LW-1 bacteria suspension
1. being carried out liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activation step by step by 25% inoculum concentration Expand fermented and cultured;
Fermentation culture conditions are as follows: in 45 DEG C, ventilation quantity 100L/min, dissolved oxygen > 2.0mg/L, tank presses 0.10Mpa condition Under, incubation time 45h;
Slant medium composition are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, agar 20g, pH value 6.2-7.0,115 DEG C of sterilizings 20min;
The composition of the liquid fermentation medium are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.2-7.0,115 DEG C go out Bacterium 20min is cooled to room temperature after sterilizing and adds 4.5mg/L parathion;
2. after fermented and cultured, fermentation liquid being placed in refrigerated centrifuge in 4 DEG C, 8000rpm, 20min is centrifuged, discards Supernatant, precipitating are diluted with sterile nutrient solution, and acquisition cell concentration is 0.95g/L Meng Shi pseudomonad LW-1 bacteria suspension;
The composition of the sterile nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgCl20.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.8-7.2,121 DEG C go out Bacterium 20min;
(2) preparation of microbial activity filler:
1. the filler of grain shape is filled into wire side hollow sphere, the mass ratio of filler and wire side hollow sphere is 2:1;
2. being sprayed the Meng Shi pseudomonad LW-1 bacteria suspension of step (1) preparation by the hole of wire side hollow sphere to granulated The surface of the filler of shape;
It is mixed 3. the wire side hollow sphere that load has filler is put into rotate in impeller;
4. again to the wire side hollow sphere surface spraying Meng Shi pseudomonad LW-1 bacteria suspension that filler is housed;
1. -4. 3 time it repeats step, makes in hollow ball surface and hole that equal appendix has bacterium cell on filler, obtain Meng Shi vacation Monad LW-1 cell concentration reaches 9.0 × 108CFU/g(Filler)Microbial activity filler, 4 DEG C save backup.
Embodiment 3: a kind of microbe stuffing of the removing containing the organic sulphur waste gas and its preparation
A kind of microbial activity filler is to be adsorbed on volcanic filling material by Meng Shi pseudomonad LW-1 bacteria suspension, and incite somebody to action Filler is seated in wire side hollow sphere and is prepared;Packing density is 50kg/m3, porosity 75%, partial size 50mm;Micro- life The mass ratio of object bacteria suspension and filler is 8: 1;Meng Shi pseudomonad LW-1 cell concentration 3.0 in microbial activity filler × 107CFU/g(filler)
The wire side hollow sphere material is polypropylene;The hollow bulb diameter 6cm of wire side, is made of, Mei Geban two hemisphere Ball surface is porous, the aperture 5mm in each hole;There is a circle reinforcing ring in the middle part of wire side hollow sphere, reinforcing ring is equipped with lock, convenient for opening Open and be closed two hemisphere.
Specific preparation process is as follows for the filler:
(1) preparation of Meng Shi pseudomonad LW-1 bacteria suspension
1. being carried out liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activation step by step by 17% inoculum concentration Expand fermented and cultured;
Fermentation culture conditions are as follows: in 40 DEG C, ventilation quantity 50L/min, dissolved oxygen > 2.0mg/L, tank presses 0.03-0.10Mpa item Under part, incubation time 50h;
Slant medium composition are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, agar 20g, pH value 6.2-7.0,115 DEG C of sterilizings 20min;
The composition of the liquid fermentation medium are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.2-7.0,115 DEG C go out Bacterium 20min is cooled to room temperature after sterilizing and adds 4.5mg/L parathion;
2. after fermented and cultured, fermentation liquid is placed in refrigerated centrifuge in 4 DEG C, 5000rpm, 10-20min is centrifuged, Liquid is discarded supernatant, precipitating is diluted with sterile nutrient solution, and acquisition cell concentration is 0.65g/L Meng Shi pseudomonad LW-1 bacteria suspension;
The composition of the sterile nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgCl20.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.8-7.2,121 DEG C go out Bacterium 20min;
(2) preparation of microbial activity filler:
1. packet filler is filled into wire side hollow sphere, the mass ratio of filler and wire side hollow sphere is 3:1;
2. being sprayed the Meng Shi pseudomonad LW-1 bacteria suspension of step (1) preparation by the hole of wire side hollow sphere to box-shaped The surface of the filler of shape;
It is mixed 3. the wire side hollow sphere that load has filler is put into rotate in impeller;
4. again to the wire side hollow sphere surface spraying Meng Shi pseudomonad LW-1 bacteria suspension that filler is housed;
1. -4. 3 time it repeats step, makes in hollow ball surface and hole that equal appendix has bacterium cell on filler, obtain Meng Shi vacation Monad LW-1 cell concentration reaches 3.0 × 107CFU/g(filler)Microbial activity filler, 4 DEG C save backup.
A kind of embodiment 4: method of the microbial activity filler processing containing the organic sulphur waste gas
The method containing the organic sulphur waste gas is handled using microbial activity filler described in embodiment 1 the present invention also provides a kind of, Specific step is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonad LW-1 to be placed in a container 1 appendix of embodiment, be passed through and contain The gas of parathion activates microbial activity filler using parathion as phosphorus source, sulphur source;Activation time is 15 days;
The concentration of parathion in the gas containing parathion being passed through is 50mg/m3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacation Monad LW-1 purifies the organic sulfur in exhaust gas, and microbial activity packing volume is 0.1m3, malathion and parathion in air inlet Concentration be respectively 17.3mg/m3And 46.7mg/m3, gas flow rate 0.05m3/ h, residence time 1.5min, purification temperature are 30℃;The activity of microbial activity filler is periodically maintained to microbial activity filler surface spraying nutrient solution, spray frequency is 3 days Spray 1 time, each spray rate are 1.0L/min, and each spray time is 10min;Gas outlet malathion and parathion it is dense Degree is reduced to 2.2mg/m3And 4.3mg/m3, removal rate respectively reaches 87.3% and 90.8%.
The composition of the nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, pH value 6.2-7.0.
A kind of embodiment 5: method of the microbial activity filler processing containing the organic sulphur waste gas
The method containing the organic sulphur waste gas is handled using microbial activity filler described in embodiment 2 the present invention also provides a kind of, Specific step is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonad LW-1 to be placed in a container 2 gained appendix of embodiment, lead to Enter the gas containing parathion, using parathion as phosphorus source, sulphur source, activates microbial activity filler;Activation time is 2 days;
The concentration of parathion in the gas containing parathion being passed through is 200mg/m3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacation Monad LW-1 purifies the organic sulfur in exhaust gas, and microbial activity packing volume is 1000m3, in air inlet, the concentration of parathion is 162.7mg/m3, the concentration of parathion-methyl is 32.1mg/m3, gas flow rate 10000m3/ h, residence time 10.0min, only Changing temperature is 65 DEG C;The activity of microbial activity filler, spray are periodically maintained to microbial activity filler surface spraying nutrient solution Frequency is to spray 1 time for 1 day, and each spray rate is 200L/min, and each spray time is 90min;Gas outlet, parathion it is dense Degree is reduced to 11.3mg/m3, the concentration of parathion-methyl is reduced to 2.8mg/m3.It is (right that their removal rate respectively reaches 93.1% Sulphur phosphorus) and 91.3% (parathion-methyl).
The composition of the nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, pH value 6.2-7.0.
A kind of embodiment 6: method of the microbial activity filler processing containing the organic sulphur waste gas
The method containing the organic sulphur waste gas is handled using microbial activity filler described in embodiment 3 the present invention also provides a kind of, Specific step is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonad LW-1 to be placed in a container 3 gained appendix of embodiment, lead to Enter the gas containing parathion, using parathion as phosphorus source, sulphur source, activates microbial activity filler;Activation time is 7 days;
The concentration of parathion in the gas containing parathion being passed through is 100mg/m3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacation Monad LW-1 purifies the organic sulfur in exhaust gas, and microbial activity packing volume is 500m3, in air inlet, the concentration of malathion For 179.2mg/m3, the concentration of parathion-methyl is 56.3mg/m3, gas flow rate 5000m3/ h, residence time 5.0min, only Changing temperature is 50 DEG C;The activity of microbial activity filler, spray are periodically maintained to microbial activity filler surface spraying nutrient solution Frequency is to spray 1 time for 2 days, and each spray rate is 100L/min, and each spray time is the gas outlet 50min., malathion Concentration is reduced to 13.9mg/m3, the concentration of parathion-methyl is reduced to 4.1mg/m3.The removal of malathion and parathion-methyl Rate respectively reaches 92.2% and 92.7%.
The composition of the nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, pH value 6.2-7.0.
Embodiment 7: experiment effect
3 gained filler of embodiment is used for the processing of following gases:
(1) exhaust gas containing parathion, gas flow 300m are handled3/ h, residence time 100s, purification temperature 30 ℃.Bioreactor continuous operation 2 months, pH 4-7, the mean air entry concentration of parathion are as follows: 25mg/m3, gas concentration is 2mg/ out m3, removal rate reaches 92%.
Contrast and experiment is shown: when ferro element is not added in nutrient solution, after reactor is run 2 months, and Meng Shi vacation unit cell Bacterium LW-1 quantity is from 3.0 × 107CFU/g increases to 7.0 × 108CFU/g.It adds when to bioreactor containing 0.02g/L iron member After the nutrient solution of element, after reactor is run 2 months, Meng Shi pseudomonad LW-1 quantity is by 3.0 × 107CFU/g increases to 1.0 × 109CFU/g increases significantly, bioreactor is enable effectively to remove the organic sulfur in exhaust gas.
The composition of the nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, pH value 6.2-7.0;Spray frequency is 2 Its spray 1 time, each spray rate are 200L/min, and each spray time is 50min.
(2) for handling the exhaust gas containing malathion of agricultural chemicals waste water treatment process generation, the concentration of malathion is 10mg/ m3, gas flow 3000m3/ h, residence time 95s, 30 DEG C of gas temperature, regular replenishment contains the battalion of 0.02g/L ferro element Nutrient solution (ibid), the removal rate of malathion is close to 100%.
Equipment is run more than 3 months, pH 4-6, Meng Shi pseudomonad (Pseudomonas monteilii) LW-1 quantity Maintain 2.0 × 107-2.5×108CFU/g, while reaching purification purpose, equipment can be run steadily in the long term.
(3) exhaust gas containing methyl mercaptan is handled, gas flow 10L/min, residence time 90s are operated under the conditions of 30 DEG C. Bioreactor continuous operation October, pH4-6, the inlet gas concentration of methyl mercaptan are as follows: 2-5mg/m3, gas concentration is lower than 0.1mg/m out3, Average removal rate: 98%.Reactor Nei Mengshi pseudomonad (Pseudomonas monteilii) LW-1 quantity be 2.0 × 107-2.5×108CFU/g, bioreactor are stable.
In above-mentioned gas treatment process, the starting period of bioreactor is one week.And under equal conditions, it will be in filler After strain replaces with the activated sludge of processing agricultural chemicals waste water, the starting period is 2 weeks-January.
The processing of 8 mixed gas of embodiment
Using the same method of embodiment 3 preparation microbial activity filler (only by fermentation medium addition 4.5mg/L to sulphur Phosphorus replaces with while adding 4.5mg/L parathion and 4.5mg/L trichloroacetaldehyde) method of the processing containing organic sulfur, chlorine exhaust gas, specifically Steps are as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonad LW-1 to be placed in a container appendix, be passed through containing parathion, The gas of trichloroacetaldehyde activates microbial activity filler;Activation time is 7 days;
The concentration of parathion in the gas containing parathion being passed through is 100mg/m3, the concentration of trichloroacetaldehyde is 100mg/m3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing organic sulfur, chlorine exhaust gas, with illiteracy Family name pseudomonad LW-1 purifies organic sulfur, chlorine in exhaust gas, and microbial activity packing volume is 500m3, in air inlet, malathion 37.7mg/m3, parathion 16.1mg/m3Trichloroacetaldehyde 9.8mg/m3;Gas flow rate is 5000m3/ h, residence time 5.0min, only Changing temperature is 50 DEG C;The activity of microbial activity filler, spray are periodically maintained to microbial activity filler surface spraying nutrient solution Frequency is to spray 1 time for 2 days, and each spray rate is 100L/min, and each spray time is the gas outlet 50min., malathion 3.2mg/m3, parathion 1.3mg/m3Trichloroacetaldehyde 2.3mg/m3.Malathion removal rate 91.5%, parathion removal rate 92% Trichloroacetaldehyde removal rate 76.5%.
The composition of the nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, pH value 6.2-7.0.

Claims (10)

1. a kind of application of microbial activity filler in purification of sulphur-containing exhaust gas, which is characterized in that the microbial activity filler It is to be adsorbed on filler by Meng Shi pseudomonad bacteria suspension, and filler is seated in wire side hollow sphere and is prepared;
The Meng Shi pseudomonad is specially Meng Shi pseudomonad (Pseudomonas monteilii) LW-1, and deposit number is CGMCC No.13748。
2. a kind of application of the microbial activity filler as described in claim 1 in purification of sulphur-containing exhaust gas, which is characterized in that institute Stating filler is one of polyurethane foamed blocks, haydite, volcanic rock or molecular sieve or a variety of;
The packing density is 20-80kg/m3, porosity 50-97%, partial size 10-100mm.
3. a kind of application of the microbial activity filler as described in claim 1 in purification of sulphur-containing exhaust gas, which is characterized in that institute The mass ratio of the microbial bacteria suspension and filler stated is 1-12: 1.
4. a kind of application of the microbial activity filler as described in claim 1 in purification of sulphur-containing exhaust gas, which is characterized in that institute Meng Shi pseudomonad LW-1 cell concentration 1.0 × 10 in the microbial activity filler stated5-9.0×108CFU/g(filler)
5. a kind of application of the microbial activity filler as described in claim 1 in purification of sulphur-containing exhaust gas, which is characterized in that institute It states filler and hollow sphere be mass ratio is 0.9-3:1.
6. a kind of application of the microbial activity filler as described in claim 1 in purification of sulphur-containing exhaust gas, which is characterized in that institute The wire side hollow sphere material stated is polyethylene, polyvinyl chloride or polypropylene.
7. a kind of application of the microbial activity filler as described in claim 1 in purification of sulphur-containing exhaust gas, which is characterized in that institute The hollow bulb diameter 6cm of the wire side stated, is made of two hemisphere, and each hemisphere surface is porous, the aperture 2-8mm in each hole;
There is a circle reinforcing ring in the middle part of the wire side hollow sphere, reinforcing ring is equipped with lock, convenient for two hemisphere of unlatching and closure.
8. a kind of application of the microbial activity filler as described in claim 1 in purification of sulphur-containing exhaust gas, which is characterized in that institute State Meng Shi pseudomonad bacteria suspension the preparation method is as follows:
1. being carried out liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activation step by step by 10-25% inoculum concentration Expand fermented and cultured;
Fermentation culture conditions are as follows: in 35-45 DEG C, ventilation quantity 10-100L/min, dissolved oxygen > 2.0mg/L, tank presses 0.03- Under the conditions of 0.10Mpa, incubation time 45-55h;
The composition of the liquid fermentation medium are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO4 0.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.2-7.0,115 DEG C go out Bacterium 20min is cooled to room temperature after sterilizing and adds 4.5mg/L parathion;
2. after fermented and cultured, fermentation liquid is placed in refrigerated centrifuge in 4 DEG C, 2000-8000rpm, 10-20min is centrifuged, Liquid is discarded supernatant, precipitating is diluted with sterile nutrient solution, and acquisition cell concentration is 0.30-0.95g/L Meng Shi pseudomonad LW-1 bacterium Suspension;
The composition of the sterile nutrient solution are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgCl20.2g, CaCl20.05g, FeSO40.02g, water 1000mL, pH value 6.8-7.2,121 DEG C of sterilizings 20min。
9. the application of a kind of microbial activity filler in purification of sulphur-containing exhaust gas as described in claim 1-8 any one, special The step of sign is, handles exhaust gas is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonad LW-1 to be placed in a container appendix, be passed through the gas containing parathion Body activates microbial activity filler using parathion as phosphorus source, sulphur source;Activation time is 2-15 days;
The concentration of parathion in the gas containing parathion being passed through is 50-200mg/m3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacation unit cell Bacterium LW-1 purifies the organic sulfur in exhaust gas, and microbial activity packing volume is 0.1-1000m3, the total concentration of organic sulfur is 20- 200mg/m3, gas flow rate 0.05-10000m3/ h, residence time 1.5-10.0min, purification temperature are 30-65 DEG C;Periodically to Microbial activity filler surface spraying nutrient solution maintains the activity of microbial activity filler, and spray frequency is to spray 1 time for 1-3 days, Each spray rate is 1.0-200L/min, and each spray time is 10-90min.
10. application of a kind of microbial activity filler in purification of sulphur-containing exhaust gas as claimed in claim 9, which is characterized in that institute The composition for the nutrient solution stated are as follows: glucose 0.5g, K2HPO40.5g, KH2PO41.5g, (NH4)2SO40.5g, NaCl 0.5g, MgSO40.2g, CaCl20.05g, FeSO40.02g, water 1000ml, pH value 6.2-7.0.
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CN1445013A (en) * 2002-03-19 2003-10-01 广东省微生物研究所 Biologic deodorization method and its device
CN106310892A (en) * 2016-10-18 2017-01-11 浙江工业大学 Spraying waste gas treatment system and application thereof
EP3178922A1 (en) * 2015-12-07 2017-06-14 Samsung Electronics Co., Ltd. Bacterial cytochrome p450 protein variant and method of reducing concentration of fluorinated methane in sample using the same
CN107930378A (en) * 2017-11-17 2018-04-20 北京沃太斯环保科技发展有限公司 For handling the filtering tower packing of VOCs gases and foul gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1445013A (en) * 2002-03-19 2003-10-01 广东省微生物研究所 Biologic deodorization method and its device
EP3178922A1 (en) * 2015-12-07 2017-06-14 Samsung Electronics Co., Ltd. Bacterial cytochrome p450 protein variant and method of reducing concentration of fluorinated methane in sample using the same
CN106310892A (en) * 2016-10-18 2017-01-11 浙江工业大学 Spraying waste gas treatment system and application thereof
CN107930378A (en) * 2017-11-17 2018-04-20 北京沃太斯环保科技发展有限公司 For handling the filtering tower packing of VOCs gases and foul gas

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