CN108671740A - A kind of application of the biological active filling material comprising Meng Shi pseudomonads in purification of sulphur-containing exhaust gas - Google Patents

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

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Publication number
CN108671740A
CN108671740A CN201810455521.4A CN201810455521A CN108671740A CN 108671740 A CN108671740 A CN 108671740A CN 201810455521 A CN201810455521 A CN 201810455521A CN 108671740 A CN108671740 A CN 108671740A
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filler
microbial activity
sulphur
purification
meng shi
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CN108671740B (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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Nanjing Jiangdao Environmental Science And Technology Research Institute Co ltd
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
    • B01D53/84Biological processes
    • 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
    • B01D53/46Removing components of defined structure
    • 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
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20Bacteria; Culture media therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/95Specific microorganisms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/55Compounds of silicon, phosphorus, germanium or arsenic
    • B01D2257/556Organic compounds
    • 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

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 pseudomonads.The Meng Shi pseudomonads are specially Meng Shi pseudomonads (Pseudomonas monteilii) LW 1, deposit number is CGMCC No.13748, the microbial activity filler is adsorbed on filler by Meng Shi pseudomonad bacteria suspensions, and filler is seated in wire side hollow ball and is prepared, the filler is used to handle the organic sulphur waste gas that contains of agricultural chemicals waste water reservoir generation, and gas flow is 100 5000m3/ h, 1.0 5.0min of residence time, 35 55 DEG C of temperature, malathion, parathion, parathion-methyl total concentration be 20 200mg/m3, malathion, parathion, parathion-methyl degradation efficiency can reach 90% or more.

Description

A kind of biological active filling material comprising Meng Shi pseudomonads 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 pseudomonads (Pseudomonas Monteilii) application of the biological active filling material of LW-1 in removing sulphur-containing exhaust gas.
Background technology:
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 (C10H14NO5PS it 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 odour taste.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, there is stimulation 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 anorexia, Nausea and vomiting, abdominal pain, hidrosis, thing Object is fuzzy, myosis, respiratory secretions increase, bronchial spasm expiratory dyspnea, pulmonary edema;Sample Symptoms shake for muscle bundle It quivers, muscle spasmus, myoparalysis;Central nervous system symptom shows as headache, dizzy, insomnia drowsiness, weak, 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 be decomposed 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 formulations of pesticide) use, and are mainly used for prevention various agricultural pest.It is prominent with certain cause to microorganism Denaturation, such as 667 μ g/ wares 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, rapid distribution to each device of whole body Official organizes, and strong bonded 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 processing procedure, 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 flow in wastewater treatment process Chlorine is spilt into from water in air, 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 is effective at present because it has many advantages, such as at low cost, easy to operate, technology cleaning, non-secondary pollution 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 organochlorine to carbon dioxide, salt 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)
Some researches show 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 it not yet finds for handling organic sulfur and organic The Meng Shi pseudomonads (Pseudomonas monteilii) of chlorine, and use Meng Shi pseudomonads processing sulfur-bearing, contain chlorine pollution The method of object.
Invention content:
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, start it is slow, the problem of filler collapses is used for a long time, the present invention provides one plant of Meng Shi pseudomonads (Pseudomonas Monteilii), and by the bacterial strain removing is applied to containing in the organic sulphur waste gas.
The Meng Shi pseudomonads, specially Meng Shi pseudomonads (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 pseudomonads (Pseudomonas monteilii) LW-1:Cell is in rod-shaped, 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 ranges (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 pseudomonads LW-1 Bacteria suspension is adsorbed on filler, and filler is seated in wire side hollow ball and is prepared, can preferably treatment and purification containing organic The exhaust gas of sulphur.
The filler is one or more in polyurethane foamed blocks, haydite, volcanic rock or molecular sieve;
The packing density is 20-80kg/m3, porosity 50-97%, grain size 10-100mm;
The mass ratio of the microbial bacteria suspension and filler is 1-12: 1;
Meng Shi pseudomonad LW-1 cell concentrations 1.0 × 10 in the microbial activity filler5-9.0×108CFU/ g(filler)
The wire side hollow ball 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 are a circle reinforcing ring, reinforcing ring to be equipped with lock in the middle part of the wire side hollow ball, convenient for opening and being closed two Hemisphere.
The specific preparation process of the filler is as follows:
(1) preparation of Meng Shi pseudomonads LW-1 bacteria suspensions
1. by liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activations, carried out by 10-25% inoculum concentrations Expand fermented and cultured step by step;
Fermentation culture conditions are:In 35-45 DEG C, ventilation quantity 10-100L/min, dissolved oxygen>2.0mg/L, tank press 0.03- Under the conditions of 0.10Mpa, incubation time 45-55h;
The group of the liquid fermentation medium becomes: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, sterilizing postcooling to room temperature add 4.5mg/L parathion;
2. after fermented and cultured, zymotic fluid being placed in refrigerated centrifuge in 4 DEG C, 2000-8000rpm, 10- is centrifuged 20min discards supernatant liquid, and precipitation is diluted with sterile nutrient solution, and acquisition cell concentration is 0.30-0.95g/L Meng Shi pseudomonads LW-1 bacteria suspensions;
The group of the sterile nutrient solution becomes: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 ball, the mass ratio of filler and wire side hollow ball For 0.9-3:1;
2. Meng Shi pseudomonad LW-1 bacteria suspensions prepared by step (1) are sprayed by the hole of wire side hollow ball to packet Or the surface of the filler of grain shape;
3. having the wire side hollow ball of filler to be put into impeller load rotates mixing;
4. again to the wire side hollow ball surface spraying Meng Shi pseudomonad LW-1 bacteria suspensions equipped with filler;
Step 1. -4. 2-3 time is repeated, makes in hollow ball surface and hole that equal appendix has bacterium cell, acquisition Meng Shi on filler Pseudomonad LW-1 cell concentrations reach 1.0 × 105-9.0×108CFU/g(filler)Microbial activity filler, 4 DEG C of preservations are standby With.
The present invention also provides a kind of the method containing the organic sulphur waste gas, specific steps are handled using mentioned microorganism active filler It is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonads 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;Soak time is 2-15 days;
A concentration of 50-200mg/m of parathion in the gas containing parathion being passed through3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacations Organic sulfur in monad LW-1 purification exhaust gas, 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 It is 1-3 days sprays 1 that phase, which maintains the activity of microbial activity filler, spray frequency to microbial activity filler surface spraying nutrient solution, Secondary, each spray rate is 1.0-200L/min, and each spray time is 10-90min;
The group of the nutrient solution becomes: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.
Advantageous effect:
1. Meng Shi pseudomonads (Pseudomonas monteilii) LW-1 of the present invention has higher degradation organic sulfur Efficiency, up to 90-100%;And the laundering period of dominant bacteria is short, and inoculation can quickly start degradation reaction in 1 week, apply 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 pseudomonads (Pseudomonas that degrades Monteilii) LW-1 appendix form 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 can be entered in the hole inside filler, the bacterium of microbial activity filler is made Cell appendix amount is high, is not easy to be lost in from bioreactor.
3. Meng Shi pseudomonads (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 secreting antibiotic Element, the siderophore that can be secreted have a clear superiority in the competition of iron.
4. Meng Shi pseudomonads (Pseudomonas monteilii) LW-1 is chemoorganotrophy type, there is catalase, It can utilize and decomposing volatile organic sulfur/organochlorine.
5. Meng Shi pseudomonads (Pseudomonas monteilii) LW-1 has antiviral activity, to TMV (Tobacco mosaics Virus), the viruses such as PVY (marmor upsilon) have inhibiting effect, use 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 ball 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.
Description of the drawings:
Fig. 1 Meng Shi pseudomonads (Pseudomonas monteilii) LW-1 phylogenetic trees.
Specific implementation mode:
In order to make the object, technical solution and advantage of this patent be 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:It is carried 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:
F16S-27(5`-AGAGTTTGATCCTGGCTCAG-3`)
R16S-1492(5`-CGGTTACCTTGTTACGACTTC-3`)
PCR reaction conditions are set as:94 DEG C of pre-degeneration 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 products are connected on PMD-18T carriers, are then transformed into bacillus coli DH 5 alpha competent cell.After converting 50 μ L of competent cell be coated on the LB culture mediums containing isopropylthiogalactoside, X-gal and ammonia benzyl.37 DEG C of constant temperature Incubator is incubated overnight, and LB liquid medium culture is carried out from 25 white single bacterium spots of each tablet picking.After culture 2 hours, Culture solution is subjected to sequencing analysis.The sequence measured uses DNAMAN softwares to carry out similitude merger first, and similitude is more than 97% sequence merger is an operating unit, and the representative sequence chosen in each operating unit utilizes BLAST and GenBank numbers Homology analysis is carried out according to the 16SrDNA gene orders in library, 1400bp or more length is chosen and is compared (Clustelx1.83), Phylogenetic Analysis (MEGA3.1), system are carried out using ortho position connection (Neighbour Joining) method Development tree is as shown in Figure 1.It is compared by DNA sequence dna, which is Meng Shi pseudomonads (Pseudomonas monteilii), It is named as Meng Shi pseudomonads (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 suspensions On, and filler is seated in wire side hollow ball and is prepared;
Packing density is 20kg/m3, porosity 90%, grain size 10mm;The mass ratio of microbial bacteria suspension and filler It is 1: 1;Meng Shi pseudomonads LW-1 cell concentrations 1.0 × 10 in microbial activity filler5CFU/g(filler)
The wire side hollow ball 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 ball, reinforcing ring is equipped with lock, convenient for opening Open and be closed two hemisphere.
The specific preparation process of the filler is as follows:
(1) preparation of Meng Shi pseudomonads LW-1 bacteria suspensions
1. by liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activations, carried out step by step by 10% inoculum concentration Expand fermented and cultured;
Fermentation culture conditions are:In 35 DEG C, ventilation quantity 10L/min, dissolved oxygen>2.0mg/L, tank press 0.03-0.10Mpa items Under part, incubation time 55h;
Slant medium group becomes: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 group of the liquid fermentation medium becomes: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, sterilizing postcooling to room temperature add 4.5mg/L parathion;
2. after fermented and cultured, zymotic fluid being placed in refrigerated centrifuge in 4 DEG C, 2000rpm, 10min is centrifuged, discards Supernatant, precipitation are diluted with sterile nutrient solution, and acquisition cell concentration is 0.30g/L Meng Shi pseudomonad LW-1 bacteria suspensions;
The group of the sterile nutrient solution becomes: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 ball, the mass ratio of filler and wire side hollow ball is 0.9:1;
2. Meng Shi pseudomonad LW-1 bacteria suspensions prepared by step (1) are sprayed by the hole of wire side hollow ball to packet The surface of the filler of shape;
3. having the wire side hollow ball of filler to be put into impeller load rotates mixing;
4. again to the wire side hollow ball surface spraying Meng Shi pseudomonad LW-1 bacteria suspensions equipped with filler;
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 vacations Monad LW-1 cell concentrations reach 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 suspensions, and will fill out Material, which is seated in wire side hollow ball, to be prepared;Packing density is 80kg/m3, porosity 50%, grain size 100mm;Micro- life The mass ratio of object bacteria suspension and filler is 12: 1;Meng Shi pseudomonads LW-1 cell concentrations 9.0 in microbial activity filler × 108CFU/g(filler)
The wire side hollow ball 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 are a circle reinforcing ring, reinforcing ring to be equipped with lock, be convenient in the middle part of wire side hollow ball Open and be closed two hemisphere.
The specific preparation process of the filler is as follows:
(1) preparation of Meng Shi pseudomonads LW-1 bacteria suspensions
1. by liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activations, carried out step by step by 25% inoculum concentration Expand fermented and cultured;
Fermentation culture conditions are:In 45 DEG C, ventilation quantity 100L/min, dissolved oxygen>2.0mg/L, tank press 0.10Mpa conditions Under, incubation time 45h;
Slant medium group becomes: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 group of the liquid fermentation medium becomes: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, sterilizing postcooling to room temperature add 4.5mg/L parathion;
2. after fermented and cultured, zymotic fluid being placed in refrigerated centrifuge in 4 DEG C, 8000rpm, 20min is centrifuged, discards Supernatant, precipitation are diluted with sterile nutrient solution, and acquisition cell concentration is 0.95g/L Meng Shi pseudomonad LW-1 bacteria suspensions;
The group of the sterile nutrient solution becomes: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 ball, the mass ratio of filler and wire side hollow ball is 2:1;
2. Meng Shi pseudomonad LW-1 bacteria suspensions prepared by step (1) are sprayed by the hole of wire side hollow ball to granulated The surface of the filler of shape;
3. having the wire side hollow ball of filler to be put into impeller load rotates mixing;
4. again to the wire side hollow ball surface spraying Meng Shi pseudomonad LW-1 bacteria suspensions equipped with filler;
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 vacations Monad LW-1 cell concentrations reach 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 suspensions, and incite somebody to action Filler is seated in wire side hollow ball and is prepared;Packing density is 50kg/m3, porosity 75%, grain size 50mm;Micro- life The mass ratio of object bacteria suspension and filler is 8: 1;Meng Shi pseudomonads LW-1 cell concentrations 3.0 in microbial activity filler × 107CFU/g(filler)
The wire side hollow ball 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 ball, reinforcing ring is equipped with lock, convenient for opening Open and be closed two hemisphere.
The specific preparation process of the filler is as follows:
(1) preparation of Meng Shi pseudomonads LW-1 bacteria suspensions
1. by liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activations, carried out step by step by 17% inoculum concentration Expand fermented and cultured;
Fermentation culture conditions are:In 40 DEG C, ventilation quantity 50L/min, dissolved oxygen>2.0mg/L, tank press 0.03-0.10Mpa items Under part, incubation time 50h;
Slant medium group becomes: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 group of the liquid fermentation medium becomes: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, sterilizing postcooling to room temperature add 4.5mg/L parathion;
2. after fermented and cultured, zymotic fluid is placed in refrigerated centrifuge in 4 DEG C, 5000rpm, 10-20min is centrifuged, Liquid is discarded supernatant, precipitation is diluted with sterile nutrient solution, and acquisition cell concentration is 0.65g/L Meng Shi pseudomonad LW-1 bacteria suspensions;
The group of the sterile nutrient solution becomes: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 ball, the mass ratio of filler and wire side hollow ball is 3:1;
2. Meng Shi pseudomonad LW-1 bacteria suspensions prepared by step (1) are sprayed by the hole of wire side hollow ball to box-shaped The surface of the filler of shape;
3. having the wire side hollow ball of filler to be put into impeller load rotates mixing;
4. again to the wire side hollow ball surface spraying Meng Shi pseudomonad LW-1 bacteria suspensions equipped with filler;
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 vacations Monad LW-1 cell concentrations reach 3.0 × 107CFU/g(filler)Microbial activity filler, 4 DEG C save backup.
Embodiment 4:A kind of method of the microbial activity filler processing containing the organic sulphur waste gas
The method containing the organic sulphur waste gas being handled using microbial activity filler described in embodiment 1 the present invention also provides a kind of, It is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonads 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;Soak time is 15 days;
A concentration of 50mg/m of parathion in the gas containing parathion being passed through3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacations Organic sulfur in monad LW-1 purification exhaust gas, 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℃;It is 3 days that the activity of microbial activity filler, spray frequency are periodically maintained to microbial activity filler surface spraying nutrient solution 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 group of the nutrient solution becomes: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 5:A kind of method of the microbial activity filler processing containing the organic sulphur waste gas
The method containing the organic sulphur waste gas being handled using microbial activity filler described in embodiment 2 the present invention also provides a kind of, It is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonads 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;Soak time is 2 days;
A concentration of 200mg/m of parathion in the gas containing parathion being passed through3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacations Organic sulfur in monad LW-1 purification exhaust gas, microbial activity packing volume is 1000m3, in air inlet, parathion it is a concentration of 162.7mg/m3, a concentration of 32.1mg/m of parathion-methyl3, gas flow rate 10000m3/ h, residence time 10.0min, only It is 65 DEG C to change temperature;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 group of the nutrient solution becomes: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 6:A kind of method of the microbial activity filler processing containing the organic sulphur waste gas
The method containing the organic sulphur waste gas being handled using microbial activity filler described in embodiment 3 the present invention also provides a kind of, It is as follows:
(1) there is the microbial activity filler of Meng Shi pseudomonads 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;Soak time is 7 days;
A concentration of 100mg/m of parathion in the gas containing parathion being passed through3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing the organic sulphur waste gas, with Meng Shi vacations Organic sulfur in monad LW-1 purification exhaust gas, microbial activity packing volume is 500m3, in air inlet, the concentration of malathion For 179.2mg/m3, a concentration of 56.3mg/m of parathion-methyl3, gas flow rate 5000m3/ h, residence time 5.0min, only It is 50 DEG C to change temperature;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 outlets 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 group of the nutrient solution becomes: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, the mean air entry of pH 4-7, parathion are a concentration of:25mg/m3, a concentration of 2mg/ of outlet 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, Meng Shi vacation unit cells Bacterium LW-1 quantity is from 3.0 × 107CFU/g increases to 7.0 × 108CFU/g.It is added containing 0.02g/L iron members when to bioreactor 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 group of the nutrient solution becomes: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) it is used to handle the exhaust gas containing malathion of agricultural chemicals waste water processing procedure generation, a concentration of 10mg/ of malathion m3, gas flow 3000m3/ h, residence time 95s, 30 DEG C of gas temperature, regular replenishment contains the battalion of 0.02g/L ferro elements Nutrient solution (is same as above), and 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, the inlet gas concentration of pH4-6, methyl mercaptan are:2-5mg/m3, go out gas concentration and be less than 0.1mg/m3, Average removal rate:98%.Reactor Nei Mengshi pseudomonads (Pseudomonas monteilii) LW-1 quantity be 2.0 × 107-2.5×108CFU/g, bioreactor are stable.
In above-mentioned gas processing procedure, 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
Microbial activity filler is prepared using 3 same method of embodiment and (fermentation medium is only added into 4.5mg/L to sulphur Phosphorus replaces with while adding 4.5mg/L parathion and 4.5mg/L trichloroacetaldehydes) 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 pseudomonads LW-1 to be placed in a container appendix, be passed through containing parathion, The gas of trichloroacetaldehyde activates microbial activity filler;Soak time is 7 days;
A concentration of 100mg/m of parathion in the gas containing parathion being passed through3, trichloroacetaldehyde it is a concentration of 100mg/m3
(2) the microbial activity filler after activation is placed in bioreactor, is passed through containing organic sulfur, chlorine exhaust gas, with illiteracy Organic sulfur, chlorine in family name pseudomonad LW-1 purification exhaust gas, 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 It is 50 DEG C to change temperature;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 outlets 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 group of the nutrient solution becomes: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 suspensions, and filler is seated in wire side hollow ball and is prepared;
The Meng Shi pseudomonads are specially Meng Shi pseudomonads (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 It is one or more in polyurethane foamed blocks, haydite, volcanic rock or molecular sieve to state filler;
The packing density is 20-80kg/m3, porosity 50-97%, grain 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 concentrations 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 is 0.9-3 that state filler and hollow ball, which be mass ratio,: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 ball 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 wire side stated, is made of two hemisphere, and each hemisphere surface is porous, the aperture 2-8mm in each hole;
There are a circle reinforcing ring, reinforcing ring to be equipped with lock in the middle part of the wire side hollow ball, convenient for opening and being closed two hemisphere.
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 The preparation method for stating Meng Shi pseudomonad bacteria suspensions is as follows:
1. by liquid fermentation medium is accessed after Meng Shi pseudomonad LW-1 slant activations, carried out step by step by 10-25% inoculum concentrations Expand fermented and cultured;
Fermentation culture conditions are:In 35-45 DEG C, ventilation quantity 10-100L/min, dissolved oxygen>2.0mg/L, tank press 0.03- Under the conditions of 0.10Mpa, incubation time 45-55h;
The group of the liquid fermentation medium becomes: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, sterilizing postcooling to room temperature add 4.5mg/L parathion;
2. after fermented and cultured, zymotic fluid is placed in refrigerated centrifuge in 4 DEG C, 2000-8000rpm, 10-20min is centrifuged, Liquid is discarded supernatant, precipitation is diluted with sterile nutrient solution, and acquisition cell concentration is 0.30-0.95g/L Meng Shi pseudomonad LW-1 bacterium Suspension;
The group of the sterile nutrient solution becomes: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 pseudomonads LW-1 to be placed in a container above-mentioned appendix, be passed through containing parathion Gas, using parathion as phosphorus source, sulphur source, activate microbial activity filler;Soak time is 2-15 days;
A concentration of 50-200mg/m of parathion in the gas containing parathion being passed through3
(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 cells Organic sulfur in bacterium LW-1 purification exhaust gas, 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 It is to spray 1 time for 1-3 days that microbial activity filler surface spraying nutrient solution, which maintains the activity of microbial activity filler, spray frequency, 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 group for the nutrient solution stated becomes: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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