CN108479376B - Method for fixing thiobacillus by using polyurethane foam material as carrier - Google Patents

Method for fixing thiobacillus by using polyurethane foam material as carrier Download PDF

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CN108479376B
CN108479376B CN201810242001.5A CN201810242001A CN108479376B CN 108479376 B CN108479376 B CN 108479376B CN 201810242001 A CN201810242001 A CN 201810242001A CN 108479376 B CN108479376 B CN 108479376B
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polyurethane
carrier
thiobacillus
polyurethane foam
bacterial liquid
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CN108479376A (en
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陈波
黄健翔
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Shanghai mestec environment (Group) Co.,Ltd.
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Shanghai Masteck Environment Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/95—Specific microorganisms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Treating Waste Gases (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)

Abstract

The invention provides a method for fixing thiobacillus by taking polyurethane foam material as a carrier, which comprises the following steps: s1, cutting the polyurethane material into a thin plate, blowing the micro-channels of the polyurethane thin plate along the cross section of the polyurethane thin plate by steam, and cooling to room temperature to obtain a polyurethane carrier; and S2, circularly leaching the polyurethane carrier by using a bacterium solution containing high-density thiobacillus, and fixing the thiobacillus on the polyurethane carrier. The polyurethane foam with low cost is used as the filler of the biotrickling waste gas treatment device to replace the traditional fillers of bamboo charcoal, ceramsite, bark and the like, and has the advantages of low cost, light weight, large specific surface area, strong adsorption capacity, ageing-resistant inert materials and good mass transfer performance. The microorganism is enriched on the surface and the inner micropores of the polyurethane foam filler by a microorganism immobilization technology, so that the number of microorganism flora in the waste gas treatment device can be increased, the tolerance of the microorganism to environmental factors can be improved, and the activity and the treatment efficiency of the microorganism are improved.

Description

Method for fixing thiobacillus by using polyurethane foam material as carrier
Technical Field
The invention relates to a method for fixing thiobacillus by taking polyurethane foam material as a carrier, wherein the carrier can be used as an integral filler of a hydrogen sulfide waste gas treatment device so as to improve the capacity and efficiency of the treatment device.
Background
In recent years, due to the expansion of population and the great improvement of living standard, the generated domestic garbage is increased day by day, the pressure on three-waste treatment is gradually increased, the influence on the environment is also increased to a quite serious degree, along with the increasing strictness of environmental protection standards and policies, the influence on the ambient atmospheric environment of a sewage treatment plant is also raised to a stricter national and local standard, and one of main waste gases generated in the sewage treatment process during hydrogen sulfide, low-concentration hydrogen sulfide is gas with extremely toxic and foul smell, and has influence on eyes, respiratory systems and central nervous systems.
In order to eliminate the odor gas such as hydrogen sulfide volatilized from the municipal sewage treatment facilities, an activated carbon adsorption method, a chemical washing method and a microbial purification method are generally adopted, and among them, the microbial purification method is widely adopted because of its advantages of low cost and high treatment efficiency. The biological purification method for treating malodorous gas generally adopts a biological trickling filter device which mainly degrades pollutants into CO through the metabolism process of microorganisms attached to the surface of a filler in a trickling filter tower2And water and inorganic salt, and the waste gas is used as nutrition or energy to generate new microbial cytoplasm to form stable and balanced micro-ecological environment, and can continuously metabolize and convert pollutants in the waste gas.
The immobilization technology of the microbial cells can gather a large number of microbes on the surface and at the micropores of the filler, thereby improving the efficiency of the treatment device. After the microbial cells are immobilized, the cell density is high, the reaction speed is high, the biological stability is good, the environmental tolerance is good, and the processing capacity and speed can be greatly improved.
In the biological trickling filter device, the filler is not only a supporting carrier for microbial growth, but also a mass transfer medium of gas phase and liquid phase, provides sufficient contact for gas phase, liquid phase and solid phase, and the performance of the filler directly influences the removal effect and the treatment cost of pollutants. The soft foam polyurethane foam has the advantages of low cost, light weight, large specific surface area, strong adsorption capacity, ageing-resistant inert material, good mass transfer performance and the like, and is a good substitute for fillers such as bamboo charcoal, bark and the like. However, the existing method only uses the soft foam polyurethane foam as a carrier, has long biofilm formation period, poor stability and persistence of the biofilm, and is easy to be ablated by environmental interference.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a method for immobilizing thiobacillus by using a polyurethane foam material as a carrier.
The invention is realized by the following technical scheme:
the invention relates to a method for fixing thiobacillus by taking polyurethane foam material as a carrier, which comprises the following steps:
s1, cutting the polyurethane material into a thin plate, blowing the micro-channels of the polyurethane thin plate along the cross section of the polyurethane thin plate by steam, and cooling to room temperature to obtain a polyurethane carrier; preferably, the micro-channels of the polyurethane sheet are blown by steam from bottom to top;
and S2, circularly leaching the polyurethane carrier by using a bacterium solution containing high-density thiobacillus, and fixing the thiobacillus on the polyurethane carrier. When the liquid containing high-density thiobacillus is used for circularly leaching the polyurethane sheet, the thiobacillus enters micropores in the inner wall of the polyurethane material, and forms stable mucosa under the action of extracellular polysaccharide to protect the growth of the thiobacillus and balance the environmental influence, so that the thiobacillus is fixed on a carrier of the polyurethane foam material.
Preferably, in step S1, the thickness of the polyurethane sheet is 8-15 cm. When the thickness of the polyurethane thin plate is less than 8cm, the pressure loss of the filler layer of the treatment device is large, and when the thickness of the polyurethane thin plate is more than 15cm, the pressure inside the treatment device is increased.
The length and the width of the polyurethane thin plate can be set according to the requirement of equipment, if the plane size of the equipment is large, the whole thin plate is manufactured unconditionally, and small thin plates can be spliced in a staggered mode.
Preferably, in step S1, the steam purging is used to remove mainly the free substances and avoid the influence of the free substances on the growth of the microorganisms, the temperature of the steam is 110-120 ℃, and the time of the steam purging is 30-60S. If the temperature is lower than 110 ℃ or the time is less than 30s during steam blowing, the effect of removing free substances cannot be achieved, and if the temperature is higher than 120 ℃ or the time is more than 60s, the structure of the polyurethane foam can be damaged, and the porosity of the polyurethane foam is influenced.
Preferably, in step S1, the polyurethane material is a flexible polyurethane foam material. The soft foam polyurethane material is a polyurethane foam material with high aperture ratio, good adsorption performance and small wind resistance.
Preferably, in step S2, the bacterial liquid includes the following components in concentration: NH (NH)4Cl 2.4g/L；KH2PO41.2g/L；K2HPO41.2g/L；MgSO4·7H2O 0.2g/L；FeSO4·7H2O 0.01g/L；CaCl20.05g/L；Na2S2O4·5H2O8g/L。
Preferably, the culture condition of the bacterial liquid is shake culture for 7-10 days at a temperature of 25-30 ℃ and a shaking speed of 180 rpm/min.
Preferably, in step S2, the concentration of the bacterial liquid is 106～108More than CFU/mL, and the volume ratio of the bacterial liquid to the polyurethane carrier is 1: 80-100. If the volume ratio of the bacterial liquid to the polyurethane carrier is lower than 1:80, the effect of the microbial biofilm can be influenced, and no enough microbes secrete extracellular polysaccharide to form a biofilm and fix microbial cells; if the volume ratio of the bacterial liquid to the polyurethane carrier is higher than 1:100, the performance of the microbial film is not obviously improved, but the cost is wasted, and the bacterial liquid and the polyurethane carrier are obtained according to experimentsData in bacteria solution concentration 106～108The marginal efficiency of the volume ratio of the bacteria liquid to the polyurethane carrier in the CFU/mL range is higher than 1:100 and is negligible.
Preferably, in step S2, the step of cyclic rinsing includes: and spraying the bacterial liquid onto the surface of the polyurethane sheet from top to bottom, gradually infiltrating the bacterial liquid through the micropores, and collecting and recycling the seepage through a bottom circulating device.
Preferably, in step S2, the flow rate of the circularly eluted bacterial liquid is (V/60) L/min, where V is the volume of the polyurethane carrier.
Preferably, in step S2, the cyclic rinsing time is 5-7 days.
Preferably, the polyurethane carrier is composed of a plurality of polyurethane thin plates overlapped.
The invention provides a method for fixing thiobacillus by taking a polyurethane foam material as a carrier, which comprises the steps of cutting the polyurethane foam material into a thin plate shape, overlapping multiple layers of the cut polyurethane foam material together to be used as a carrier for the immobilization of the thiobacillus, firstly, blowing a micro-pore channel of polyurethane by using low saturated water vapor, removing free substances, and ensuring the smoothness of the whole pore channel; then, high-concentration thiobacillus liquid is used for circularly leaching the polyurethane foam material carrier, the extracellular polysaccharide of bacteria is gathered in the pore channel to form stable mucosa in the leaching process, the thiobacillus can be fixed between the inner wall of the polyurethane foam material and the mucosa or adhered to the surface of the mucosa, and the like, so that the polyurethane foam material carrier containing a large amount of thiobacillus is obtained, and the carrier can be used in a hydrogen sulfide waste gas treatment device and greatly improves the treatment capacity and efficiency of the device.
Compared with the prior art, the invention has the following beneficial effects:
1. the polyurethane foam with low cost is used as the filler of the biotrickling waste gas treatment device to replace the traditional fillers of bamboo charcoal, ceramsite, bark and the like, and has the advantages of low cost, light weight, large specific surface area, strong adsorption capacity, ageing-resistant inert materials and good mass transfer performance. The invention not only has the advantages of the common polyurethane foam carrier, but also flexibly designs the shape and the size of the polyurethane foam carrier in modes of splicing and stacking, and the like, and can avoid the problems of unbalanced aperture ratio and the like caused by a polyurethane production process, so that a treatment device is more efficient and stable, and other waste polyurethane foam can be flexibly used as a filler carrier.
2. The microorganism is enriched on the surface and the inner micropores of the polyurethane foam filler by a microorganism immobilization technology, so that the number of microorganism flora in the waste gas treatment device can be increased, the tolerance of the microorganism to environmental factors can be improved, and the activity and the treatment efficiency of the microorganism are improved. The invention fixes the thiobacillus microorganism on the polyurethane foam carrier, thereby obviously improving the removal efficiency of the microorganism deodorization device on sulfur-containing odor substances such as hydrogen sulfide and the like.
3. The invention can form a stable and long-term microbial film on the polyurethane foam micro-channel by pre-immobilization, thereby improving the stability and efficiency of the treatment device;
the invention has short period of forming the biological membrane and high stability and persistence of the biological membrane.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
The bio-trickling filter device for detecting the efficiency of the immobilized thiobacillus in the following embodiment is a commonly used biological waste gas treatment device, and comprises a glass fiber reinforced plastic box body (1 m wide, 1m long and 1.6 m high), a circulating spray system, an air system and a polyurethane foam packing layer, wherein the circulating spray system consists of a spray head on the upper part of the packing layer, a filtrate collection system on the lower part of the packing layer and a submersible pump.
Example 1
The embodiment relates to a method for fixing thiobacillus by taking a polyurethane foam material as a carrier, which specifically comprises the following steps:
preparation of high-density thiobacillus-containing bacterial liquid
The activated thiobacillus strain was inoculated into the following medium: NH (NH)4Cl 2.4g/L；KH2PO41.2g/L；K2HPO41.2g/L；MgSO4·7H2O 0.2g/L；FeSO4·7H2O 0.01g/L；CaCl20.05g/L；Na2S2O4·5H2O8 g/L. Shaking table shake culture at 25 deg.C and 180rpm/min for 7-10 days with a bacterial concentration of 108CFU/mL。
Preparation of polyurethane foam filler
The polyurethane foam material is cut into flat plates with the length and the width of 1m and the thickness of 10cm, and the flat plates are stacked and paved on a bottom plate part of a filler layer of the treatment device, and the filling height of the filler is about 1 m. When the micro-channels of the polyurethane sheet are purged from bottom to top by steam, the temperature of the steam is 120 ℃, and the time of the steam purging is 60 s.
The thiobacillus is fixed on the polyurethane foam filler carrier
And (3) introducing the cultured bacterial liquid into a water tank at the bottom of the treatment device, and circularly leaching the polyurethane foam carrier filler through a circular leaching system, wherein the flow rate of the bacterial liquid is (V/60) L/min, V is the volume of the polyurethane foam material, the circular leaching time is 5-7 days, and the volume ratio of the bacterial liquid to the polyurethane carrier is 1: 80.
Detection of processing capacity of thiobacillus thuringiensis for hydrogen sulfide
Introducing 180mg/m into the biological trickling filter3H of (A) to (B)2S gas, the gas reaches a stable operation state after being ventilated for one week, and H of the gas outlet is detected at the moment2S gas concentration, calculated H2The removal rate of S gas reaches more than 99 percent, and the formed biological membrane has good stability and good persistence.
Example 2
The embodiment relates to a method for fixing thiobacillus by taking a polyurethane foam material as a carrier, which specifically comprises the following steps:
preparation of high-density thiobacillus bacterial liquid
Inoculating activated Thiobacillus strainsIn the culture medium: NH (NH)4Cl 2.4g/L；KH2PO41.2g/L；K2HPO41.2g/L；MgSO4·7H2O 0.2g/L；FeSO4·7H2O 0.01g/L；CaCl20.05g/L；Na2S2O4·5H2O8 g/L. Shaking table shake culture at 25 deg.C and 180rpm/min for 7-10 days until the bacterial concentration reaches 108CFU/mL or more.
Preparation of polyurethane foam filler
Polyurethane foam materials are cut into strips with the length of 1m, the width of 0.1 m and the thickness of 10cm, two adjacent layers of crossed codes are spliced on a bottom plate of a filler layer of a processing device, a through seam from bottom to top is avoided, and the filling height of the filler is about 1 m. When the micro-channels of the polyurethane sheet are purged from bottom to top by steam, the temperature of the steam is 110 ℃, and the time of the steam purging is 30 s.
The thiobacillus is fixed on the polyurethane foam filler carrier
And (3) introducing the cultured bacterial liquid into a water tank at the bottom of the treatment device, wherein the flow rate of the bacterial liquid for circularly leaching the polyurethane foam carrier filler through a circulating leaching system is (V/60) L/min, wherein V is the volume of the polyurethane foam material, and the circulating leaching time is 5-7 days. The volume ratio of the bacterial liquid to the polyurethane carrier is 1: 100.
Detection of processing capacity of thiobacillus thuringiensis for hydrogen sulfide
Introducing 180mg/m into the biological trickling filter3H of (A) to (B)2S gas, the gas reaches a stable operation state after being ventilated for one week, and H of the gas outlet is detected at the moment2S gas concentration, calculated H2The removal rate of S gas reaches more than 99 percent, and the formed biological membrane has good stability and good persistence.
Example 3
The present example relates to a method for immobilizing thiobacillus by using polyurethane foam as a carrier, which is substantially the same as example 1 except that: polyurethane foam materials are cut into flat plates with the length and the width of each 1m and the thickness of 8cm, and the flat plates are stacked and paved on a bottom plate part of a filler layer of a processing device, and the filling height of the filler is about 1 m. Detection fixationThe capacity of thiobacillus thiofidus to process hydrogen sulfide, calculated H2The removal rate of S gas reaches more than 99 percent, and the formed biological membrane has good stability and good persistence.
Example 4
The present example relates to a method for immobilizing thiobacillus by using polyurethane foam as a carrier, which is substantially the same as example 2 except that: polyurethane foam materials are cut into long strips with the length of 1m, the width of 0.1 m and the thickness of 15cm, two adjacent layers of crossed codes are spliced on a bottom plate of a filler layer of a processing device, so that a through seam from bottom to top is avoided, and the filling height of the filler is about 1.05 m. Detecting the processing capacity of the immobilized thiobacillus to hydrogen sulfide, and calculating H2The removal rate of S gas reaches more than 99 percent, and the formed biological membrane has good stability and good persistence.
Example 5
The present example relates to a method for immobilizing thiobacillus by using polyurethane foam as a carrier, which is substantially the same as example 1 except that: when the micro-channels of the polyurethane sheet are purged by steam from bottom to top, the temperature of the steam is 115 ℃, and the time of purging by the steam is 50 s; the volume ratio of the bacterial liquid to the polyurethane carrier is 1: 90. Detecting the processing capacity of the immobilized thiobacillus to hydrogen sulfide, and calculating H2The removal rate of S gas reaches more than 99 percent, and the formed biological membrane has good stability and good persistence.
Comparative example 1
This comparative example relates to a method for immobilizing thiobacillus using polyurethane foam as a carrier, the preparation method of which is substantially the same as that of example 1, except that: in the step (2), in the preparation of the polyurethane foam filler, the polyurethane foam carrier filler is directly circularly leached without adopting steam to purge the micro-channels of the polyurethane foam sheet. Detecting the processing capacity of the immobilized thiobacillus to hydrogen sulfide, and calculating the H2The removal rate of S gas reaches more than 95%, and the formed biological membrane has poor stability and poor persistence.
Comparative example 2
The comparative example relates to a process for preparing a polyurethaneThe method for fixing thiobacillus by using ester foam material as carrier is basically the same as that of the example 1, except that: in the preparation of the polyurethane foam filler of step (2), the polyurethane foam is not cut into a flat plate shape, but the uncut polyurethane foam is directly filled. Detecting the processing capacity of the immobilized thiobacillus to hydrogen sulfide, and calculating the H2The removal rate of S gas reaches more than 95%, and the formed biological membrane has poor stability and poor persistence.
Comparative example 3
This comparative example relates to a method for immobilizing thiobacillus using polyurethane foam as a carrier, the preparation method of which is substantially the same as that of example 1, except that: in the step of fixing thiobacillus on the polyurethane foam filler carrier in the step (3), the cultured bacterium liquid is directly sprayed on the polyurethane foam filler and cultured for 2 weeks under the conditions of proper temperature and pH value to form a biological membrane. Detecting the processing capacity of the immobilized thiobacillus to hydrogen sulfide, and calculating the H2The removal rate of S gas reaches more than 95%, and the formed biological membrane has general stability and general persistence.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (5)

1. A method for immobilizing thiobacillus by using a polyurethane foam material as a carrier is characterized by comprising the following steps:
s1, cutting the polyurethane material into a thin plate, purging microchannels of the polyurethane thin plate along the cross section of the polyurethane thin plate by using steam, wherein the temperature of the steam is 110-120 ℃, the time of purging by using the steam is 30-60S, and cooling to room temperature to obtain a polyurethane carrier;
s2, circularly leaching the polyurethane carrier by using a bacterium solution containing high-density thiobacillus, and fixing the thiobacillus on the polyurethane carrierThe concentration of the thiobacillus in the bacterial liquid is 106～108CFU/mL, wherein the volume ratio of the bacterial liquid to the polyurethane carrier is 1: 80-100; the step of cyclic leaching comprises: spraying the bacterial liquid onto the surface of the polyurethane carrier from top to bottom, enabling the bacterial liquid to gradually seep downwards through micropores in the polyurethane carrier, and collecting seepage through a bottom circulating device for recycling; the time of the cyclic leaching is 5-7 days;
in step S2, each liter of the bacterial liquid includes the following components: NH (NH)4Cl 2.4g/L；KH2PO41.2g/L；K2HPO41.2g/L；MgSO4·7H2O 0.2g/L；FeSO4·7H2O 0.01g/L；CaCl20.05g/L；Na2S2O4·5H2O8g/L；
The culture condition of the bacterial liquid is that shaking culture is carried out on a shaking table at 180rpm/min for 7-10 days at the temperature of 25-30 ℃.
2. The method for immobilizing thiobacillus with polyurethane foam as a carrier of claim 1, wherein in step S1, the thickness of the polyurethane sheet is 8-15 cm.
3. The method for immobilizing thiobacillus with polyurethane foam as a carrier in claim 1, wherein in step S1, the polyurethane material is flexible polyurethane foam.
4. The method for immobilizing Thiobacillus thioparus with polyurethane foam as a carrier in claim 1, wherein in step S2, the flow rate of the circularly eluted bacterial liquid is (V/60) L/min, wherein V is the volume of the polyurethane carrier.
5. The method for immobilizing Thiobacillus thioparus with polyurethane foam as a carrier in claim 1, wherein the polyurethane carrier is composed of a plurality of polyurethane sheets overlapped.
CN201810242001.5A 2018-03-22 2018-03-22 Method for fixing thiobacillus by using polyurethane foam material as carrier Active CN108479376B (en)

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CN110270216A (en) * 2019-07-04 2019-09-24 上海梅思泰克环境股份有限公司 It is a kind of using polyurethane material as the biological treatment exhaust device of filler
CN113773469B (en) * 2021-09-03 2022-12-13 北京城市排水集团有限责任公司 Composite polyurethane filler, preparation method and application

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CN102002408A (en) * 2010-12-16 2011-04-06 哈尔滨工业大学 Marsh gas biological desulphurization energy-saving method
CN103266099A (en) * 2013-05-29 2013-08-28 中国科学院生态环境研究中心 Ochrobactrum anthropi SL1 active filler and preparation method thereof
CN104694527A (en) * 2015-03-24 2015-06-10 山东大学 Method for strengthening sanitary sewage treatment capacity of constructed wetland through fixed type bacillus with polymeric sponges as carrier
CN107096374A (en) * 2017-05-12 2017-08-29 南京科技职业学院 A kind of method that enhanced biological drop filter tower handles toluene waste gas

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