CN111807502A - Method for preparing composite modified polyurethane foam microorganism immobilization carrier - Google Patents

Method for preparing composite modified polyurethane foam microorganism immobilization carrier Download PDF

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CN111807502A
CN111807502A CN201910295415.9A CN201910295415A CN111807502A CN 111807502 A CN111807502 A CN 111807502A CN 201910295415 A CN201910295415 A CN 201910295415A CN 111807502 A CN111807502 A CN 111807502A
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silicon
based mineral
polyether
polyether polyol
catalyst
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庄毅璇
王磊
林明
刘雷
左晶
李建
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Shenzhen Hongkong Institution Of Industry Education & Research Environmental Engineering Technique Co ltd
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Binzhou Ier Environment Protection Engineering Technique Co ltd
Pku Hkust Shenzhen Hongkong Environmental Protection Engineering Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/101—Arranged-type packing, e.g. stacks, arrays
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/105—Characterized by the chemical composition
    • C02F3/108—Immobilising gels, polymers or the like
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Water Supply & Treatment (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biological Treatment Of Waste Water (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a method for preparing a composite modified polyurethane foam microorganism immobilized carrier. The method comprises the following steps: s1, modifying the silicon-based mineral material by using an organic template agent to obtain a silicon-based mineral modified material; s2, mixing polyether polyol, silicone oil, water, a silicon-based mineral modified material, an amine catalyst, a pore-opening agent and liquid paraffin, stirring uniformly, and then carrying out ultrasonic treatment; s3, mixing polyether polyol and a tin catalyst, stirring uniformly at the temperature of 85-95 ℃, and adding toluene diisocyanate; and S4, mixing the mixture obtained in the step S2 with the mixture obtained in the step S3, uniformly stirring, foaming and curing.

Description

Method for preparing composite modified polyurethane foam microorganism immobilization carrier
Technical Field
The invention belongs to the technical field of polluted water treatment, and particularly relates to a method for preparing a composite modified polyurethane foam microorganism immobilized carrier.
Background
Microorganisms play an important role in the removal of pollutants, and thus biodegradation is considered to be a relatively efficient, economical and energy-efficient wastewater treatment technique. When sewage is treated by utilizing the microbial technology, microorganisms are generally directly inoculated in the sewage to be treated, and pollutants are removed through physiological activities such as absorption, transformation, metabolism and the like of the microorganisms. But because of environmental factors, easy loss and the like, the treatment effect of the direct adding mode is not very ideal. The microorganism immobilization technology can solve the above problems to some extent.
Compared with physical, chemical and traditional biological methods, the microbial immobilization technology has the advantages of economy, high efficiency, easily controlled reaction, high efficiency and high density of microorganisms and the like, thereby being a waste water treatment technology which is researched more at present. However, the microorganism immobilization carrier can inhibit the biological activity of cells and reduce the mass transfer rate of the system. Therefore, the key to the microbial immobilization technology is the properties of the immobilization support material employed. The ideal immobilized carrier material has the characteristics of no toxicity to microorganisms, good mass transfer performance, stable property, long service life, low price and the like.
The microbial immobilized carrier material adopted at present mainly comprises three types of organic polymer carriers, inorganic carriers and composite carriers. The natural polymer gel carrier is easy to be eroded by various ions in the process of treating wastewater, and can be gradually dissolved, so that the service life is shortened; the synthesized polymer gel carrier generally has higher strength, but has poorer mass transfer performance, and has influence on cell activity when cell fixation is carried out. The inorganic carrier has the defects of high density, limited microbial adsorption, easy shedding and the like. The optimization of the carrier process to facilitate the immobilization of microorganisms is an important direction for the development of microorganism immobilization technology in recent years. According to the performance characteristics of organic materials and inorganic materials, the two materials can be combined to form a composite carrier material, and the performance is complemented so as to improve the performance of the carrier material.
Disclosure of Invention
One aspect of the inventive concept provides a method for preparing a composite modified polyurethane foam microorganism immobilization carrier. The method comprises the following steps: s1, modifying the silicon-based mineral material by using an organic template agent to obtain a silicon-based mineral modified material; s2, mixing polyether polyol, silicone oil, water, a silicon-based mineral modified material, an amine catalyst, a pore-opening agent and liquid paraffin, stirring uniformly, and then carrying out ultrasonic treatment; s3, mixing polyether polyol and a tin catalyst, stirring uniformly at the temperature of 85-95 ℃, and adding toluene diisocyanate; and S4, mixing the mixture obtained in the step S2 with the mixture obtained in the step S3, uniformly stirring, foaming and curing.
Further, in step S1, the silicon-based mineral material slurry with a mass percentage of 0.05 wt% to 0.50 wt% and the organic template agent aqueous solution with a mass percentage of 0.03 wt% to 0.50 wt% may be mixed according to a mass ratio of 1:2 to 1:6, and then stirred at a temperature of 25 ℃ to 80 ℃ for 3h to 8h, filtered, vacuum-dried to a constant weight, ground and sieved to obtain the silicon-based mineral modified material.
Further, the silicon-based mineral material may include at least one of sepiolite, attapulgite, zeolite, fumed silica, diatomaceous earth, and montmorillonite.
Further, the organic templating agent may include one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, ethylenediamine, n-butylamine, and pyrrolidine.
Further, in step S2, the mass percentages of the polyether polyol, the silicone oil, the water, the silicon-based mineral modified material, the amine catalyst, the cell opener, and the liquid paraffin may be 70 wt% to 80 wt%, 2 wt% to 5 wt%, 5 wt% to 12 wt%, 1 wt% to 6 wt%, 2 wt% to 5 wt%, 3 wt% to 8 wt%, and 1 wt% to 3 wt%, respectively.
Further, the amine catalyst may include one or more of N, N-dimethylcyclohexylamine, triethylamine, NMM, triethanolamine, pyridine, and DMEA; the cell opener may comprise a linear hydrocarbon or a cyclic hydrocarbon.
Further, in step S3, polyether polyol and tin catalyst are mixed and stirred at 85-95 ℃ for 5-30 min, then toluene diisocyanate is added and stirred at 100-220 rad/min for 2-30 min and then cooled to room temperature,
wherein, the mass percentages of the polyether polyol, the tin catalyst and the toluene diisocyanate can be 65 wt% -70 wt%, 25 wt% -30 wt% and 1 wt% -5 wt%, respectively.
Further, the tin-based catalyst may include one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and dibutyltin bis (dodecylthio) tin.
Further, in step S4, the mixture obtained in step S2 and the mixture obtained in step S3 may be mixed in a mass ratio of 3-10: 1.
Further, in steps S2 and S3, the polyether polyol may include one or more of polyether diol, polyether triol, polyether tetraol, and hydroxyl-free polyether.
The method for preparing the composite modified polyurethane foam microorganism immobilization carrier according to the present inventive concept can achieve at least one of the following advantageous effects:
firstly, the composite modified polyurethane foam microorganism immobilization carrier prepared by the method has the advantages of low cost, long service life, good microorganism immobilization performance, no toxicity to microorganisms and the like.
Secondly, in the preparation method of the invention, the porosity of the polyurethane foam is improved after the silicon-based mineral modified material is added, and the transfer of the matrix and the metabolite is facilitated while the microbial immobilization amount is increased.
Thirdly, the composite modified polyurethane foam microorganism immobilization carrier prepared by the method contains a large number of active chemical groups such as imino, amino, hydroxyl and the like, is beneficial to solidifying microorganisms by a carrier combination method, has small influence on the activity of the microorganisms, and is beneficial to maintaining the activity of the immobilized microorganisms.
Drawings
The foregoing and/or other features and aspects of the inventive concept will become apparent and appreciated from the following description of the exemplary embodiments, taken in conjunction with the accompanying drawings.
FIG. 1 is a flowchart of a method for preparing a composite modified polyurethane foam microorganism-immobilized carrier according to the inventive concept.
FIG. 2 is COD of example 1 according to the inventive conceptCrConcentration and COD removal rate as a function of time.
Fig. 3 is a graph of ammonia nitrogen concentration and removal rate over time according to example 1 of the inventive concept.
Fig. 4 is a graph comparing the COD removal rate of example 1 according to the inventive concept with that of comparative example 1.
Fig. 5 is a graph comparing the removal of ammonia nitrogen of example 1 according to the inventive concept with the removal of ammonia nitrogen of comparative example 1.
Fig. 6 is a graph comparing tolerance to phenol of the immobilized microorganism obtained according to example 2 of the inventive concept with that of the immobilized microorganism obtained according to comparative example 2.
Fig. 7 is a graph comparing the degradation rate of phenol by the immobilized microorganisms obtained in example 2 according to the inventive concept with that of the immobilized microorganisms obtained in comparative example 2.
Detailed Description
Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention, however, should not be construed as limited to the exemplary embodiments set forth herein. In the following, like reference numerals refer to like parts throughout.
FIG. 1 is a flowchart of a method for preparing a composite modified polyurethane foam microorganism-immobilized carrier according to the inventive concept.
As shown in fig. 1, the method for preparing a composite modified polyurethane foam microorganism immobilization carrier according to the inventive concept comprises the steps of: s1, modifying the silicon-based mineral material by using an organic template agent to obtain a silicon-based mineral modified material; s2, mixing polyether polyol, silicone oil, water, a silicon-based mineral modified material, an amine catalyst, a pore-opening agent and liquid paraffin, stirring uniformly, and then carrying out ultrasonic treatment; s3, mixing polyether polyol and a tin catalyst, stirring uniformly at the temperature of 85-95 ℃, and adding toluene diisocyanate; and S4, mixing the mixture obtained in the step S2 with the mixture obtained in the step S3, uniformly stirring, foaming and curing.
In step S1, 0.05 wt% to 0.50 wt% of the silicon-based mineral material slurry and 0.03 wt% to 0.50 wt% of the organic template aqueous solution are mixed according to the mass ratio of 1:2 to 1:6, and then stirred at 25 ℃ to 80 ℃ for 3h to 8h, filtered, vacuum-dried to constant weight, ground and sieved to obtain the silicon-based mineral modified material. Specifically, firstly, mixing a silicon-based mineral material with water to prepare a silicon-based mineral material slurry with a mass percentage of 0.05 wt% -0.50 wt% (preferably, 0.05 wt% -0.20 wt%), and mixing an organic template with water to prepare an organic template aqueous solution with a mass percentage of 0.03 wt% -0.50 wt% (preferably, 0.03 wt% -0.30 wt%), and mixing the two in proportion; and then stirring the obtained mixture at the temperature of 25-80 ℃ for 3-8 h, cooling to room temperature, performing suction filtration by using a third sand core funnel, performing vacuum drying at the temperature of 85-95 ℃ to constant weight, and grinding and sieving by using a 400-mesh sieve to obtain the silicon-based mineral modified material.
In one embodiment of the inventive concept, since the silicon-based mineral material is structurally such that trivalent aluminum is easily isomorphously replaced by divalent magnesium, each layer surface has a negative charge, and the excess negative charge is passed through the adsorbed cations (e.g., Na) between the layers+、K+、Ca2+Etc.) to be easily exchanged with inorganic or organic cations, both organic or biological cations can be introduced by ion exchange. According to the inventive concept of the present invention, the silicon-based mineral material may include at least one of sepiolite, attapulgite, zeolite, fumed silica, diatomaceous earth, and montmorillonite.
According to an embodiment of the inventive concept, the organic templating agent may include one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, ethylenediamine, n-butylamine, and pyrrolidine, and particularly, the organic templating agent may include cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
The organic template agent is utilized to modify the silicon-based mineral material, so that the silicate surface of the silicon-based mineral material is changed from hydrophilicity to lipophilicity, the surface energy of the silicon-based mineral material is reduced, the intermiscibility of the silicon-based mineral material with a polymer matrix and a monomer is improved, and various functional groups can be carried in by organic cations, and the functional groups are reacted by a polymer, so that the cohesiveness between the silicon-based mineral material and an organic polymer is improved.
Then, in step S2, the polyether polyol, the silicone oil, the water, the silicon-based mineral modified material, the amine catalyst, the cell opener, and the liquid paraffin may be mixed, and stirred for 5min to 10min to be uniformly mixed, and then subjected to ultrasonic treatment for 5min to 10 min. In one embodiment of the inventive concept, the mass percentages of the polyether polyol, the silicone oil, the water, the silicon-based mineral-modified material, the amine-based catalyst, the cell opener, and the liquid paraffin may be 70 wt% to 80 wt%, 2 wt% to 5 wt%, 5 wt% to 12 wt%, 1 wt% to 6 wt%, 2 wt% to 5 wt%, 3 wt% to 8 wt%, and 1 wt% to 3 wt%, respectively.
In an embodiment of the inventive concept, the amine-based catalyst may include one or more of N, N-dimethylcyclohexylamine, triethylamine, NMM, triethanolamine, pyridine, and DMEA, and particularly, may include triethylamine.
The cell opener may include a linear hydrocarbon or a cyclic hydrocarbon compound, and specifically, the cell opener may include a liquid or gel-like linear hydrocarbon or cyclic hydrocarbon compound. In the process of preparing polyurethane foam, the cell opening agent can increase the pressure of foam gas in closed cells before curing, and the gas pressure in the closed cells is increased due to the temperature rise in the curing process to break through membrane-shaped cell walls, so that the cells are opened.
Next, in step S3, the polyether polyol and the tin-based catalyst may be mixed and stirred at a temperature of 85 deg.C to 95 deg.C for 5min to 30min (preferably, 5min to 10min), then Toluene Diisocyanate (TDI) is added and stirred at 100rad/min to 220rad/min (preferably, 150rad/min to 220rad/min) for 2min to 30min (preferably, 2min to 8min) and then cooled to room temperature. In one embodiment of the inventive concept, the mass percentages of the polyether polyol, the tin-based catalyst, and the toluene diisocyanate may be 65 wt% to 75 wt%, 25 wt% to 35 wt%, and 1 wt% to 5 wt%, respectively.
In an embodiment of the inventive concept, the tin-based catalyst may include one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and dibutyltin bis (dodecylthio) tin, and particularly, may include stannous octoate.
Further, in steps S2 and S3, the polyether polyol (or referred to as "polyether") may include one or more of polyether diol, polyether triol, polyether tetraol, and hydroxyl-free polyether. In the present invention, polyether-330 may be used. Polyether-330, as used herein, refers to a soft bubble polyether having a starter functionality of 3 and an average relative molecular weight of 3000 to produce the polyether.
Next, in step S4, the mixture obtained in step S2 may be mixed with the mixture obtained in step S3 and stirred at 150rad/min to 220rad/min for 10S to 15S; then, foaming the mixture at room temperature for 30-60 min, and curing the mixture at the temperature of 50-65 ℃ for 1-2 h to obtain the composite modified polyurethane foam microorganism immobilized carrier.
In one embodiment of the inventive concept, the mixture obtained in step S2 and the mixture obtained in step S3 may be mixed in a mass ratio of 3-10: 1.
The composite modified polyurethane foam microorganism immobilization carrier prepared by the steps S1 to S4 contains a large number of active chemical groups such as imino, amino, hydroxyl and the like, is favorable for immobilizing microorganisms by a carrier combination method, has small influence on the activity of the microorganisms, and is favorable for maintaining the activity of the immobilized microorganisms; and the porosity of the polyurethane foam is improved after the silicon-based mineral modified material is added, so that the fixed amount of microorganisms is increased, and the transfer of a matrix and metabolites is facilitated.
The composite modified polyurethane foam microorganism immobilized carrier has wide sources of selected materials and low price.
The method for preparing the composite modified polyurethane foam microorganism-immobilized carrier of the present invention will be described below with specific examples and with reference to FIGS. 2 to 7.
FIG. 2 is COD of example 1 according to the inventive conceptCrConcentration and COD removal rate as a function of time. Fig. 3 is a graph of ammonia nitrogen concentration and removal rate over time according to example 1 of the inventive concept. Fig. 4 is a graph comparing the COD removal rate of example 1 according to the inventive concept with that of comparative example 1. Fig. 5 is a graph comparing the removal of ammonia nitrogen of example 1 according to the inventive concept with the removal of ammonia nitrogen of comparative example 1. Fig. 6 is a graph comparing tolerance to phenol of the immobilized microorganism obtained according to example 2 of the inventive concept with that of the immobilized microorganism obtained according to comparative example 2. Fig. 7 is a graph comparing the degradation rate of phenol by the immobilized microorganisms obtained in example 2 according to the inventive concept with that of the immobilized microorganisms obtained in comparative example 2.
Example 1
The preparation method comprises the following steps: mixing 0.05 wt% of sepiolite slurry and 0.08 wt% of hexadecyltrimethylammonium chloride aqueous solution according to the mass ratio of 1:2, stirring for 3 hours at 75 ℃, cooling to room temperature, performing suction filtration by using a third sand core funnel, performing vacuum drying at 90 ℃ to constant weight, and grinding through a 400-mesh sieve to obtain the sepiolite modified material. Then, polyether-330, silicone oil, water, a sepiolite modified material, triethylamine, a soft bubble pore forming agent (model KY-1218, Yunzhen NJh K.K.) and liquid paraffin were mixed, stirred at a high speed for 8min, and treated with ultrasonic waves for 8min to obtain a mixture A, wherein the mass percentages of the polyether-330, the silicone oil, the water, the sepiolite modified material, the triethylamine, the soft bubble pore forming agent and the liquid paraffin were 72 wt%, 3 wt%, 8 wt%, 5 wt%, 4 wt%, 6 wt% and 2 wt%, respectively. Next, polyether-330 and stannous octoate were mixed and stirred at a high speed for 8min at a temperature of 85 ℃, then Toluene Diisocyanate (TDI) was rapidly added and stirred at 220rad/min for 5min and then cooled to room temperature to obtain a mixture B, wherein the mass percentages of polyether-330, stannous octoate and TDI were 70 wt%, 29 wt% and 1 wt%. And then, mixing the mixture A and the mixture B according to the ratio of 4:1, stirring for 10s at 220rad/min, stopping, foaming for 60min at room temperature, and curing for 2h at 60 ℃ to obtain the sepiolite composite modified polyurethane foam microorganism immobilized carrier.
Example 2
The preparation method comprises the following steps: mixing 0.10 wt% of sepiolite slurry and 0.05 wt% of hexadecyl trimethyl ammonium bromide aqueous solution according to the mass ratio of 1:4, stirring for 3.5 hours at 80 ℃, cooling to room temperature, performing suction filtration by using a third sand core funnel, performing vacuum drying at 95 ℃ to constant weight, and grinding through a 400-mesh sieve to obtain the sepiolite modified material. Then, polyether-330, silicone oil, water, sepiolite modified material, triethylamine, soft foam pore forming agent (model KY-1218, Yuzhen Miao science and technology Limited, Shenzhen), and liquid paraffin were mixed, stirred at high speed for 10min, and treated with ultrasonic waves for 10min to obtain a mixture A, wherein the mass percentages of polyether-330, silicone oil, water, sepiolite modified material, triethylamine, soft foam pore forming agent, and liquid paraffin were 70 wt%, 5 wt%, 10 wt%, 3 wt%, 4 wt%, 7 wt%, and 1 wt%, respectively. Next, polyether-330 and stannous octoate were mixed and stirred at a high speed at a temperature of 95 ℃ for 5min, then TDI was rapidly added and stirred at 180rad/min for 5min and then cooled to room temperature to obtain a mixture B, wherein the mass percentages of polyether-330, stannous octoate and TDI were 66 wt%, 30 wt% and 4 wt%. And then, mixing the mixture A and the mixture B according to the ratio of 9:1, stirring for 15s at 180rad/min, stopping, foaming for 45min at room temperature, and curing for 1.5h at 65 ℃ to obtain the sepiolite composite modified polyurethane foam microorganism immobilized carrier.
Comparative example 1:
a sepiolite composite polyurethane foam microorganism-immobilized carrier was prepared in substantially the same manner as in example 1, except that unmodified sepiolite was used.
Comparative example 2:
a sepiolite composite polyurethane foam microorganism-immobilized carrier was prepared in substantially the same manner as in example 2, except that unmodified sepiolite was used.
Evaluation example 1:
the microorganism-immobilized carrier prepared in example 1 and the microorganism-immobilized carrier prepared in comparative example 1 were cut into 2cm × 2cm × 2cm cubes, and each of them was fed into a reactor for treating domestic sewage to conduct an experiment. The biochemical reactor for treating the domestic sewage is made of organic glass, the effective volume is 15.7L, the main body part consists of a reaction area and an aeration device, the diameter is 20cm, and the total height is 50 cm.
The experimental conditions are as follows: the experiment adopts a continuous operation mode, the inflow rate is controlled by a peristaltic pump, the flow rate is 2.6L/h, the hydraulic retention time is 8h, and the aeration intensity is 4m3/m2H, controlling the dissolved oxygen in the reactor to be about 3mg/L, wherein the filling rate of the sepiolite composite modified polyurethane foam microorganism immobilized carrier is 50%. In addition, the parameters of the inlet water quality are as follows: CODCrThe concentration is 236mg/L-434mg/L, NH3The concentration of N is 22.7mg/L to 43.1mg/L,
as can be seen from FIGS. 2 and 3, after 8 days of treatmentCOD of effluent quality to which the microorganism-immobilized carrier prepared in example 1 was addedCrThe concentration is about 50mg/L, the ammonia nitrogen concentration is about 5.00mg/L, and the effluent quality can reach the first-class A standard. Further, as can be seen from fig. 4 and 5, the microbial-immobilized carrier of example 1 has an increased COD removal rate and an increased ammonia nitrogen removal rate of about 12% and about 14.6%, respectively, as compared to the unmodified microbial-immobilized carrier of comparative example 1.
Evaluation example 2:
preparation of the immobilized microorganism of the invention: cutting the sepiolite composite modified polyurethane foam microorganism immobilization carrier prepared in the embodiment 2 into cubes of 2cm multiplied by 2 cm; adding 25% of carriers and 4g of XA05 high-efficiency phenol degrading bacteria in the effective volume of an immobilization reactor into the immobilization reactor (the effective volume of the immobilization reactor is 5L); adding 75% of the effective volume of nutrient solution (containing 400mg/L phenol) into the immobilization reactor, maintaining the temperature at 30 deg.C, adjusting pH value in the immobilization reactor to 7.5 with sodium bicarbonate, and then starting aeration; adding efficient microorganisms and a small amount of inorganic salts every day in the first three days, and simultaneously, paying attention to adjusting the pH value in the immobilization reactor; after 6 days, the immobilization is completed, the carrier is filtered out and washed with normal saline to obtain the immobilized microorganism, and the immobilized microorganism is stored at the temperature of 5 ℃ for later use.
Preparation of immobilized microorganism of comparative example: the immobilized microorganism of the comparative example was prepared in the same manner as the immobilized microorganism of the present invention except that the sepiolite composite polyurethane foam microorganism-immobilized carrier obtained in comparative example 2 was used.
The immobilized microorganism of the invention and the immobilized microorganism of the comparative example are respectively added into a bioreactor for treating wastewater containing high-concentration phenol, the filling rate of the immobilized microorganism is 50 percent, the bottom of the bioreactor is provided with a micropore aeration head, the aeration intensity is 6m3/m2H, reaction time 10 hours. Here, a glass column having an effective volume of 20L was used as the bioreactor.
As can be seen from FIG. 6, the degradation rate of phenol by the immobilized microorganism of the comparative example was decreased when the concentration of phenol in the influent was more than 1000mg/L, whereas the degradation rate of phenol by the immobilized microorganism of the present invention was decreased when the concentration of phenol in the influent was more than 2000mg/L, indicating that the tolerance of the immobilized microorganism obtained using the carrier of example 2 of the present invention to phenol was significantly better than the degradation rate of phenol by the immobilized microorganism obtained using the unmodified carrier of comparative example 2.
Furthermore, as can be seen from fig. 7, the degradation rate of phenol by the immobilized microorganism obtained using the support of example 2 was significantly higher than that of phenol by the immobilized microorganism obtained using the unmodified support of comparative example 2. Furthermore, when the initial concentration of phenol was 1500mg/L, the degradation rate of phenol by the immobilized microorganism obtained using the carrier of example 2 was 300 mg/L.multidot.h.
As a summary and a review, the present invention proposes a method for preparing a composite modified polyurethane foam microorganism immobilization carrier. According to the invention concept, the silicon-based mineral modified material is combined with polyurethane to form the composite modified polyurethane foam microorganism immobilization carrier, so that the problem of poor mass transfer of the traditional microorganism immobilization carrier can be solved. In addition, the silicon-based mineral modified material is combined with polyurethane, so that the composite modified polyurethane foam microorganism immobilization carrier contains a large number of active chemical groups such as imino, amino, hydroxyl and the like, and is favorable for immobilizing microorganisms.
Although the present invention has been described in connection with the exemplary embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims.

Claims (10)

1. A method for preparing a composite modified polyurethane foam microorganism immobilization carrier, comprising the steps of:
s1, modifying the silicon-based mineral material by using an organic template agent to obtain a silicon-based mineral modified material;
s2, mixing polyether polyol, silicone oil, water, a silicon-based mineral modified material, an amine catalyst, a pore-opening agent and liquid paraffin, stirring uniformly, and then carrying out ultrasonic treatment;
s3, mixing polyether polyol and a tin catalyst, stirring uniformly at the temperature of 85-95 ℃, and adding toluene diisocyanate;
and S4, mixing the mixture obtained in the step S2 with the mixture obtained in the step S3, uniformly stirring, foaming and curing.
2. The method according to claim 1, wherein in step S1, the silicon-based mineral material slurry with the mass percentage of 0.05 wt% -0.50 wt% and the organic template agent aqueous solution with the mass percentage of 0.03 wt% -0.50 wt% are mixed according to the mass ratio of 1:2-1:6, and then stirred for 3h-8h at the temperature of 25 ℃ to 80 ℃, filtered, vacuum-dried to constant weight, ground and sieved to obtain the silicon-based mineral modified material.
3. The method of claim 1, wherein the silicon-based mineral material comprises at least one of sepiolite, attapulgite, zeolite, fumed silica, diatomaceous earth, and montmorillonite clay.
4. The method of claim 1, wherein the organic templating agent comprises one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, ethylenediamine, n-butylamine, and pyrrolidine.
5. The method of claim 1, wherein the polyether polyol, the silicone oil, the water, the silicon-based mineral-modified material, the amine-based catalyst, the cell opener, and the liquid paraffin are 70 wt% to 80 wt%, 2 wt% to 5 wt%, 5 wt% to 12 wt%, 1 wt% to 6 wt%, 2 wt% to 5 wt%, 3 wt% to 8 wt%, and 1 wt% to 3 wt%, respectively, in step S2.
6. The method of claim 1, wherein the amine catalyst comprises one or more of N, N-dimethylcyclohexylamine, triethylamine, NMM, triethanolamine, pyridine, and DMEA; the cell opener comprises a linear hydrocarbon or a cyclic hydrocarbon compound.
7. The method according to claim 1, wherein in step S3, the polyether polyol and the tin catalyst are mixed and stirred at a temperature of 85 ℃ to 95 ℃ for 5min to 30min, then toluene diisocyanate is added and stirred at 100rad/min to 220rad/min for 2min to 30min and then cooled to room temperature,
wherein the mass percentages of the polyether polyol, the tin catalyst and the toluene diisocyanate are 65-70 wt%, 25-30 wt% and 1-5 wt%, respectively.
8. The method of claim 1, wherein the tin-based catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and dibutyltin bis (dodecylthio) tin.
9. The method according to claim 1, wherein, in step S4, the mixture obtained in step S2 and the mixture obtained in step S3 are mixed in a mass ratio of 3-10: 1.
10. The method of claim 1, wherein in steps S2 and S3, the polyether polyol comprises one or more of a polyether diol, a polyether triol, a polyether tetraol, and a hydroxyl free polyether.
CN201910295415.9A 2019-04-12 2019-04-12 Method for preparing composite modified polyurethane foam microorganism immobilization carrier Pending CN111807502A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101619310A (en) * 2009-07-22 2010-01-06 兰州交通大学 Immobilized carrier of nano-attapulgite clay compounded hydrophilic urethane foam microorganisms
CN103483532A (en) * 2013-09-23 2014-01-01 安徽济峰节能材料有限公司 Modified polyurethane foaming plastic
CN105440304A (en) * 2015-12-14 2016-03-30 青岛水务集团有限公司科技中心 Preparation method of modified montmorillonite-containing reticulated polyurethane microbial carrier

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101619310A (en) * 2009-07-22 2010-01-06 兰州交通大学 Immobilized carrier of nano-attapulgite clay compounded hydrophilic urethane foam microorganisms
CN103483532A (en) * 2013-09-23 2014-01-01 安徽济峰节能材料有限公司 Modified polyurethane foaming plastic
CN105440304A (en) * 2015-12-14 2016-03-30 青岛水务集团有限公司科技中心 Preparation method of modified montmorillonite-containing reticulated polyurethane microbial carrier

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