CN113087283B - Foam immobilized microorganism filler for sewage treatment and preparation method thereof - Google Patents
Foam immobilized microorganism filler for sewage treatment and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a foam-shaped immobilized microorganism filler for sewage treatment, which is prepared from polyether polyol, isocyanate, a foam homogenizing agent, a catalyst, a foaming agent, a chain extender and a mixed auxiliary material by taking composite polyurethane foam as a carrier to fix white rot fungi; the mixed auxiliary material is formed by mixing biomass charcoal and a chelating adsorbent, wherein the biomass charcoal is obtained by soaking crop straws and/or shells in potassium chloride and magnesium chloride solution after carbonization, and the chelating adsorbent takes montmorillonite as a matrix and introduces reactive groups through surface grafting. The invention also discloses a preparation method of the foam-shaped immobilized microorganism filler, which comprises the steps of preparing composite polyurethane foam by adopting a one-step foaming process, and then condensing and solidifying white rot fungi by adopting sodium carboxymethylcellulose-hydroxypropyl chitosan, so that the foam has large pore volume and uniform foam pores, has good removal effect on ammonia nitrogen, organic matters and heavy metal pollution, and has long service life.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a foam-shaped immobilized microorganism filler for sewage treatment and a preparation method thereof.
Background
With the development of industry and the acceleration of urban process, water resources in China face two challenges of increasing severity: shortage of water resources and pollution of water environment. Due to the relative lag of sewage treatment facilities construction, urban river with flood control, drainage and transportation functions becomes a place for receiving urban sewage and even solid waste, so that COD and NH in water body are caused 3 Organic pollution indexes such as N, TP, TN, volatile phenol and the like and heavy metal pollutants such as Cu, cr and the like exceed the standard. The river pollution problem threatens the water resources of the city and restricts the sustainable development of the city.
At present, the water body is polluted by rich nutrient element nitrogen and phosphorus, and meanwhile, the pollution of some organic refractory substances is also related, especially natural or artificial synthetic organic pollutants with serious harm to human health and environment are more and more remarkable in the characteristic of the water body pollution; more and more organic and inorganic pollutants enter the water body and the pollutants are accumulated and exposed in the water environment for a long time, and various pollution effects show synergistic or antagonistic effects, so that the problem of urban surface water body pollution is more complicated. The water pollution directly affects the development of ecological environment, industrial and agricultural production and the stability of society, causes great loss to national economy and lives and properties of people, and has serious threat to the life quality and health level of people.
Aiming at the pollution state of surface water, the conventional water body restoration technology mainly comprises the following steps: physical repair, chemical repair, biological repair. The physical repair method comprises sediment dredging, water diversion and changing, filtering, coagulating sedimentation, chemical adding air floatation and the like, and can effectively remove pollutants such as fine suspended particles, algae, solid impurities, phosphate and the like in the water, but the physical repair method has relatively high investment cost in the early stage of surface water repair and high maintenance cost in the later stage, is time-consuming and energy-consuming, has short maintenance time and cannot be controlled from the source. The chemical restoration method is mainly used for algae, phosphorus and denitrification treatment of surface water, such as adding chemical agents to kill algae, adding ferric salt to promote precipitation of phosphorus, and adding lime to denitrify, and can be used as an emergency measure to generate a water purifying effect in a short time; however, as the conditions of complex pollutant components and various types in the water body occur, chemical agents need to be frequently changed, the dosage of the agents is larger, the later-period influence on aquatic ecology is difficult to evaluate, secondary pollution is easy to cause, other pollution loads of the water body can be increased, and the treatment cost is higher. The bioremediation method mainly comprises a biostable pond, a biomembrane method, aeration reoxygenation, biological liquid growth promotion and the like, is generally summarized as a microbial remediation and plant remediation technology, and utilizes the metabolism of microorganisms and plants to degrade and remove pollutants, so that the method has the advantages of low cost, no secondary pollution to the environment and the like, and is widely applied. Traditional microbial remediation is by way of degradation by free dominant microorganisms, but free microorganisms have the following problems: the concentration of effective degrading bacteria in unit volume is low, the reactor is started slowly, the bacteria are easy to run off, the bacteria compete with indigenous bacteria to be in the weakness, the toxicity resistance infringement capability is poor, the reactor is sensitive to the violent hydraulic condition change, and the like.
In order to solve the above problems, the development of immobilized bacteria algae treatment technology is a research hotspot for many scholars at present, such as: domestic sewage is treated by using polyvinyl alcohol-sodium alginate immobilized nitrifying bacteria, and the screened multiple substances capable of degrading Chemical Oxygen Demand (COD) Cr ) The immobilization of microorganisms on different carriers and the like have been reported successively. However, after the bacteria and algae are immobilized, the growth, the morphology, the metabolism and the like of the bacteria and algae can be changed, and the artificially synthesized filler carrier is usually composed of inorganic materials such as ceramsite, activated carbon particles and the like, and the fillers do not contain nutrition, so that the problems of low biological activity, long reactor starting time and the like are easily caused, and the water quality purification of various composite pollutants is difficult to be suitable for.
Disclosure of Invention
Aiming at the complex characteristic of water pollution, the invention provides a foam-shaped immobilized microorganism filler for sewage treatment, which takes composite polyurethane foam added with biomass charcoal and chelating adsorbent as a carrier to solidify white rot fungi, improves the adsorption performance and biological affinity of the carrier, and achieves the purposes of complexing and decomposing composite pollutants; the invention also provides a preparation method of the foam-shaped immobilized microorganism filler.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the foam-shaped immobilized microorganism filler for sewage treatment is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, 115-125 parts of isocyanate, 0.25-1 part of foam stabilizer, 0.2-0.4 part of catalyst, 3-5 parts of foaming agent, 0.5-1 part of chain extender and 8-10 parts of mixed auxiliary material; the mixed auxiliary material is formed by mixing biomass charcoal and a chelating adsorbent according to the mass ratio of 1:3-6;
the chelating adsorbent is prepared by the following steps: dispersing montmorillonite in an ethanol aqueous solution, adding gamma-aminopropyl trimethoxy silane, stirring for 4-6 hours at 50-70 ℃, then carrying out solid-liquid separation, extracting and washing the solid with ethanol, carrying out vacuum drying, and grinding to obtain silanized montmorillonite; dispersing silanized montmorillonite in 2-4wt% oxalic acid aqueous solution, adding tyrosine, oscillating for 12-20 h at 50-70 ℃, dropwise adding ethylenediamine aqueous solution to adjust the solution to be neutral, continuing oscillating for 3-4 h, then carrying out solid-liquid separation, washing the solid with water, and carrying out vacuum drying to obtain the chelating adsorbent; wherein the dosage ratio of montmorillonite, gamma-aminopropyl trimethoxy silane and tyrosine is 10: (4-5) and (3-4).
Preferably, the biomass charcoal is prepared by the following steps: washing, air-drying and crushing crop straws and/or shells, heating to 450-550 ℃ at a speed of 5-10 ℃/min under an anaerobic condition, carbonizing at a constant temperature for 50-80 min, cooling to normal temperature, grinding and sieving, then placing into an aqueous solution containing 0.03-0.06 mol/L potassium chloride and 0.2-0.3 mol/L magnesium chloride, vibrating and soaking for 15-25 h, carrying out solid-liquid separation, and drying the solid at 85-105 ℃ to obtain biomass charcoal.
Preferably, the polyether polyol adopts one or more than two of amine-terminated polyether, dihydroxypolyether and trihydroxy polyether; wherein the molecular weight of the amine-terminated polyether is 200-1000, and the amine value is more than 100 mg KOH/g; the molecular weight of the dihydroxyl polyether and the trihydroxy polyether is 1500-3500, and the hydroxyl value is 15-60 mg KOH/g.
Preferably, the isocyanate is toluene diisocyanate and/or diphenylmethane diisocyanate; the foam homogenizing agent is methyl silicone oil; the catalyst is triethylenediamine; the foaming agent is deionized water; the chain extender is triethanolamine.
Preferably, in the preparation step of the chelating adsorbent, the volume fraction of ethanol in the aqueous solution of ethanol is 85-95%.
Further, the addition amount of montmorillonite in the ethanol aqueous solution is 20-30 g/L; the adding amount of the silanized montmorillonite in the oxalic acid aqueous solution is 28-45 g/L.
The preparation method of the foam-shaped immobilized microorganism filler for sewage treatment comprises the following steps:
(1) Weighing the raw materials according to parts by weight; preheating polyether polyol at 40-45 ℃, adding a foam homogenizing agent, a catalyst, a chain extender and a foaming agent, uniformly stirring, adding a mixed auxiliary material, uniformly stirring, adding isocyanate, uniformly dispersing, pouring into a mould at 50-60 ℃ for foaming, expanding and shaping, and curing at room temperature for 24-48 hours after mould opening to obtain composite polyurethane foam;
(2) Preparing a solid culture medium and a liquid culture medium respectively, performing expansion culture on white rot fungi in the solid culture medium, then placing spores on the solid culture medium in the liquid culture medium, performing constant-temperature culture at 30-35 ℃ for 4-7 days, collecting hypha and placing the hypha in an aqueous solution of 1-2 wt% hydroxypropyl chitosan to obtain a microorganism suspension;
(3) And (3) cutting, cleaning, drying and sterilizing the composite polyurethane foam obtained in the step (1), immersing the composite polyurethane foam in an aqueous solution of 0.5-1 wt% of sodium carboxymethylcellulose for 30-60 min, taking out the composite polyurethane foam, draining, then placing the composite polyurethane foam in the microbial suspension obtained in the step (2), vibrating and curing for 24-72 h, taking out the composite polyurethane foam, and drying the composite polyurethane foam.
Preferably, the concentration of the components contained in the solid medium in step (2) is: 200 g/L potato extract, 20 g/L glucose and 20/g/L, KH agar 2 PO 4 3 g/L、MgSO 4 ·7H 2 O 1.5 g/L。
Preferably, the concentration of the components contained in the liquid medium in the step (2) is respectively: glucose 20 g/L, ammonium tartrate 0.2 g/L, KH 2 PO 4 2 g/L、MgSO 4 ·7H 2 O 0.25 g/L、CaCl 2 0.1 g/L、MnSO 4 ·4H 2 O 5 mg/L、VB 1 5 mg/L, 150 mL/L of trace elements; wherein, the microelement solution comprises the following components: naCl 1.0 g/L, feSO 4 ·7H 2 O 100 mg/L、ZnSO 4 ·7H 2 O 100 mg/L、CoSO 4 ·7H 2 O 100 mg/L、CuSO 4 ·5H 2 O 10 mg/L、KAl(SO 4 ) 2 100 mg/L、H 3 BO 3 10 mg/L、Na 2 MoO 4 10 mg/L。
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a one-step foaming process to prepare the composite polyurethane foam, and adds a proper amount of biomass charcoal and chelating adsorbent as heterogeneous nucleating agents, and as the biomass charcoal and the chelating adsorbent are light in weight and large in specific surface area, more contact areas can be provided between a polymer and a gas phase to improve the nucleation state, the foaming system is low in viscosity and good in rheological property, so that the prepared composite polyurethane foam is large in pore volume and uniform in pore size, and the adsorption property and the water treatment effect of the foamed immobilized microorganism filler are improved.
(2) The biomass charcoal is obtained by carbonizing crop straws and/or shells and then soaking the carbonized biomass charcoal in a potassium chloride and magnesium chloride solution, and the active sites of the biomass charcoal can be increased by soaking the carbonized biomass charcoal in the salt solution; the chelating adsorbent adopts montmorillonite as a matrix, and reactive groups are introduced through surface grafting, so that a series of chemical reactions can be carried out with heavy metals in water; the mixed auxiliary material formed by mixing the two can improve the adsorption and complexation performance of the foam-shaped immobilized microorganism filler on the composite pollutants; the mixed auxiliary material has good biological affinity, is beneficial to the immobilization and catabolism of white rot fungi, and can further transform the chemical form of pollutants through the secretion of metabolic substances or the oxidation-reduction effect of the white rot fungi, thereby achieving the effect of degrading the pollutants.
(3) The composite polyurethane foam adopts sodium carboxymethyl cellulose-hydroxypropyl chitosan to coagulate and solidify white rot fungi, overcomes the problems of loss of white rot fungi, poor toxicity resistance infringement capability, sensitivity to drastic change of hydraulic conditions and the like, is beneficial to multiplication of solidified microorganisms, does not need additional carbon sources in the water treatment process, has good removal effect on ammonia nitrogen, organic matters and heavy metal pollution, does not produce secondary pollution, and has good recycling effect and long service life.
Detailed Description
In order to make the technical objects, technical solutions and advantageous effects of the present invention more apparent, the technical solutions of the present invention will be further described with reference to specific examples, which are intended to illustrate the present invention but are not to be construed as limiting the present invention, and specific techniques or conditions are not specified in the examples, and are performed according to techniques or conditions described in the literature in the art or according to the product specifications.
The raw materials used in the following examples are all common commercial products, the white rot fungiPhanerochaete chrysosporium is selected and purchased from China center for type culture Collection of microorganisms, and the preservation number is 40299; the montmorillonite has a particle size of 1250 mesh and a density of 1.6 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyether polyol adopts trihydroxy polyether (N-330); the isocyanate adopts Toluene Diisocyanate (TDI); the foam homogenizing agent is methyl silicone oil; the catalyst is triethylenediamine; the foaming agent is deionized water; the chain extender is triethanolamine; the sodium carboxymethyl cellulose is purchased from Zhengzhou Mingxin chemical products, food grade,CAS： 9004-32-4the method comprises the steps of carrying out a first treatment on the surface of the The hydroxypropyl chitosan was purchased from the western-style first grass biotechnology company, cat No.: SH-03-02.
The solid culture medium comprises the following components in concentration: 200 g/L potato extract, 20 g/L glucose and 20/g/L, KH agar 2 PO 4 3 g/L、MgSO 4 ·7H 2 O1.5 g/L. The concentration of the components contained in the liquid culture medium is respectively as follows: glucose 20 g/L, ammonium tartrate 0.2 g/L, KH 2 PO 4 2 g/L、MgSO 4 ·7H 2 O 0.25 g/L、CaCl 2 0.1 g/L、MnSO 4 ·4H 2 O 5 mg/L、VB 1 5 mg/L, 150 mL/L of trace elements; wherein, the microelement solution comprises the following components: naCl 1.0 g/L, feSO 4 ·7H 2 O 100 mg/L、ZnSO 4 ·7H 2 O 100 mg/L、CoSO 4 ·7H 2 O 100 mg/L、CuSO 4 ·5H 2 O 10 mg/L、KAl(SO 4 ) 2 100 mg/L、H 3 BO 3 10 mg/L、Na 2 MoO 4 10 mg/L。
Example 1
The foam-shaped immobilized microorganism filler for sewage treatment is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, 120 parts of isocyanate, 0.5 part of foam stabilizer, 0.3 part of catalyst, 4 parts of foaming agent, 0.8 part of chain extender and 9 parts of mixed auxiliary material; wherein the mixed auxiliary material is formed by mixing biomass charcoal and chelating adsorbent according to the mass ratio of 1:4.
The biomass charcoal is prepared by the following steps: washing, air-drying and crushing crop straws and/or shells, heating to 500 ℃ at a speed of 5 ℃/min under an anaerobic condition, carbonizing at a constant temperature for 60 min, cooling to the normal temperature, grinding and sieving, then placing in an aqueous solution containing 0.05 mol/L potassium chloride and 0.25 mol/L magnesium chloride, vibrating and soaking for 20 h, performing solid-liquid separation, taking solids, and drying at 90 ℃ to obtain biomass charcoal.
The chelating adsorbent is prepared by the following steps: dispersing montmorillonite in ethanol water solution (volume fraction is 90%), adding gamma-aminopropyl trimethoxy silane (the addition amount of montmorillonite in ethanol water solution is 25 g/L, the addition amount of gamma-aminopropyl trimethoxy silane is 10 g/L), stirring at 60deg.C for 5 h, then performing solid-liquid separation, extracting and washing the solid with ethanol, vacuum drying, and grinding to obtain silanized montmorillonite; dispersing silanized montmorillonite in 3 wt% oxalic acid aqueous solution (the dosage of the oxalic acid aqueous solution is the same as the volume of ethanol aqueous solution), adding tyrosine (the dosage of tyrosine in the oxalic acid aqueous solution is 10 g/L), oscillating 16 h at 60 ℃, dropwise adding ethylenediamine aqueous solution to adjust the solution to be neutral, continuing oscillating 3 h, then carrying out solid-liquid separation, washing the solid with water, and drying in vacuum to obtain the chelating adsorbent. Wherein the dosage ratio of montmorillonite, gamma-aminopropyl trimethoxy silane and tyrosine is 5:2:2.
The preparation method of the foam-shaped immobilized microorganism filler for sewage treatment comprises the following steps:
(1) Weighing the raw materials according to parts by weight; preheating polyether polyol at 40-45 ℃, adding a foam homogenizing agent, a catalyst, a chain extender and a foaming agent, stirring uniformly (stirring for 2 min), adding a mixed auxiliary material, stirring uniformly (stirring for 2 min), adding isocyanate, dispersing uniformly (stirring at a high speed for 5-10 s), rapidly pouring into a mould at 55 ℃ for foaming, expanding and shaping (about 5 min), and curing at room temperature for 48 h after mould opening to obtain a composite polyurethane foam;
(2) Preparing a solid culture medium and a liquid culture medium respectively, performing expansion culture on white rot fungi in the solid culture medium, then placing spores on the solid culture medium in the liquid culture medium, performing constant-temperature culture at 30-35 ℃ for 5 days, collecting mycelia and placing the mycelia in a 2 wt% hydroxypropyl chitosan aqueous solution to obtain a microorganism suspension (the weight of the mycelia is calculated by wet weight, and the adding amount of the mycelia in the hydroxypropyl chitosan aqueous solution is 40 g/L);
(3) Cutting the composite polyurethane foam obtained in the step (1) into a block-shaped matrix (2 cm multiplied by 2 cm multiplied by 1 cm), cleaning, drying and sterilizing, immersing 20 blocks of the block-shaped matrix in 800 mL mass percent of 1 wt% sodium carboxymethylcellulose aqueous solution for 45 min, taking out, draining, then placing in 800 mL microorganism suspension obtained in the step (2), vibrating, solidifying for 48 h, taking out and drying to obtain the polyurethane foam.
In order to verify the treatment effect of potassium chloride and magnesium chloride, the treated biomass charcoal and untreated biomass charcoal (after crop straws and/or shells are washed, air-dried and crushed, the temperature is raised to 500 ℃ at a speed of 5 ℃/min under the anaerobic condition, and then the biomass charcoal is carbonized at a constant temperature for 60 minutes, cooled to the normal temperature, ground and sieved) are respectively recorded as a sample A and a sample B, and are used as adsorption samples for carrying out adsorption test on ammonia nitrogen. The adsorption test method comprises the following steps: under normal temperature, adding 0.5 g adsorption sample into ammonium chloride solution with ammonia nitrogen concentration of 100 mg/L of 50 mL, oscillating 24 h in a constant temperature oscillator, taking out, filtering with 0.45 μm filter membrane, collecting 1 mL filtrate in 50 mL colorimetric tube, diluting with water to marked line, measuring residual ammonia nitrogen content in the filtrate, and calculating adsorption quantity q= (C) of adsorption sample 0 -C t ) W, where C 0 100 mg/L, and W is the amount of the adsorbed sample (i.e., 10 g/L). The adsorption amounts of the sample A and the sample B were 3.56 mg/g and 2.37 mg/g, respectively, as measured. Therefore, the adsorption of the biomass charcoal treated by the potassium chloride and the magnesium chloride is obviously improved, which indicates that potassium ions and magnesium ions can replace impurities in the pore canal of the biomass charcoal, and the microscopic space is changed, so that the adsorption performance and the ion exchange capacity of the biomass charcoal are improved.
Example 2
The foam-shaped immobilized microorganism filler for sewage treatment is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, 115 parts of isocyanate, 0.25 part of foam stabilizer, 0.4 part of catalyst, 5 parts of foaming agent, 1 part of chain extender and 10 parts of mixed auxiliary material; wherein the mixed auxiliary material is formed by mixing biomass charcoal and chelating adsorbent according to the mass ratio of 1:6.
Example 3
The foam-shaped immobilized microorganism filler for sewage treatment is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, 125 parts of isocyanate, 1 part of foam stabilizer, 0.2 part of catalyst, 3 parts of foaming agent, 0.5 part of chain extender and 8 parts of mixed auxiliary material; wherein the mixed auxiliary material is formed by mixing biomass charcoal and chelating adsorbent according to the mass ratio of 1:3.
Example 2 and example 3 both use the method of example 1 to prepare biomass charcoal, chelating adsorbent, and foam-like immobilized microbial filler.
Through detection, the foam-shaped immobilized microorganism filler prepared in the embodiment 1-3 has certain elasticity, is not easy to break, has the pore diameter ranging from 1.05 mm to 1.36 mm and the average density ranging from 0.28 g/cm to 0.30 g/cm 3 The number of bacteria solidified on each foam-like microorganism-immobilized filler (2 cm ×2 cm ×1 cm) was about 1.2×10 on average 8 And each.
The foam-like microorganism-immobilized filler obtained in example 1 was subjected to column packing treatment, the column had a cross-sectional diameter of 1m and a height of 1m, and 100 pieces of the filler were packed, and a screen was added near the upper end of the column to prevent the filler from floating on the water surface. Simulating a polluted water sample, wherein the indexes are as follows: pH 7.15, NH 4 + N50 mg/L, TP 2.5.5 mg/L (inorganic phosphorus), pb 2+ Is 25 mug/L, cu 2+ The concentration of (C) was 20. Mu.g/L, and the concentration of 2-chlorophenol was 100. Mu.g/L. Injecting a polluted water sample into the column, treating the polluted water sample by using the prepared filler column, and carrying out hydraulic retention on the polluted water sample under the condition of room temperature by 8 h, wherein the interval aeration is 2 h (4 times of aeration, 30 minutes each time), and the concentration of each pollutant in the effluent is as follows: NH (NH) 4 + -N 1.4 mg/L、TP 0.4 mg/L、Pb 2+ Is 7.9 mug/L, cu 2 + The concentration of (C) was 6.7. Mu.g/L, and the concentration of 2-chlorophenol was 33.2. Mu.g/L.Therefore, the foam immobilized microorganism filler prepared by the invention does not inactivate microorganisms, can be used for purifying various composite polluted water bodies, and has the removal rate of ammonia nitrogen, phosphorus, heavy metals and organic pollutants of more than 60 percent.
Comparative example 1
The foam-shaped immobilized microorganism filler for sewage treatment is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, 120 parts of isocyanate, 0.5 part of foam stabilizer, 0.3 part of catalyst, 4 parts of foaming agent and 0.8 part of chain extender.
Comparative example 1 a foam-like immobilized microorganism filler was prepared by the method of example 1.
Comparative example 2
A foam filler for sewage treatment adopts polyurethane foam and free white rot fungi (the mass ratio of the polyurethane foam to the white rot fungi is 1:0.8), wherein the polyurethane foam is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, 120 parts of isocyanate, 0.5 part of foam stabilizer, 0.3 part of catalyst, 4 parts of foaming agent and 0.8 part of chain extender; preparation of polyurethane foam: preheating polyether polyol at 40-45 ℃, adding a foam stabilizer, a catalyst, a chain extender and a foaming agent, stirring uniformly (stirring for 2 min), adding isocyanate, dispersing uniformly (stirring at a high speed for 5-10 s), rapidly pouring into a mould at 55 ℃ for foaming, expanding and shaping (about 5 min), and curing at room temperature for 48 h after mould opening.
Constructing an artificial wetland, plant and microorganism composite system, wherein the artificial wetland is of an upward subsurface flow wetland (10 m multiplied by 4 m multiplied by 1 m), and an impermeable layer, a supporting layer (pebble thickness 15 cm), a packing layer (packing thickness 40 cm), a filter screen layer and a guide-discharge layer (coarse sand thickness 20 cm) are sequentially paved in the artificial wetland from bottom to top; laying water distribution pipes in the supporting layer, uniformly arranging planting baskets at intervals in the guide and drainage layer, wherein the planting baskets are of an inner layer structure and an outer layer structure, sandy loam (thickness 20 and cm) is filled in the inner layer space, wetland plants (cattail plants) are planted, and filling materials are filled between the inner layer and the outer layer of the planting basket; the filler is respectively selected from the foam-shaped immobilized microorganism filler prepared in the example 1 and the comparative example 1, and the polyurethane foam prepared in the comparative example 2 and free white rot fungus.
The pretreated (flocculating settling) domestic sewage is selected, and the indexes of the inlet water are as follows: pH is 6.5-7.5, COD Cr 105-125 mg/L, NH 4 + N is 36-41 mg/L, TP 1.8-2.0 mg/L, pb 2+ 1.4-1.5 mug/L, hg 2+ 3.0 to 3.1. Mu.g/L. The artificial wetland is filled with water for the first time, 6 h is filled with water, the water stops 24 h, water is continuously fed (water starts to be discharged from the artificial wetland), the water feeding interval is controlled to be 6 h (water feeding time length is 6 h), namely 6 h is discharged after each water stop, water is discharged for sampling test (every 6 h), and the detection results of pollutants are shown in table 1; example 1 was monitored 5 times in succession and the results are shown in table 2.
Table 1 results of water quality test of example and comparative example effluent
Table 2 example 1 results of cycle test effluent quality test
As can be seen from tables 1 and 2, the absorption and enrichment functions of the root systems of the wetland plants and the decomposition and metabolism functions of microorganisms can be cooperated to achieve the effect of purifying water quality, but the foam-shaped immobilized microorganism filler prepared by the invention is superior to the comparative example, has good removal effect on ammonia nitrogen, phosphorus, organic matters, heavy metals and the like contained in the water body, and the quality of the effluent water reaches the national surface water environment quality IV standard. The embodiment 1 uses the composite polyurethane foam as an immobilization carrier, promotes the white rot strain to enhance the tolerance to sewage through a film forming effect, and ensures the normal metabolic function of degrading pollutants; in contrast, in comparative example 2, though the white rot fungus is used in a very high amount, the non-immobilized strain is not protected by a carrier system in the early growth stage, the growth is inhibited by pollutants in a water body, the metabolic function of the degradation pollutants is obviously weakened, and the water treatment effect is poor. Especially, biomass charcoal and chelating adsorbent are added in the preparation of polyurethane foam, the removal rate of heavy metals and organic matters is obviously improved, the recycling performance is stable, the polyurethane foam can be repeatedly used for a long time, the problem that thalli are reduced along with the discharge of water is solved, and the adsorption and removal effects of filler on pollutants are improved. In a word, the foam-shaped immobilized microorganism filler prepared by the invention is used for sewage treatment, can improve the pollutant removal effect of the constructed wetland, has short hydraulic retention time and remarkable purification effect, and has practical application value.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. A foam-like immobilized microbial filler for sewage treatment, characterized in that: the composite polyurethane foam is used as a carrier, sodium carboxymethyl cellulose-hydroxypropyl chitosan is adopted for coagulation and fixation of white rot fungi, and the composite polyurethane foam is prepared from the following raw materials in parts by weight: 100 parts of polyether polyol, 115-125 parts of isocyanate, 0.25-1 part of foam stabilizer, 0.2-0.4 part of catalyst, 3-5 parts of foaming agent, 0.5-1 part of chain extender and 8-10 parts of mixed auxiliary material; the mixed auxiliary material is formed by mixing biomass charcoal and a chelating adsorbent according to the mass ratio of 1:3-6;
the chelating adsorbent is prepared by the following steps: dispersing montmorillonite in an ethanol aqueous solution, adding gamma-aminopropyl trimethoxy silane, stirring for 4-6 hours at 50-70 ℃, then carrying out solid-liquid separation, extracting and washing the solid with ethanol, carrying out vacuum drying, and grinding to obtain silanized montmorillonite; dispersing silanized montmorillonite in 2-4wt% oxalic acid aqueous solution, adding tyrosine, oscillating for 12-20 h at 50-70 ℃, dropwise adding ethylenediamine aqueous solution to adjust the solution to be neutral, continuing oscillating for 3-4 h, then carrying out solid-liquid separation, washing the solid with water, and carrying out vacuum drying to obtain the chelating adsorbent; wherein the dosage ratio of montmorillonite, gamma-aminopropyl trimethoxy silane and tyrosine is 10: (4-5) and (3-4);
the biomass charcoal is prepared by the following steps: washing, air-drying and crushing crop straws and/or shells, heating to 450-550 ℃ at a speed of 5-10 ℃/min under an anaerobic condition, carbonizing at a constant temperature for 50-80 min, cooling to normal temperature, grinding and sieving, then placing into an aqueous solution containing 0.03-0.06 mol/L potassium chloride and 0.2-0.3 mol/L magnesium chloride, vibrating and soaking for 15-25 h, carrying out solid-liquid separation, and drying the solid at 85-105 ℃ to obtain biomass charcoal.
2. The foam-like immobilized microorganism packing for sewage treatment according to claim 1, wherein: the polyether polyol adopts one or more than two of amine-terminated polyether, dihydroxyl polyether and trihydroxy polyether; wherein the molecular weight of the amine-terminated polyether is 200-1000, and the amine value is more than 100 mg KOH/g; the molecular weight of the dihydroxyl polyether and the trihydroxy polyether is 1500-3500, and the hydroxyl value is 15-60 mg KOH/g.
3. The foam-like immobilized microorganism packing for sewage treatment according to claim 1, wherein: the isocyanate is toluene diisocyanate and/or diphenylmethane diisocyanate; the foam homogenizing agent is methyl silicone oil; the catalyst is triethylenediamine; the foaming agent is deionized water; the chain extender is triethanolamine.
4. The foam-like immobilized microorganism packing for sewage treatment according to claim 1, wherein: in the preparation step of the chelating adsorbent, the volume fraction of ethanol in the ethanol aqueous solution is 85-95%.
5. The foam-like immobilized microorganism packing for sewage treatment according to claim 4, wherein: the addition amount of montmorillonite in the ethanol aqueous solution is 20-30 g/L; the adding amount of the silanized montmorillonite in the oxalic acid aqueous solution is 28-45 g/L.
6. A method for preparing the foam-like immobilized microorganism packing for sewage treatment according to any one of claims 1 to 5, comprising the steps of:
(1) Weighing the raw materials according to parts by weight; preheating polyether polyol at 40-45 ℃, adding a foam homogenizing agent, a catalyst, a chain extender and a foaming agent, uniformly stirring, adding a mixed auxiliary material, uniformly stirring, adding isocyanate, uniformly dispersing, pouring into a mould at 50-60 ℃ for foaming, expanding and shaping, and curing at room temperature for 24-48 hours after mould opening to obtain composite polyurethane foam;
(2) Preparing a solid culture medium and a liquid culture medium respectively, performing expansion culture on white rot fungi in the solid culture medium, then placing spores on the solid culture medium in the liquid culture medium, performing constant-temperature culture at 30-35 ℃ for 4-7 days, collecting hypha and placing the hypha in an aqueous solution of 1-2 wt% hydroxypropyl chitosan to obtain a microorganism suspension;
(3) And (3) cutting, cleaning, drying and sterilizing the composite polyurethane foam obtained in the step (1), immersing the composite polyurethane foam in an aqueous solution of 0.5-1 wt% of sodium carboxymethylcellulose for 30-60 min, taking out the composite polyurethane foam, draining, then placing the composite polyurethane foam in the microbial suspension obtained in the step (2), vibrating and curing for 24-72 h, taking out the composite polyurethane foam, and drying the composite polyurethane foam.
7. The method for preparing a foam-like solid-supported microbial filler for sewage treatment according to claim 6, wherein the concentration of the components contained in the solid medium in the step (2) is: 200 g/L potato extract, 20 g/L glucose and 20/g/L, KH agar 2 PO 4 3 g/L、MgSO 4 1.5 g/L。
8. The method for preparing the foam-like immobilized microorganism filler for sewage treatment according to claim 6, wherein: the concentration of the components contained in the liquid culture medium in the step (2) is respectively as follows: glucose 20 g/L, KH 2 PO 4 2 g/L、MgSO 4 0.25 g/L、CaCl 2 0.1 g/L、MnSO 4 5 mg/L、VB 1 5 mg/L, 0.2 g/L of ammonium tartrate and 150 mL/L of trace elements.
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