CN108892231B

CN108892231B - Method for manufacturing biological enhanced membrane reactor and application of reactor in coking wastewater treatment

Info

Publication number: CN108892231B
Application number: CN201810809094.5A
Authority: CN
Inventors: 易志芳; 刘林; 戚仲凯
Original assignee: Nanjing Shunshuida Environmental Protection Technology Co ltd
Current assignee: Nanjing Shunshuida Environmental Protection Technology Co ltd
Priority date: 2018-07-23
Filing date: 2018-07-23
Publication date: 2021-06-01
Anticipated expiration: 2038-07-23
Also published as: CN108892231A

Abstract

The invention relates to a biological reinforced membrane reactor, a manufacturing method and application thereof in coking wastewater treatment, belonging to the technical field of biological membranes. The filler is formed by compounding temperature-sensitive gel taking N-isopropyl acrylamide as a main temperature-sensitive monomer and inorganic porous microspheres, and the porous composite filler has a hollow porous structure, so that more bacterial culture media can be contained, a slow release effect can be effectively generated in the treatment process, and the activity of bacteria is improved; meanwhile, as the porous temperature-sensitive gel is used as a carrier, when the temperature is 30-35 ℃ and is near the critical temperature, the porous temperature-sensitive gel can shrink obviously, so that the culture medium in the porous microspheres can be slowly released; and because the coking wastewater contains oily substances, the oily substances can be gathered on the surface of the porous filler after long-term operation, and the porosity of the surface of the porous filler is reduced, so that the surface of the temperature-sensitive gel filler is expanded by cooling the temperature-sensitive gel filler to be below the critical temperature, pollutants adsorbed on the surface of the temperature-sensitive gel filler can be quickly eliminated, and the filler is quickly regenerated.

Description

Method for manufacturing biological enhanced membrane reactor and application of reactor in coking wastewater treatment

Technical Field

The invention relates to a biological reinforced membrane reactor, a manufacturing method and application thereof in coking wastewater treatment, belonging to the technical field of biological membranes.

Background

The biofilm wastewater treatment technology is a technology for fixing microorganisms on a carrier to form a biofilm so as to degrade pollutants in wastewater, so that the correct selection of the carrier is very important for improving the wastewater treatment effect. The advent of organic synthetic materials in the 60's of the 20 th century, such as corrugated, tubular and honeycomb organic synthetic fillers made of polyethylene, polystyrene and polyamide, etc., which have high specific surface area and porosity, has enabled rapid development of biofilm-process sewage treatment technology, which has now become one of the major sewage treatment methods juxtaposed to the activated sludge process. The basic principle of the biological fluidized bed is as follows: the waste water and the return water of the water discharged from the biological fluidized bed reactor are mixed with air at the inlet of the oxygenation equipment, then enter from the bottom of the reactor, pass through the reactor from bottom to top, so that the continuous material is kept in a fluidized working state, and the waste water treated by the biofilm on the filler flows into a secondary sedimentation tank to settle the suspended biomass and discharge qualified water except part of the waste water flowing back to the inlet of the anaerobic equipment.

Biofilm carriers can be classified into suspended fillers and suspended fillers such as fixed fillers, soft fillers, semi-soft fillers and composite fillers according to the classification of the carrier materials. The suspension type filler comprises soft, semi-soft and combined fillers. The soft filler is mainly represented by soft fiber filler. The basic structure of the soft filler is that a soft fiber bundle is tied on a central rope and needs to be fixed on an auxiliary bracket during installation, which overcomes some disadvantages of the honeycomb filler. The variability of the gaps of the soft filler avoids the blocking phenomenon; the fiber yarn has a large quantity, thereby having huge theoretical specific surface area, low manufacturing cost and convenient processing. However, the soft filler generally causes the phenomenon of fiber bundle agglomeration after 1 year of use. Over time, the agglomeration phenomenon will be more and more severe. There are studies showing that: the soft fiber filler is in a floating state in water, and the collision and cutting to the gas-water mixed fluid are weak and are not enough to cut large bubbles into small bubbles, so that the transfer rate of oxygen is influenced. Aiming at the defects of both entanglement and filament breakage of the soft filler, experts in the industry improve the soft filler, namely, the semi-soft filler developed later is represented by BS type semi-soft filler. The semi-soft filler has smaller theoretical specific surface area than the soft filler, higher manufacturing cost than the soft filler, smooth surface and relatively poorer microorganism adhesion performance. The combined filler is designed on the basis of the advantages of large specific surface area, easy film formation, no agglomeration of semi-soft filler and uniform gas distribution of soft filler, and takes YDT elastic three-dimensional filler as an example. The YDT elastic three-dimensional filler L5 is used for film hanging and bubble cutting by utilizing dense filament yarns, has large specific surface area, more biological film amount, higher oxygen utilization ratio than that of a soft filler material, no blockage and long service life. The YDT filler film-passing test carried out by Meixiang and the like finds that: the YDT filler is easy to form a film and accumulate mud.

Disclosure of Invention

The invention provides a novel biological reinforced membrane reactor, which utilizes the thermal shrinkage type temperature-sensitive gel and hollow porous microspheres to be compounded as a carrier, utilizes the temperature sensitivity and porosity of the carrier, and effectively improves the wastewater treatment effect after membrane hanging.

The technical scheme is as follows:

a bio-enhanced membrane reactor is characterized in that a thermal shrinkage type temperature-sensitive gel and hollow porous microsphere compound is filled in the reactor.

The manufacturing method of the bio-enhanced membrane reactor comprises the following steps of:

step a: mixing methacrylic acid, N' -methylene bisacrylamide, azobisisobutyronitrile and ethanol according to a weight ratio of 10: 3-4: 0.2-0.5: 500-750, heating to react, firstly reacting for 20-30 min at 80-85 ℃, then evaporating the solvent to make the volume of the reaction liquid be 1/2-2/3, continuing to react for 40-50 min at 85-90 ℃, dispersing the reactant in deionized water, then performing centrifugal separation to obtain monodisperse polymer microspheres, dispersing the polymer microspheres in 5-10 wt% of NaOH solution, wherein the mass ratio of the polymer microspheres to the NaOH solution is 1: 80-100, soaking for 15-20 h, and then centrifuging and separating out the polymer microspheres; soaking the polymer microspheres in an aqueous solution containing 3-5 wt% of manganese chloride, wherein the mass percentage of the polymer microspheres in the aqueous solution of manganese chloride is 0.5-1 wt%, and after soaking for 10-15 h, centrifuging the polymer microspheres to obtain Mn²⁺@ polymeric microspheres; then adding Mn²⁺@ polymer microspheres are dispersed in 40-50 vol.% ethanol aqueous solution, and Mn²⁺The method comprises the following steps of @ enabling the concentration of polymer microspheres in an ethanol aqueous solution to be 2-4 wt%, adding chitosan and aluminum nitrate into the ethanol aqueous solution to enable the concentrations of the chitosan and the aluminum nitrate to be 0.5-1 wt% and 2.2-2.8 wt% respectively, then adding ammonia water to adjust the pH value to 8.0-8.5, standing for 10-20 hours for aging to enable aluminum sol to be generated on the surfaces of the microspheres, centrifugally separating products, cleaning with deionized water, roasting for 2-4 hours at 700-800 ℃, and removing the chitosan and polymers inside to obtain hollow porous alumina microspheres; (the purpose of this step is to prepare alumina microspheres with hollow, porous surface)

Step b: mixing hollow porous alumina microspheres with an ethanol solution of a silane coupling agent KH560 according to a weight ratio of 1: 20-25, wherein the concentration of a silane coupling agent KH560 in an ethanol solution is 5-10 wt%, carrying out a grafting reaction at 65-70 ℃, wherein the reaction time is 1-4 h, and after the reaction, carrying out centrifugal separation on a product to obtain hollow porous alumina microspheres grafted with the silane coupling agent; (the purpose of this step is to graft KH560 on the surface of the alumina microspheres, which can be polymerized with the monomer in step d and embedded in the network of the temperature-sensitive gel)

Step c: placing the hollow porous alumina microspheres in a liquid culture medium, vacuumizing and degassing to enable the culture medium to enter the microspheres, and centrifuging the microspheres again; (the purpose of this step is to load the medium inside the alumina microspheres)

Step d: mixing 50-55 parts of N-isopropyl acrylamide, 3-8 parts of N-butoxy methyl acrylamide, 35-40 parts of acrylamide, 25-28 parts of pore-forming agent polyethylene glycol and 700-950 parts of deionized water, adding 30-35 parts of microspheres obtained in the step c, 4-8 parts of cross-linking agent N, N ' -methylene bisacrylamide, 2-4 parts of accelerator N, N, N ', N ' -tetramethyl ethylenediamine and 3-6 parts of initiator ammonium persulfate, reacting for 10-15 hours at 50-60 ℃, taking out the gel, washing the unreacted monomers and pore-forming agent with deionized water, crushing into particles, and performing vacuum drying to obtain the compound of the thermal shrinkage type temperature-sensitive gel and the hollow porous microspheres of the bio-enhanced membrane reactor. (the purpose of this step is to crosslink the alumina microspheres with other polyacrylamide monomers to form an organic-inorganic composite)

Preferably, the liquid medium is an LB medium.

Preferably, the molecular weight of the polyethylene glycol is in the range of 2000 to 4000.

The use of the above-mentioned bio-enhanced membrane reactor for treating coking wastewater.

Preferably, in the application, the wastewater is introduced into a reactor and subjected to aeration treatment, wherein the oxygen content is 3-5 mg/L in the aeration process.

Preferably, in the application, the treatment temperature range is 30-35 ℃.

Preferably, in the application, after the treatment, the composite filler is filtered, the temperature is reduced to 20-25 ℃ to make the gel expand, and the gel is soaked in water containing a surfactant to remove oily pollutants on the surface and regenerate the filler.

Advantageous effects

The bio-enhanced membrane reactor adopts the filler formed by compounding the temperature-sensitive gel taking N-isopropyl acrylamide as a main temperature-sensitive monomer and the inorganic porous microspheres, and the porous composite filler has a hollow porous structure and can contain more bacterial culture media, so that the slow release effect can be effectively generated in the treatment process, and the activity of bacteria is improved; meanwhile, as the porous temperature-sensitive gel is used as a carrier, when the temperature is 30-35 ℃ and the temperature is near the critical temperature (LCST), the porous temperature-sensitive gel can shrink obviously, so that the culture medium in the porous microspheres can be slowly released; and because the coking wastewater contains oily substances, the oily substances can be gathered on the surface of the porous filler after long-term operation, and the porosity of the surface of the porous filler is reduced, so that the surface of the temperature-sensitive gel filler is expanded by cooling the temperature-sensitive gel filler below LCST, pollutants adsorbed on the surface of the temperature-sensitive gel filler can be quickly eliminated, and the filler is quickly regenerated.

Drawings

Fig. 1 is an SEM photograph of the porous hollow microspheres prepared in example 1.

FIG. 2 is a photomicrograph of the composite gel carrier prepared in example 1.

FIG. 3 is a comparison of COD removal rate of the composite gel prepared in the application example in the operation process of treating coking wastewater.

FIG. 4 is a comparison of nitrogen and nitrogen removal rate of the composite gel prepared in the application example in a running process for treating coking wastewater.

Detailed Description

The following examples illustrate the technical solution of the present invention in detail, and the percentages refer to mass percentages unless otherwise specified.

EXAMPLE 1 preparation of composite Filler

Step a: mixing methacrylic acid, N' -methylene bisacrylamide, azobisisobutyronitrile and ethanol according to a weight ratio of 10: 3: 0.2: 500, heating to react, firstly reacting for 20min at 80 ℃, then evaporating the solvent to make the volume of the reaction solution equal to the original 1/2, continuing to react for 40min at 85 ℃, dispersing the reactant in deionized water, then performing centrifugal separation to obtain monodisperse polymer microspheres, then dispersing the polymer microspheres in 5wt% NaOH solution, wherein the mass ratio of the polymer microspheres to the NaOH solution is 1: 80, soaking for 15h, and then centrifuging and separating out the polymer microspheres; soaking the polymer microspheres in an aqueous solution containing 3wt% of manganese chloride, wherein the mass percentage of the polymer microspheres in the aqueous solution of manganese chloride is 0.5wt%, and after soaking for 10 hours, centrifugally separating the polymer microspheres to obtain Mn²⁺@ polymeric microspheres; then adding Mn²⁺@ Polymer microspheres dispersed in 40vol.% aqueous ethanol solution, Mn²⁺The method comprises the following steps of @ 2wt% of polymer microspheres in an ethanol water solution, adding chitosan and aluminum nitrate into the ethanol water solution to enable the concentrations of the chitosan and the aluminum nitrate to be 0.5wt% and 2.2wt% respectively, then adding ammonia water to adjust the pH value to 8.0-8.5, standing for 10 hours for aging to enable aluminum sol to be generated on the surfaces of the microspheres, centrifugally separating products, cleaning with deionized water, roasting at 700 ℃ for hours, and removing the chitosan and polymers inside to obtain hollow porous alumina microspheres;

step b: mixing hollow porous alumina microspheres with an ethanol solution of a silane coupling agent KH560 according to a weight ratio of 1: 20, wherein the concentration of the silane coupling agent KH560 in an ethanol solution is 5wt%, grafting reaction is carried out at 65 ℃ for 1h, and after the reaction, the product is centrifugally separated to obtain the hollow porous alumina microspheres grafted with the silane coupling agent;

step c: placing the hollow porous alumina microspheres in an LB culture medium, vacuumizing and degassing to enable the culture medium to enter the microspheres, and centrifuging the microspheres again;

step d: mixing 50 parts of N-isopropyl acrylamide, 3 parts of N-butoxy methacrylamide, 35 parts of acrylamide, 25 parts of pore-forming agent polyethylene glycol (molecular weight range is 2000-4000) and 700 parts of deionized water, adding 30 parts of microspheres obtained in the step c, 4 parts of cross-linking agent N, N ' -methylene bisacrylamide, 2 parts of accelerant N, N, N ', N ' -tetramethyl ethylenediamine and 3 parts of initiator ammonium persulfate, reacting for 10 hours at 50 ℃, taking out gel, washing unreacted monomers and pore-forming agent by deionized water, crushing into granules, and performing vacuum drying to obtain the compound of the thermal shrinkage type temperature-sensitive gel and the hollow porous microspheres of the bio-enhanced membrane reactor.

Example 2 preparation of composite Filler

Step a: mixing methacrylic acid, N' -methylene bisacrylamide, azobisisobutyronitrile and ethanol according to a weight ratio of 10: 4: 0.5: 750, mixing, heating to react, firstly reacting for 30min at 85 ℃, then evaporating the solvent to make the volume of the reaction solution equal to the original 2/3, continuing to react for 50min at 90 ℃, dispersing the reactant in deionized water, then performing centrifugal separation to obtain monodisperse polymer microspheres, then dispersing the polymer microspheres in 10wt% of NaOH solution, wherein the mass ratio of the polymer microspheres to the NaOH solution is 1: 100, soaking for 20 hours, and then centrifugally separating out the polymer microspheres; soaking the polymer microspheres in an aqueous solution containing 5wt% of manganese chloride, wherein the mass percentage of the polymer microspheres in the aqueous solution of manganese chloride is 1wt%, and after soaking for 15h, centrifugally separating the polymer microspheres to obtain Mn²⁺@ polymeric microspheres; then adding Mn²⁺@ Polymer microspheres dispersed in 50vol.% ethanol aqueous solution, Mn²⁺The method comprises the following steps of @ the concentration of polymer microspheres in an ethanol aqueous solution is 4wt%, adding chitosan and aluminum nitrate into the ethanol aqueous solution to enable the concentrations of the chitosan and the aluminum nitrate to be 1wt% and 2.8wt% respectively, then adding ammonia water to adjust the pH value to 8.0-8.5, standing for 20 hours for aging to enable aluminum sol to be generated on the surfaces of the microspheres, centrifugally separating products, cleaning with deionized water, roasting for 4 hours at 800 ℃, and removing the chitosan and internal polymers to obtain hollow porous alumina microspheres;

step b: mixing hollow porous alumina microspheres with an ethanol solution of a silane coupling agent KH560 according to a weight ratio of 1: 25, wherein the concentration of the silane coupling agent KH560 in the ethanol solution is 10wt%, the grafting reaction is carried out at 70 ℃, the reaction time is 4h, and after the reaction, the product is centrifugally separated to obtain the hollow porous alumina microspheres grafted with the silane coupling agent;

step d: mixing 55 parts of N-isopropyl acrylamide, 8 parts of N-butoxy methacrylamide, 40 parts of acrylamide, 28 parts of pore-forming agent polyethylene glycol (molecular weight range is 2000-4000) and 950 parts of deionized water, adding 35 parts of the microspheres obtained in the step c, 8 parts of cross-linking agent N, N ' -methylene bisacrylamide, 4 parts of accelerating agent N, N, N ', N ' -tetramethyl ethylenediamine and 6 parts of initiator ammonium persulfate, reacting for 15 hours at 60 ℃, taking out the gel, washing the gel with deionized water to remove unreacted monomers and pore-forming agent, crushing the gel into particles, and performing vacuum drying to obtain the compound of the thermal shrinkage type temperature-sensitive gel and the hollow porous microspheres of the bio-enhanced membrane reactor.

Example 3 preparation of composite Filler

Step a: mixing methacrylic acid, N' -methylene bisacrylamide, azobisisobutyronitrile and ethanol according to a weight ratio of 10: 3: 0.3: 650, heating to react, reacting for 25min at 82 ℃, evaporating the solvent to make the volume of the reaction solution equal to the original 1/2, continuing to react for 45min at 87 ℃, dispersing the reactant in deionized water, performing centrifugal separation to obtain monodisperse polymer microspheres, dispersing the polymer microspheres in 6wt% NaOH solution, wherein the mass ratio of the polymer microspheres to the NaOH solution is 1: 90, soaking for 16 hours, and then centrifugally separating out the polymer microspheres; soaking the polymer microspheres in an aqueous solution containing 3-5 wt% of manganese chloride, wherein the mass percentage of the polymer microspheres in the aqueous solution of manganese chloride is 0.6wt%, and after soaking for 13h, centrifuging the polymer microspheres to obtain Mn²⁺@ polymeric microspheres; then adding Mn²⁺@ Polymer microspheres dispersed in 45vol.% ethanol aqueous solution, Mn²⁺The concentration of the @ polymer microsphere in ethanol water solution is 3wt%, and the microsphere is dissolved in ethanol waterAdding chitosan and aluminum nitrate into the solution to respectively enable the concentrations of the chitosan and the aluminum nitrate to be 0.6wt% and 2.6wt%, then adding ammonia water to adjust the pH value to 8.0-8.5, standing for 15h for aging to enable aluminum sol to be generated on the surface of the microsphere, centrifugally separating the product, cleaning with deionized water, roasting for 3h at 750 ℃, and removing the chitosan and the internal polymer to obtain the hollow porous alumina microsphere;

step b: mixing hollow porous alumina microspheres with an ethanol solution of a silane coupling agent KH560 according to a weight ratio of 1: 22, wherein the concentration of the silane coupling agent KH560 in an ethanol solution is 6wt%, grafting reaction is carried out at 68 ℃ for 2h, and after the reaction, the product is centrifugally separated to obtain the hollow porous alumina microspheres grafted with the silane coupling agent;

step d: mixing 52 parts of N-isopropyl acrylamide, 5 parts of N-butoxy methacrylamide, 36 parts of acrylamide, 27 parts of pore-forming agent polyethylene glycol (molecular weight range is 2000-4000) and 850 parts of deionized water, adding 32 parts of microspheres obtained in the step c, 6 parts of cross-linking agent N, N ' -methylene bisacrylamide, 3 parts of accelerant N, N, N ', N ' -tetramethyl ethylenediamine and 5 parts of initiator ammonium persulfate, reacting for 12 hours at 55 ℃, taking out the gel, washing the gel with deionized water to remove unreacted monomers and pore-forming agent, crushing the gel into particles, and performing vacuum drying to obtain the compound of the thermal shrinkage type temperature-sensitive gel and the hollow porous microspheres of the bio-enhanced membrane reactor.

Comparative example 1

The differences from example 3 are: the microspheres obtained in step c are directly mixed with the prepared gel, rather than directly polymerized with the monomer.

Step a: mixing methacrylic acid, N' -methylene bisacrylamide, azobisisobutyronitrile and ethanol according to a weight ratio of 10: 3: 0.3: 650, heating to react at 82 deg.C for 25min, and evaporating solvent to make the volume of the reaction liquid equal to the original volume1/2, continuing to react for 45min at 87 ℃, dispersing the reactant in deionized water, then centrifugally separating to obtain monodisperse polymer microspheres, and dispersing the polymer microspheres in 6wt% NaOH solution, wherein the mass ratio of the polymer microspheres to the NaOH solution is 1: 90, soaking for 16 hours, and then centrifugally separating out the polymer microspheres; soaking the polymer microspheres in an aqueous solution containing 3-5 wt% of manganese chloride, wherein the mass percentage of the polymer microspheres in the aqueous solution of manganese chloride is 0.6wt%, and after soaking for 13h, centrifuging the polymer microspheres to obtain Mn²⁺@ polymeric microspheres; then adding Mn²⁺@ Polymer microspheres dispersed in 45vol.% ethanol aqueous solution, Mn²⁺The method comprises the following steps of @ 3wt% of polymer microspheres in an ethanol aqueous solution, adding chitosan and aluminum nitrate into the ethanol aqueous solution to enable the concentrations of the chitosan and the aluminum nitrate to be 0.6wt% and 2.6wt% respectively, then adding ammonia water to adjust the pH value to 8.0-8.5, standing for 15 hours for aging to enable aluminum sol to be generated on the surfaces of the microspheres, centrifugally separating products, cleaning with deionized water, roasting for 3 hours at 750 ℃, and removing the chitosan and internal polymers to obtain hollow porous alumina microspheres;

step d: mixing 52 parts of N-isopropyl acrylamide, 5 parts of N-butoxy methacrylamide, 36 parts of acrylamide, 27 parts of pore-forming agent polyethylene glycol (molecular weight range is 2000-4000) and 850 parts of deionized water, then adding 6 parts of cross-linking agent N, N ' -methylene bisacrylamide, 3 parts of accelerant N, N, N ', N ' -tetramethyl ethylenediamine and 5 parts of initiator ammonium persulfate, reacting for 12 hours at 55 ℃, taking out the gel, washing the unreacted monomer and pore-forming agent with deionized water, crushing into particles, vacuum drying, and mixing with 32 parts of microspheres obtained in the step c to obtain the compound of the thermal shrinkage type temperature-sensitive gel and the hollow porous microspheres of the bio-enhanced membrane reactor.

Comparative example 2

The differences from example 2 are: the LB medium is mixed directly with the gel, rather than being supported directly inside the microspheres.

Step a: mixing methacrylic acid, N' -methylene bisacrylamide, azobisisobutyronitrile and ethanol according to a weight ratio of 10: 3: 0.3: 650, heating to react, reacting for 25min at 82 ℃, evaporating the solvent to make the volume of the reaction solution equal to the original 1/2, continuing to react for 45min at 87 ℃, dispersing the reactant in deionized water, performing centrifugal separation to obtain monodisperse polymer microspheres, dispersing the polymer microspheres in 6wt% NaOH solution, wherein the mass ratio of the polymer microspheres to the NaOH solution is 1: 90, soaking for 16 hours, and then centrifugally separating out the polymer microspheres; soaking the polymer microspheres in an aqueous solution containing 3-5 wt% of manganese chloride, wherein the mass percentage of the polymer microspheres in the aqueous solution of manganese chloride is 0.6wt%, and after soaking for 13h, centrifuging the polymer microspheres to obtain Mn²⁺@ polymeric microspheres; then adding Mn²⁺@ Polymer microspheres dispersed in 45vol.% ethanol aqueous solution, Mn²⁺The method comprises the following steps of @ 3wt% of polymer microspheres in an ethanol aqueous solution, adding chitosan and aluminum nitrate into the ethanol aqueous solution to enable the concentrations of the chitosan and the aluminum nitrate to be 0.6wt% and 2.6wt% respectively, then adding ammonia water to adjust the pH value to 8.0-8.5, standing for 15 hours for aging to enable aluminum sol to be generated on the surfaces of the microspheres, centrifugally separating products, cleaning with deionized water, roasting for 3 hours at 750 ℃, and removing the chitosan and internal polymers to obtain hollow porous alumina microspheres;

step c: mixing 52 parts of N-isopropyl acrylamide, 5 parts of N-butoxy methacrylamide, 36 parts of acrylamide, 27 parts of pore-forming agent polyethylene glycol (molecular weight range is 2000-4000) and 850 parts of deionized water, adding 32 parts of microspheres obtained in the step b, 6 parts of cross-linking agent N, N ' -methylene bisacrylamide, 3 parts of accelerant N, N, N ', N ' -tetramethyl ethylenediamine and 5 parts of initiator ammonium persulfate, reacting at 55 ℃ for 12 hours, taking out the gel, washing the unreacted monomers and pore-forming agent by using deionized water, crushing the gel into particles, performing vacuum drying, and mixing the particles with 15 parts of LB culture medium to obtain the compound of the thermal shrinkage type gel and the hollow porous microspheres of the bio-enhanced membrane reactor.

Application example

The coking wastewater sample is subjected to filtration treatment of coarse-filtered sand, wherein COD is 2300-2700 ppm, nitrogen is 830-850 ppm, and B/C is 0.4-0.5. The adopted activated sludge is return sludge of a secondary sedimentation tank in coking wastewater treatment, and the mass concentration is 18-22 mg/L.

The filler is loaded in a 100L reactor, the filling amount is 30%, and the coking wastewater and pollution are mixed according to the weight ratio of 100: 1, pumping into a reactor, and simultaneously carrying out aeration treatment in the reactor, wherein the aeration rate is 8L/h, the temperature of the reactor is controlled at 32-34 ℃, a stable biofilm is formed on the surface of a carrier after the reactor is operated for 7 days, the reactor is continuously operated for 10 days, the hydraulic retention time of wastewater is adjusted to be 6h, and the water quality condition of effluent is inspected.

After 10 days of operation, the COD removal rate and the ammonia nitrogen removal rate of the effluent are respectively shown in the following tables:

as can be seen from the table, the biofilm reactor adopted by the invention has better effect of treating the coking wastewater. In addition, it can be seen from example 3 and comparative example 1 that, by crosslinking the porous microspheres with the hydrogel, bacteria can be effectively grown on the surfaces of the gel and the microspheres loaded with the culture medium, improving the treatment efficiency, while if the microspheres are directly mixed with the gel, the culture medium which cannot be released from the microspheres promotes the growth of bacteria on the surfaces of the gel. As can be seen from example 3 and comparative example 2, the culture medium can be effectively released slowly in the water treatment process by loading the culture medium in the interior of the microspheres, and the treatment effect is promoted.

After the 10-day treatment is finished, the filler in the example 3 is taken out, soaked in water containing 0.5 percent of sodium octadecyl benzene sulfonate at the temperature of 30-35 ℃ and 20-25 ℃ for 10 hours respectively, then a treatment test of coking wastewater is carried out, after a biofilm is generated after 7 days, the treatment is continued for 10 days, the treatment parameters are the same as the previous test, and the water quality of the treated wastewater is as follows:

	COD removal rate%	The ammonia nitrogen removal rate%
			Treatment group at 30-35 DEG C	60.2	62.4
20 to 25 ℃ treatment group	73.8	71.2

As can be seen from the above table, after the gel is soaked by water with the temperature lower than LCST, the gel expands, and can remove oily substances in the accumulated coking wastewater, so that the recovery of the porosity of the gel and the microspheres is facilitated, and the growth effect of bacteria is improved, while for a treatment group with the temperature of 30-35 ℃, the gel cannot be effectively expanded, so that the regeneration effect of the filler is poor. But the removal effect of the run was inferior to that of the 1 st test due to the failure to supplement the medium.

Claims

1. A manufacturing method of a biological reinforced membrane reactor is characterized in that a reactor is filled with a compound of thermal shrinkage type temperature-sensitive gel and hollow porous microspheres, and the preparation process of the compound of the thermal shrinkage type temperature-sensitive gel and the hollow porous microspheres comprises the following steps:

step a: mixing methacrylic acid, N' -methylene bisacrylamide, azobisisobutyronitrile and ethanol according to a weight ratio of 10: 3-4: 0.2-0.5: 500-750, heating to react, firstly reacting for 20-30 min at 80-85 ℃, then evaporating the solvent to make the volume of the reaction liquid be 1/2-2/3, continuing to react for 40-50 min at 85-90 ℃, dispersing the reactant in deionized water, then performing centrifugal separation to obtain monodisperse polymer microspheres, dispersing the polymer microspheres in 5-10 wt% of NaOH solution, wherein the mass ratio of the polymer microspheres to the NaOH solution is 1: 80-100, soaking for 15-20 h, and then centrifuging and separating out the polymer microspheres; soaking the polymer microspheres in an aqueous solution containing 3-5 wt% of manganese chloride, wherein the mass percentage of the polymer microspheres in the aqueous solution of manganese chloride is 0.5-1 wt%, and after soaking for 10-15 h, centrifuging the polymer microspheres to obtain Mn²⁺@ polymeric microspheres; then adding Mn²⁺@ polymer microspheres are dispersed in 40-50 vol.% ethanol aqueous solution, and Mn²⁺The method comprises the following steps of @ enabling the concentration of polymer microspheres in an ethanol aqueous solution to be 2-4 wt%, adding chitosan and aluminum nitrate into the ethanol aqueous solution to enable the concentrations of the chitosan and the aluminum nitrate to be 0.5-1 wt% and 2.2-2.8 wt% respectively, then adding ammonia water to adjust the pH value to 8.0-8.5, standing for 10-20 hours for aging to enable aluminum sol to be generated on the surfaces of the microspheres, centrifugally separating products, cleaning with deionized water, roasting for 2-4 hours at 700-800 ℃, and removing the chitosan and polymers inside to obtain hollow porous alumina microspheres;

step b: mixing hollow porous alumina microspheres with an ethanol solution of a silane coupling agent KH560 according to a weight ratio of 1: 20-25, performing grafting reaction on a silane coupling agent KH560 in an ethanol solution at a concentration of 5-10 wt% at 65-70 ℃ for 1-4 h, and after the reaction, performing centrifugal separation on the product to obtain hollow porous alumina microspheres grafted with the silane coupling agent;

step c: placing the hollow porous alumina microspheres in a liquid culture medium, vacuumizing and degassing to enable the culture medium to enter the microspheres, and centrifuging the microspheres again;

step d: mixing 50-55 parts of N-isopropyl acrylamide, 3-8 parts of N-butoxy methyl acrylamide, 35-40 parts of acrylamide, 25-28 parts of pore-forming agent polyethylene glycol and 700-950 parts of deionized water, adding 30-35 parts of microspheres obtained in the step c, 4-8 parts of cross-linking agent N, N ' -methylene bisacrylamide, 2-4 parts of accelerator N, N, N ', N ' -tetramethyl ethylenediamine and 3-6 parts of initiator ammonium persulfate, reacting for 10-15 hours at 50-60 ℃, taking out the gel, washing the unreacted monomers and pore-forming agent with deionized water, crushing into particles, and performing vacuum drying to obtain the compound of the thermal shrinkage type temperature-sensitive gel and the hollow porous microspheres of the bio-enhanced membrane reactor.

2. The method of manufacturing a bio-enhanced membrane reactor of claim 1, wherein the liquid medium is LB medium.

3. The method of manufacturing a bio-enhanced membrane reactor of claim 1, wherein the molecular weight of the polyethylene glycol is in the range of 2000 to 4000.

4. The application of the biological reinforced membrane reactor in treating coking wastewater is characterized in that,

the bio-enhanced membrane reactor manufactured by the method of manufacturing a bio-enhanced membrane reactor of claim 1.

5. The use of claim 4, wherein the wastewater is introduced into a reactor and subjected to aeration treatment, wherein the aeration treatment is performed to ensure that the oxygen content is 3-5 mg/L.

6. Use according to claim 4, wherein the treatment temperature is in the range of 30 to 35 ℃.

7. The use according to claim 4, wherein after the treatment, the composite filler is filtered, cooled to 20-25 ℃ to swell the gel, and soaked in water containing a surfactant to remove oily pollutants on the surface and regenerate the filler.