CN113998781A - Sewage autotrophic denitrification treatment process - Google Patents

Sewage autotrophic denitrification treatment process Download PDF

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Publication number
CN113998781A
CN113998781A CN202111653246.5A CN202111653246A CN113998781A CN 113998781 A CN113998781 A CN 113998781A CN 202111653246 A CN202111653246 A CN 202111653246A CN 113998781 A CN113998781 A CN 113998781A
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polyurethane foam
modified
zeolite
prepared
carbon fiber
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CN113998781B (en
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路青
王静霞
邵东旭
高洁
王永锋
易向阳
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Hebei Haiying Environmental Safety Technology Co ltd
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Hebei Haiying Environmental Safety Technology 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
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2806—Anaerobic processes using solid supports for microorganisms
    • 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
    • C02F3/30—Aerobic and anaerobic processes
    • C02F3/302—Nitrification and denitrification treatment
    • C02F3/305—Nitrification and denitrification treatment characterised by the denitrification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/166—Nitrites
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

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  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biological Treatment Of Waste Water (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

The invention discloses a sewage autotrophic denitrification and denitrification treatment process, belongs to the field of sewage treatment, and particularly relates to an iron matrix carrier. The oil absorption multiple of the polyurethane foam obtained by the invention is increased and is 10-13; the tensile strength of the polyurethane foam is improved, and the tensile strength is 0.16-0.22 MPa; the denitrification treatment process has good effect of removing nitrate nitrogen and total nitrogen.

Description

Sewage autotrophic denitrification treatment process
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a sewage autotrophic denitrification treatment process.
Background
Biological treatment technology is one of the most widely applied methods for modern sewage treatment. Nitrogen pollution is an important cause of water pollution, and domestic sewage contains certain nitrogen, so that denitrification treatment is almost a necessary treatment step in the sewage treatment process. The commonly used biological denitrification process consists of a nitrification reaction and a denitrification reaction. The basic principle of the conventional biological denitrification treatment method is that the nitrogen pollutants in the polluted water bodies such as domestic sewage, polluted surface water and the like mainly comprise ammonia nitrogen and nitrate: ammonia nitrogen is oxidized into nitrite under the action of ammonia oxidizing bacteria, and further oxidized into nitrate under the action of nitrite oxidizing bacteria; the nitrate is reduced into nitrogen gas under the action of denitrifying bacteria and discharged out of the water body, thereby completely denitrifying.
In general, heterotrophic denitrification is used in water treatment processes, i.e., organic matter is required as an electron donor to provide a carbon source and an energy source for microbial growth. In the heterotrophic denitrification process, the sewage treatment process is comprehensively influenced by various complex factors, the dosage of the organic carbon source is not easy to control, the problems of organic matter residue and the like in effluent are easily caused, and the operation cost is increased.
Different from heterotrophic denitrifying bacteria, autotrophic denitrifying bacteria can use inorganic substances such as hydrogen, sulfur and the like as electron donors and inorganic carbon as a carbon source to complete the conversion from nitrate to nitrogen. The denitrification process based on the autotrophic denitrification process does not need to add an organic carbon source, has less sludge production and has good application prospect. In the actual polluted water treatment, from multiple angles of process principle, equipment structure, control elements and the like, the integrated reaction device and the process method for simultaneously removing ammonia nitrogen and nitrate are developed, and the method has good application prospect and important practical significance.
Disclosure of Invention
The invention aims to provide a sewage autotrophic denitrification treatment process with good denitrification effect.
The technical scheme adopted by the invention for realizing the purpose is as follows:
an autotrophic denitrification and denitrification treatment process for sewage, comprising the following steps: respectively carrying out denitrification treatment on the sewage in an aerobic treatment tank, an intermediate sedimentation tank and an autotrophic denitrification tank to obtain denitrified water; inoculating activated sludge containing autotrophic denitrifying bacteria into an autotrophic denitrification pool, wherein an iron matrix carrier is used in the autotrophic denitrification pool, the iron matrix carrier is obtained by mixing, granulating and calcining pyrite particles, polyurethane foam, an adhesive and a liquid agent, and the polyurethane foam contains modified carbon fibers and modified zeolite; the modified carbon fiber is prepared by modifying carbon fiber with disodium laureth sulfosuccinate, and the modified zeolite is prepared by modifying zeolite with dodecyl trimethyl ammonium bromide.
Preferably, the aerobic treatment tank is inoculated with activated sludge containing ammonia oxidizing bacteria and nitrite oxidizing bacteria.
Preferably, the iron matrix support is packed in a fixed bed, used in the form of a fixed bed.
Preferably, the binder is starch.
Preferably, the polyurethane foam is used in an amount of 20 to 40 wt% of the pyrite granule.
Preferably, the binder is used in an amount of 10 to 30 wt% of the pyrite granule.
Preferably, the sewage enters an aerobic treatment tank through a water inlet system, and ammonia nitrogen in the sewage is oxidized into nitrate; the sewage passing through the aerobic treatment tank enters an intermediate sedimentation tank, and the carried-out water-insoluble substances are discharged after sedimentation; the sewage passing through the intermediate sedimentation tank enters an autotrophic denitrification tank to reduce nitrate into nitrogen; discharging the treated water.
Preferably, the aerobic treatment tank is inoculated with activated sludge, and the activated sludge contains ammonia oxidizing bacteria and nitrite oxidizing bacteria.
More preferably, an aeration system is arranged in the aerobic treatment tank to provide sufficient oxygen for the microorganisms enriched on the organic biofilm carriers.
Preferably, the autotrophic denitrification tank is inoculated with activated sludge containing autotrophic denitrifying bacteria by using an iron matrix carrier. An oxygen limiting system is arranged in the autotrophic denitrification tank to provide anaerobic conditions for the microorganisms enriched on the iron matrix carrier.
More preferably, the oxygen limitation system can monitor the concentration of the dissolved oxygen in the autotrophic denitrification tank, and when the concentration of the dissolved oxygen is too high, the oxygen limitation system automatically adjusts the aeration amount to ensure the dissolved oxygen environment required by the autotrophic denitrification reaction, and the concentration of the dissolved oxygen is controlled to be below 3 mg/L.
Preferably, the denitrification treatment process of the invention comprises a preparation method of the iron matrix carrier.
More preferably, in the preparation of the polyol mixed solution, the polyol, the catalyst, the stabilizer, the foaming agent, and the chain extender are mixed and stirred uniformly to obtain the polyol mixed solution.
More preferably, in the preparation of the polyol mixture, the polyol is polyether polyol N220.
More preferably, in the preparation of the polyol mixture, the catalyst is a mixture of triethanolamine and dibutyltin dilaurate, the catalyst contains 50-80 wt% dibutyltin dilaurate, and the amount of the catalyst is 1-5 wt% of the polyol.
More preferably, in the preparation of the polyol mixture, the stabilizer is dimethicone, and the amount of the stabilizer used is 0.6 to 2.1 wt% of the polyol.
More preferably, in the preparation of the polyol mixture, the foaming agent is water, and the amount of the foaming agent used is 3 to 7 wt% of the polyol.
More preferably, in the preparation of the polyol mixed solution, the chain extender is 4-hydroxy butanol, and the using amount of the chain extender is 3-9 wt% of the polyol.
More preferably, a functional agent can be added into the polyol mixed solution, wherein the functional agent is di-o-tolyl carbonate, and the using amount of the functional agent is 0.5-3 wt% of the polyol. The invention discovers that after di-o-tolyl carbonate is further used in the preparation of the polyurethane foam, the obtained polyurethane foam has higher oil absorption performance and further improved tensile strength under the condition of common use with other reagents, and the iron matrix carrier prepared by the polyurethane foam is used in a denitrification treatment process, so that the removal rate of nitrate nitrogen is further improved, and the better sewage treatment effect is achieved.
More preferably, in the preparation of the modified carbon fiber, the carbon fiber is added into the mixed cleaning solution for ultrasonic treatment for 6-18 h, taken out and dried, then the carbon fiber is added into the modified solution for ultrasonic treatment for 3-12 h, taken out and dried at the temperature of 80-100 ℃ to obtain the modified carbon fiber.
More preferably, in the preparation of the modified carbon fiber, the mixed cleaning solution is prepared by mixing acetone and deionized water, and the content of the acetone in the mixed cleaning solution is 60-80 wt%.
Still more preferably, in the preparation of the modified carbon fiber, the carbon fiber is used in an amount of 10 to 30 wt% of the mixed cleaning liquid.
Still more preferably, in the preparation of the modified carbon fiber, the modified solution is prepared by adding disodium laureth sulfosuccinate into deionized water and mixing, and the content of disodium laureth sulfosuccinate in the modified solution is 3-8 wt%.
Still more preferably, in the preparation of the modified carbon fiber, the carbon fiber is used in an amount of 10 to 30 wt% based on the modification solution.
More preferably, in the preparation of the modified zeolite, the zeolite is washed by deionized water and dried, then the zeolite is added into the modified solution, the ultrasonic treatment is carried out for 2-6 h, the zeolite is taken out and dried at the temperature of 40-80 ℃, and then the modified zeolite is calcined at the temperature of 300-500 ℃ for 1-3 h, thus obtaining the modified zeolite.
Still more preferably, in the preparation of the modified zeolite, the modified solution is prepared by adding dodecyl trimethyl ammonium bromide into deionized water and mixing, and the content of the dodecyl trimethyl ammonium bromide in the modified solution is 2-10 wt%.
Still more preferably, in the preparation of the modified zeolite, the zeolite is used in an amount of 10 to 50 wt% of the modification solution.
More preferably, in the preparation of the isocyanate composite liquid, the modified carbon fiber and the modified zeolite are added into the isocyanate, and are stirred and mixed uniformly to obtain the isocyanate composite liquid.
More preferably, in the preparation of the isocyanate complex liquid, the isocyanate is PAPI.
More preferably, the modified carbon fiber is used in an amount of 0.5 to 4 wt% based on the isocyanate in the preparation of the isocyanate composite liquid.
Still more preferably, the modified zeolite is used in an amount of 1 to 6 wt% based on the isocyanate in the preparation of the isocyanate composite liquid.
More preferably, in the preparation of the polyurethane foam, the isocyanate complex liquid is added into the polyol mixed liquid, stirred, mixed uniformly, foamed and treated at the temperature of 50-80 ℃ for 12-36 h to obtain the polyurethane foam. The modified carbon fibers and the modified zeolite are used for preparing the polyurethane foam, gas is generated in the preparation process of the polyurethane foam to form a foam structure, the modified carbon fibers and the modified zeolite which are mixed are compounded in the polyurethane foam, so that the tensile strength of the polyurethane foam is improved, the modified carbon fibers and the modified zeolite can be partially arranged in the polyurethane foam and can be partially exposed on the surface of the polyurethane foam, a cross structure is formed in foam holes, the adsorption performance of the polyurethane foam is further enhanced, the foam structure of the polyurethane foam can enable autotrophic denitrifying bacteria to be better filmed after being used for preparing an iron matrix carrier, higher reaction points for the autotrophic denitrifying bacteria to play a role can be provided under the structure of the prepared iron matrix carrier, and the removal effect of nitrate and nitrogen in sewage is improved.
Still more preferably, in the preparation of polyurethane foam, the amount of the isocyanate compound liquid is 120-160 wt% of the polyol mixture liquid.
More preferably, in the preparation of the iron matrix carrier, the pyrite particles, the polyurethane foam, the adhesive and the liquid agent are mixed and granulated, and calcined for 1-3 hours at the temperature of 300-500 ℃ to obtain the iron matrix carrier.
Still more preferably, the polyurethane foam is used in an amount of 20-40 wt% of the pyrite granule in the preparation of the iron matrix support.
Still more preferably, in the preparation of the iron matrix carrier, the binder is starch and is used in an amount of 10-30 wt% of the pyrite granule.
Still more preferably, in the preparation of the iron matrix carrier, the liquid agent is deionized water, and the amount of the liquid agent is 60-100 wt% of the pyrite granule.
The invention discloses a preparation method of polyurethane foam, which comprises the following steps: mixing modified carbon fibers and modified zeolite in isocyanate to obtain isocyanate composite liquid; mixing a catalyst, a stabilizer, a foaming agent and a chain extender into polyol to obtain polyol mixed solution; carrying out foaming treatment on the isocyanate composite liquid and the polyol mixed liquid to obtain polyurethane foam; the modified carbon fiber is prepared by modifying carbon fiber with disodium laureth sulfosuccinate, and the modified zeolite is prepared by modifying zeolite with dodecyl trimethyl ammonium bromide.
The invention discloses polyurethane foam prepared by the method.
The invention discloses an iron matrix carrier, which comprises: the polyurethane foam is prepared by mixing, granulating and calcining raw materials containing the polyurethane foam.
The invention discloses application of modified carbon fibers and modified zeolite in preparation of carriers and/or sewage treatment.
According to the invention, disodium laureth sulfosuccinate is adopted to modify carbon fibers to prepare modified carbon fibers, dodecyltrimethylammonium bromide is adopted to modify zeolite to prepare modified zeolite, polyurethane foam containing the modified carbon fibers and the modified zeolite is used for preparing an iron matrix carrier, and then the iron matrix carrier is used in an autotrophic denitrification tank for sewage denitrification treatment, and the obtained product and denitrification treatment process have the following beneficial effects: the oil absorption multiple of the polyurethane foam is increased, and is 10-13; the tensile strength of the polyurethane foam is improved, and the tensile strength is 0.16-0.22 MPa; the denitrification treatment process has good effect of removing nitrate nitrogen and total nitrogen. Therefore, the invention is a sewage autotrophic denitrification denitrogenation treatment process with good denitrogenation effect.
Drawings
FIG. 1 is an infrared view of a modified carbon fiber;
FIG. 2 is a graph of oil absorption times for polyurethane foams;
FIG. 3 is a graph of the tensile strength of polyurethane foam;
FIG. 4 is a graph of nitrate and nitrogen removal from an autotrophic denitrification tank;
FIG. 5 is a graph of total nitrogen removal for a denitrification process.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a sewage autotrophic denitrification denitrogenation treatment process,
the sewage enters an aerobic treatment tank through a water inlet system, and ammonia nitrogen in the sewage is oxidized into nitrate; the sewage passing through the aerobic treatment tank enters an intermediate sedimentation tank, and the carried-out water-insoluble substances are discharged after sedimentation; the sewage passing through the intermediate sedimentation tank enters an autotrophic denitrification tank to reduce nitrate into nitrogen; discharging the treated water.
And inoculating activated sludge in the aerobic treatment tank, wherein the activated sludge contains ammonia oxidizing bacteria and nitrite oxidizing bacteria. An aeration system is arranged in the aerobic treatment tank to provide sufficient oxygen for the microorganisms enriched on the organic biofilm carrier.
In the autotrophic denitrification pool, an iron matrix carrier is used for inoculating activated sludge, and the activated sludge contains autotrophic denitrifying bacteria. The iron matrix carrier is filled in a fixed bed, an oxygen limiting system is arranged in an autotrophic denitrification pool in the form of the fixed bed, and anaerobic conditions are provided for the microorganisms enriched on the iron matrix carrier. The oxygen limiting system can monitor the concentration of dissolved oxygen in the autotrophic denitrification tank, and when the concentration of the dissolved oxygen is too high, the oxygen limiting system automatically adjusts the aeration amount to ensure the dissolved oxygen environment required by the autotrophic denitrification reaction, and the concentration of the dissolved oxygen is controlled to be below 3 mg/L.
The iron matrix carrier is prepared by the following steps:
preparing a polyol mixed solution: mixing polyol, a catalyst, a stabilizer, a foaming agent and a chain extender, and uniformly stirring to obtain a polyol mixed solution; the polyol is polyether polyol N220, the catalyst is a mixture of triethanolamine and dibutyltin dilaurate, the catalyst contains 80 wt% of dibutyltin dilaurate, the using amount of the catalyst is 3 wt% of the polyol, the stabilizer is dimethyl silicone oil, the using amount of the stabilizer is 1.5 wt% of the polyol, the foaming agent is water, the using amount of the foaming agent is 5 wt% of the polyol, the chain extender is 4-hydroxy butanol, and the using amount of the chain extender is 6 wt% of the polyol.
Preparing modified carbon fibers: adding carbon fibers into the mixed cleaning solution, carrying out ultrasonic treatment for 12 hours, taking out, drying, then adding the carbon fibers into the modified solution, carrying out ultrasonic treatment for 6 hours, taking out, and drying at the temperature of 90 ℃ to obtain modified carbon fibers; the mixed cleaning solution is formed by mixing acetone and deionized water, the content of the acetone in the mixed cleaning solution is 70 wt%, the usage amount of the carbon fiber is 20 wt% of the mixed cleaning solution, the modified solution is prepared by adding disodium laureth sulfosuccinate into the deionized water and mixing, the content of the disodium laureth sulfosuccinate in the modified solution is 5 wt%, and the usage amount of the carbon fiber is 20 wt% of the modified solution.
Preparation of modified zeolite: washing zeolite with deionized water, drying, adding zeolite into the modified solution, performing ultrasonic treatment for 4 h, taking out, drying at the temperature of 60 ℃, and calcining at the temperature of 400 ℃ for 2 h to obtain modified zeolite; the modified solution is prepared by adding dodecyl trimethyl ammonium bromide into deionized water and mixing, wherein the content of the dodecyl trimethyl ammonium bromide in the modified solution is 8 wt%, and the usage amount of zeolite is 30 wt% of the modified solution.
Preparing isocyanate composite liquid: adding the modified carbon fiber and the modified zeolite into isocyanate, and stirring and mixing uniformly to obtain isocyanate composite liquid; the isocyanate is PAPI, the usage amount of the modified carbon fiber is 1.5 wt% of the isocyanate, and the usage amount of the modified zeolite is 2.5 wt% of the isocyanate.
Preparation of polyurethane foam: adding the isocyanate composite liquid into the polyol mixed liquid, stirring and mixing uniformly, foaming, and then treating at the temperature of 70 ℃ for 24 hours to obtain the polyurethane foam. The usage amount of the isocyanate composite liquid is 130 wt% of the polyol mixed liquid.
Iron matrix carrier: mixing and granulating pyrite particles, polyurethane foam, an adhesive and a liquid agent, and calcining for 2 hours at the temperature of 400 ℃ to obtain the iron matrix carrier. The usage amount of the polyurethane foam is 30 wt% of the pyrite granule, the adhesive is starch, the usage amount of the starch is 20 wt% of the pyrite granule, the liquid agent is deionized water, and the usage amount of the liquid agent is 80 wt% of the pyrite granule.
Example 2:
a sewage autotrophic denitrification denitrogenation treatment process,
this example is different from example 1 only in that the modified carbon fiber was used in an amount of 3.6 wt% and the modified zeolite was used in an amount of 4.4 wt% based on the isocyanate in the preparation of the isocyanate composite liquid.
Example 3:
a sewage autotrophic denitrification denitrogenation treatment process,
the sewage enters an aerobic treatment tank through a water inlet system, and ammonia nitrogen in the sewage is oxidized into nitrate; the sewage passing through the aerobic treatment tank enters an intermediate sedimentation tank, and the carried-out water-insoluble substances are discharged after sedimentation; the sewage passing through the intermediate sedimentation tank enters an autotrophic denitrification tank to reduce nitrate into nitrogen; discharging the treated water.
And inoculating activated sludge in the aerobic treatment tank, wherein the activated sludge contains ammonia oxidizing bacteria and nitrite oxidizing bacteria. An aeration system is arranged in the aerobic treatment tank to provide sufficient oxygen for the microorganisms enriched on the organic biofilm carrier.
In the autotrophic denitrification pool, an iron matrix carrier is used for inoculating activated sludge, and the activated sludge contains autotrophic denitrifying bacteria. The iron matrix carrier is filled in a fixed bed, an oxygen limiting system is arranged in an autotrophic denitrification pool in the form of the fixed bed, and anaerobic conditions are provided for the microorganisms enriched on the iron matrix carrier. The oxygen limiting system can monitor the concentration of dissolved oxygen in the autotrophic denitrification tank, and when the concentration of the dissolved oxygen is too high, the oxygen limiting system automatically adjusts the aeration amount to ensure the dissolved oxygen environment required by the autotrophic denitrification reaction, and the concentration of the dissolved oxygen is controlled to be below 3 mg/L.
The iron matrix carrier is prepared by the following steps:
preparing a polyol mixed solution: mixing polyol, a catalyst, a stabilizer, a foaming agent, a chain extender and a functional agent, and uniformly stirring to obtain a polyol mixed solution; the polyol is polyether polyol N220, the catalyst is a mixture of triethanolamine and dibutyltin dilaurate, the catalyst contains 80 wt% of dibutyltin dilaurate, the using amount of the catalyst is 3 wt% of the polyol, the stabilizer is dimethyl silicone oil, the using amount of the stabilizer is 1.5 wt% of the polyol, the foaming agent is water, the using amount of the foaming agent is 5 wt% of the polyol, the chain extender is 4-hydroxy butanol, the using amount of the chain extender is 6 wt% of the polyol, the functional agent is di-o-tolyl carbonate, and the using amount of the functional agent is 1.3 wt% of the polyol.
Preparing modified carbon fibers: adding carbon fibers into the mixed cleaning solution, carrying out ultrasonic treatment for 12 hours, taking out, drying, then adding the carbon fibers into the modified solution, carrying out ultrasonic treatment for 6 hours, taking out, and drying at the temperature of 90 ℃ to obtain modified carbon fibers; the mixed cleaning solution is formed by mixing acetone and deionized water, the content of the acetone in the mixed cleaning solution is 70 wt%, the usage amount of the carbon fiber is 20 wt% of the mixed cleaning solution, the modified solution is prepared by adding disodium laureth sulfosuccinate into the deionized water and mixing, the content of the disodium laureth sulfosuccinate in the modified solution is 5 wt%, and the usage amount of the carbon fiber is 20 wt% of the modified solution.
Preparation of modified zeolite: washing zeolite with deionized water, drying, adding zeolite into the modified solution, performing ultrasonic treatment for 4 h, taking out, drying at the temperature of 60 ℃, and calcining at the temperature of 400 ℃ for 2 h to obtain modified zeolite; the modified solution is prepared by adding dodecyl trimethyl ammonium bromide into deionized water and mixing, wherein the content of the dodecyl trimethyl ammonium bromide in the modified solution is 8 wt%, and the usage amount of zeolite is 30 wt% of the modified solution.
Preparing isocyanate composite liquid: adding the modified carbon fiber and the modified zeolite into isocyanate, and stirring and mixing uniformly to obtain isocyanate composite liquid; the isocyanate is PAPI, the usage amount of the modified carbon fiber is 1.5 wt% of the isocyanate, and the usage amount of the modified zeolite is 2.5 wt% of the isocyanate.
Preparation of polyurethane foam: adding the isocyanate composite liquid into the polyol mixed liquid, stirring and mixing uniformly, foaming, and then treating at the temperature of 70 ℃ for 24 hours to obtain the polyurethane foam. The usage amount of the isocyanate composite liquid is 130 wt% of the polyol mixed liquid.
Iron matrix carrier: mixing and granulating pyrite particles, polyurethane foam, an adhesive and a liquid agent, and calcining for 2 hours at the temperature of 400 ℃ to obtain the iron matrix carrier. The usage amount of the polyurethane foam is 30 wt% of the pyrite granule, the adhesive is starch, the usage amount of the starch is 20 wt% of the pyrite granule, the liquid agent is deionized water, and the usage amount of the liquid agent is 80 wt% of the pyrite granule.
Example 4:
a sewage autotrophic denitrification denitrogenation treatment process,
this example is different from example 3 only in that the amount of the functional agent used in the preparation of the polyol mixture was 2.6 wt% based on the polyol.
Comparative example 1:
this comparative example is compared to example 2, except that the modified zeolite was replaced with the unmodified zeolite in the formulation of the isocyanate composite liquid.
Comparative example 2:
this comparative example is different from example 2 only in that the modified carbon fiber was replaced with the unmodified carbon fiber in the preparation of the isocyanate composite liquid.
Comparative example 3:
this comparative example is different from example 2 only in that in the preparation of the isocyanate composite liquid, the modified zeolite was replaced with the unmodified zeolite, and the modified carbon fiber was replaced with the unmodified carbon fiber.
Test example 1:
1. infrared characterization of modified carbon fibers
Test samples: the modified carbon fiber obtained in example 1. Tabletting with potassium bromide and infrared spectrum analysis.
The infrared spectrum of the modified carbon fiber prepared by the invention is shown in figure 1, which showsIn 3200--1The infrared absorption peak of the carbon fiber with hydroxyl between is 1650-1750 cm-1The infrared absorption peak of carbonyl is 1081 cm-1Infrared absorption peak of carbon-oxygen carbon in ether bond at 1116cm-1The infrared absorption peak of the sulfur-oxygen double bond indicates that the modified carbon fiber is successfully obtained.
2. Oil absorption test for polyurethane foams
Test samples: the obtained polyurethane foams were prepared in the respective examples and comparative examples.
Cutting the sample into 3 cm × 3 cm × 3 cm, weighing, soaking in peanut oil, taking out after 48 hr, wiping off surface peanut oil, and weighing.
The oil absorption times are calculated according to the following formula:
oil absorption multiple = (weight after oil absorption-weight before oil absorption)/weight before oil absorption.
The oil absorption times of the polyurethane foam prepared by the invention are shown in figure 2, wherein A is example 1, B is example 2, C is example 3, D is example 4, E is comparative example 1, F is comparative example 2, G is comparative example 3, the oil absorption times of the polyurethane foam prepared in example 1 are 10.3, the oil absorption times of the polyurethane foam prepared in example 2 are 11.2, the oil absorption times of the polyurethane foam prepared in comparative example 1 are 8.6, the oil absorption times of the polyurethane foam prepared in comparative example 2 are 8.7, the oil absorption times of the polyurethane foam prepared in comparative example 3 are 8.4, and compared with comparative example 3, example 2 shows that the oil absorption performance of the polyurethane foam is improved after the carbon fiber and zeolite used in the preparation of the polyurethane foam are modified, and compared with comparative example 3, the oil absorption performance of the polyurethane foam in example 2 is improved by 33.33%, example 2 shows that, compared with comparative examples 1-2, in the preparation of polyurethane foam, only the carbon fibers or zeolite used were modified, the improvement of oil absorption property of polyurethane foam was weaker than the effect of modifying and using the carbon fibers and zeolite at the same time; the oil absorption capacity of the polyurethane foam prepared in example 3 was 12.1, the oil absorption capacity of the polyurethane foam prepared in example 4 was 12.6, and the use of di-o-tolyl carbonate in the preparation of the polyurethane foam in example 4 showed a further improvement in the oil absorption performance of the polyurethane foam, compared to example 2, and the oil absorption performance of the polyurethane foam of example 4 was 12.50% higher than that of example 2.
The polyurethane foam prepared by the method has the advantage that the oil absorption multiple is increased and is 10-13.
3. Tensile Strength testing of polyurethane foams
Test samples: the obtained polyurethane foams were prepared in the respective examples and comparative examples.
And (3) adopting an electronic universal tester to test the tensile strength of the sample, referring to the method of GB/T6344-2008.
The tensile strength of the polyurethane foam prepared according to the present invention is shown in FIG. 3, wherein A is example 1, B is example 2, C is example 3, D is example 4, E is comparative example 1, F is comparative example 2, G is comparative example 3, the tensile strength of the polyurethane foam prepared in example 1 is 0.17 MPa, the tensile strength of the polyurethane foam prepared in example 2 is 0.18 MPa, the tensile strength of the polyurethane foam prepared in comparative example 1 is 0.14 MPa, the tensile strength of the polyurethane foam prepared in comparative example 2 is 0.15 MPa, the tensile strength of the polyurethane foam prepared in comparative example 3 is 0.14 MPa, and example 2 shows that the tensile properties of the polyurethane foam are improved after the carbon fiber and zeolite used in preparing the polyurethane foam are modified, compared to comparative example 3, the oil absorption of the polyurethane foam of example 2 is improved by 28.57%, and the example 2 shows that, compared with the comparative examples 1-2, the improvement of the tensile property of the polyurethane foam is weaker than the effect of modifying and using the carbon fiber and the zeolite at the same time after only the carbon fiber or the zeolite used in the preparation of the polyurethane foam is modified; the tensile strength of the polyurethane foam prepared in example 3 was 0.20 MPa, the tensile strength of the polyurethane foam prepared in example 4 was 0.21 MPa, and example 4 showed that the use of di-o-tolyl carbonate in the preparation of the polyurethane foam further improved the tensile properties of the polyurethane foam compared to example 2, and the tensile properties of the polyurethane foam of example 4 were improved by 16.67% compared to example 2.
The tensile strength of the polyurethane foam prepared by the invention is improved, and the tensile strength is 0.16-0.22 MPa.
4. Measurement of Denitrification Property of polyurethane foam
The process for testing the denitrified nitrogen comprises the following steps: in the test, the cleaning performance of the autotrophic denitrification tank on nitrate nitrogen is only tested, so that activated sludge is not collected in the aerobic treatment tank, and the aerobic treatment tank and the intermediate sedimentation tank only have the function of water inlet; the comparative processes were carried out for each of the examples and comparative examples described above.
The removal rates of nitrate nitrogen after the processes of the respective examples and comparative examples were prepared in 500 mg/L, as shown in FIG. 4, wherein A was example 1, B was example 2, C was example 3, D was example 4, E was comparative example 1, F was comparative example 2, G was comparative example 3, the removal rate of nitrate nitrogen by the method of example 1 was 89.26%, the removal rate of nitrate nitrogen by the method of example 2 was 91.69%, the removal rate of nitrate nitrogen by the method of comparative example 1 was 76.41%, the removal rate of nitrate nitrogen by the method of comparative example 2 was 78.03%, the removal rate of nitrate nitrogen by the method of comparative example 3 was 72.64%, and example 2 compared with comparative example 3 showed that the removal rate of nitrate nitrogen by autotrophic denitrifying bacteria was improved after the modified carbon fiber and the modified zeolite were used to prepare an iron matrix carrier for an autotrophic denitrification tank in a sewage treatment process, compared with the comparative example 3, the removal rate of the nitrate nitrogen is improved by 9.05% in the example 2, and compared with the comparative examples 1-2, the improvement of the removal effect of the nitrate nitrogen is shown after the polyurethane foam is prepared by only using the modified carbon fiber or the modified zeolite and then used for preparing the iron matrix carrier and using the iron matrix carrier in the autotrophic denitrification tank, so that the improvement of the removal effect of the final nitrate nitrogen is shown to be better due to the use of the modified carbon fiber and the modified zeolite; the method of example 3 showed 94.59% and the method of example 4 showed 95.92% removal of nitrate nitrogen, and the comparison of example 4 with example 2 shows that the removal of nitrate nitrogen was improved by 4.23% compared to example 2 when the iron-based carrier finally using the polyurethane foam was applied to the autotrophic denitrification tank after the polyurethane foam was prepared using di-o-tolyl carbonate, and example 4 showed that the removal of nitrate nitrogen was improved by 4.23% compared to example 2.
Testing the total nitrogen removal process: in this test, the total nitrogen removal performance of the processes of the above examples and comparative examples on the wastewater was tested. The total nitrogen content of the wastewater used in the test was 380 mg/L (nitrate nitrogen content: about 120 mg/L).
The total nitrogen removal rate of the above-mentioned sewage after the treatment by the processes of the respective examples and comparative examples is shown in fig. 5, wherein a is example 1, B is example 2, C is example 3, D is example 4, E is comparative example 1, F is comparative example 2, G is comparative example 3, the total nitrogen removal rate by the method of example 1 is 95.34%, the total nitrogen removal rate by the method of example 2 is 96.26%, the total nitrogen removal rate by the method of comparative example 1 is 92.86%, the total nitrogen removal rate by the method of comparative example 2 is 91.64%, the total nitrogen removal rate by the method of comparative example 3 is 90.34%, and example 2 shows that, compared with comparative example 3, after the modified carbon fibers and the modified zeolite are used in the preparation of polyurethane foam, the iron matrix carrier is prepared and used in the autotrophic denitrification tank in the sewage treatment process, the total nitrogen removal effect by the autotrophic denitrifying bacteria is improved, compared with the comparative example 3, the removal rate of the total nitrogen is improved by 5.92% in the example 2, and compared with the comparative examples 1-2, the improvement of the removal effect of the total nitrogen is shown after the polyurethane foam is prepared by only using the modified carbon fibers or the modified zeolite and then used for preparing the iron matrix carrier and using the iron matrix carrier in the autotrophic denitrification tank, so that the improvement of the final removal effect of the total nitrogen is shown to be better due to the use of the modified carbon fibers and the modified zeolite; the method of example 3 showed 97.49% of total nitrogen removal, the method of example 4 showed 98.62% of total nitrogen removal, and the method of example 4 compared to example 2 showed that the iron-based carrier finally using the polyurethane foam after the polyurethane foam was prepared using di-o-tolyl carbonate was applied to the autotrophic denitrification tank, which increased the total nitrogen removal, and the method of example 4 increased the total nitrogen removal by 2.36% compared to example 2.
The denitrification treatment process has good effect of removing nitrate nitrogen and total nitrogen.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.

Claims (10)

1. An autotrophic denitrification and denitrification treatment process for sewage, comprising the following steps: respectively carrying out denitrification treatment on the sewage in an aerobic treatment tank, an intermediate sedimentation tank and an autotrophic denitrification tank to obtain denitrified water; inoculating activated sludge containing autotrophic denitrifying bacteria into the autotrophic denitrification pool, wherein an iron matrix carrier is used in the autotrophic denitrification pool, the iron matrix carrier is obtained by mixing, granulating and calcining pyrite particles, polyurethane foam, an adhesive and a liquid agent, and the polyurethane foam contains modified carbon fibers and modified zeolite; the modified carbon fiber is prepared by modifying carbon fiber with disodium laureth sulfosuccinate, and the modified zeolite is prepared by modifying zeolite with dodecyl trimethyl ammonium bromide.
2. The process of claim 1, wherein the process comprises the following steps: and the aerobic treatment tank is inoculated with activated sludge containing ammonia oxidizing bacteria and nitrite oxidizing bacteria.
3. The process of claim 1, wherein the process comprises the following steps: the iron matrix carrier is packed in a fixed bed and used in the form of a fixed bed.
4. The process of claim 1, wherein the process comprises the following steps: the adhesive is starch.
5. The process of claim 1, wherein the process comprises the following steps: the polyurethane foam is used in an amount of 20-40 wt% of the pyrite granule.
6. The process of claim 1, wherein the process comprises the following steps: the amount of the binder used is 10-30 wt% of the pyrite granule.
7. A method of preparing a polyurethane foam comprising: mixing modified carbon fibers and modified zeolite in isocyanate to obtain isocyanate composite liquid; mixing a catalyst, a stabilizer, a foaming agent and a chain extender into polyol to obtain polyol mixed solution; carrying out foaming treatment on the isocyanate composite liquid and the polyol mixed liquid to obtain polyurethane foam; the modified carbon fiber is prepared by modifying carbon fiber with disodium laureth sulfosuccinate, and the modified zeolite is prepared by modifying zeolite with dodecyl trimethyl ammonium bromide.
8. A polyurethane foam prepared by the process of claim 7.
9. An iron matrix carrier comprising: obtained by mixing, granulating and calcining a raw material comprising the polyurethane foam of claim 8.
10. The modified carbon fiber and the modified zeolite are used for preparing a carrier and/or treating sewage, the modified carbon fiber is prepared by modifying carbon fiber with disodium laureth sulfosuccinate, and the modified zeolite is prepared by modifying zeolite with dodecyl trimethyl ammonium bromide.
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