CN114426696A - Polyurethane filler and preparation method and application thereof - Google Patents

Polyurethane filler and preparation method and application thereof Download PDF

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Publication number
CN114426696A
CN114426696A CN202010987619.1A CN202010987619A CN114426696A CN 114426696 A CN114426696 A CN 114426696A CN 202010987619 A CN202010987619 A CN 202010987619A CN 114426696 A CN114426696 A CN 114426696A
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polyurethane
parts
water
filler
polyurethane foam
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CN114426696B (en
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曹宗仑
孙杰
龚小芝
郦和生
杨晏泉
张英雄
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • 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
    • C02F3/307—Nitrification and denitrification treatment characterised by direct conversion of nitrite to molecular nitrogen, e.g. by using the Anammox process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
    • C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/15—N03-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/16—Total nitrogen (tkN-N)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

The invention provides a polyurethane filler and a preparation method and application thereof. The polyurethane filler provided by the invention comprises polyurethane foam and Na2SO3A ferrous salt, hydroxylamine and a crosslinking agent. The slow-release polyurethane filler provided by the invention is integrally flexibleThe toughness is good, and the reactor can be cut at will to adapt to reactors of different sizes and shapes, so that the starting speed of the reactor can be increased, and the impact resistance can be enhanced.

Description

Polyurethane filler and preparation method and application thereof
Technical Field
The invention relates to a polyurethane filler and a preparation method and application thereof.
Background
Anaerobic nitrogen oxide bacteria with CO in anaerobic ammonia oxidation process2As a carbon source, with NO2 -As electron acceptor, NH4+Is an electron donor, generates nitrogen (byproduct trace nitrate nitrogen), and realizes the denitrification of the wastewater. Greatly shortens the process of oxidizing and reducing ammonia nitrogen to nitrogen, saves a large amount of energy and materials and saves the operation cost compared with the traditional nitrification-denitrification process. Although the anammox reaction has many advantages, there are still many problems in practical application. Anaerobic nitrogen-oxidizing bacteria are slow-growing microorganisms, have a generation cycle of about 11 days, are sensitive to light, oxygen and the like, have strict requirements on the storage environment, and cause long start time of anaerobic nitrogen-oxidizing reaction. The first set of industrial anammox apparatus operated with netherlands winterdan was started for three years, and the start-up time of the current anammox reactor often required more than one year. The reasons for slow start-up of anammox are mainly: (1) the anammox is easily influenced by external interference factors and has strict requirements on temperature, pH, dissolved oxygen, nitrite concentration and the like; (2) competition and inhibition by other bacteria: at the initial stage of starting the process, the number of anaerobic ammonium oxidation bacteria in the reactor is small, and the mixed bacteria are more dominant and inhibit the proliferation of the mixed bacteria; (3) if no filler is used in the starting process of the process, the problem of sludge loss and anaerobism often existAmmonia oxidizing bacteria are also lost.
The filler is used in the starting process, so that a relatively stable living environment can be provided for the anammox bacteria, the concentration of the anammox bacteria at partial point positions in the reactor is relatively high, the proliferation of the anammox bacteria is facilitated, and the starting time of the anammox process is shortened. The surface of the polyurethane filler is provided with certain cationic active groups, hydroxyl groups and other hydrophilic groups, so that the attachment of microorganisms with negative charges in sewage is facilitated. The using effect of the composite filler is better than that of the traditional filler, such as zeolite, ceramic rings and the like.
CN103951048A discloses preparation and application of an anaerobic ammonium oxidation bacteria immobilized fixed bioactive filler based on a reticular carrier, wherein prepared reticular polyethylene and other materials are used as carriers, an anaerobic ammonium oxidation bacteria suspension and a polyvinyl alcohol mixed solution are added, and anaerobic ammonium oxidation bacteria are attached to the carriers under the soaking of a saturated boric acid solution, so that the efficiency of an anaerobic ammonium oxidation reactor is improved. The method can effectively improve the growth rate of the anammox bacteria and shorten the starting time, but the anammox bacteria liquid required by the raw materials is rare, the attachment mode is simple, and attachments are easy to fall off under the condition of large shearing force, so that the treatment effect is influenced.
CN201510697742.9 discloses a dephosphorization filler, which is composed of polyurethane foam bonded sponge iron and activated carbon. According to the prior art, sponge iron, activated carbon and polyurethane foam are combined together by means of the self adhesive property of the polyurethane foam, the advantages of electrochemistry and easy attachment of organic porous carrier microorganisms and closer contact with iron elements are exerted, and the purpose of removing phosphorus is achieved by fully utilizing multiple functions of microbial action, physical adsorption, chemical flocculation precipitation, electrochemistry and the like. However, in the filler, the sponge iron, the activated carbon and the polyurethane foam are combined by the viscosity of the polyurethane foam, the binding force is weak, the filler structure is easy to damage when the filler is impacted by water power, the activated carbon, the iron powder and the like easily flow out along with the effluent, the system is unstable, and certain limitations exist in practical application.
Disclosure of Invention
Aiming at the technical problem of overlong starting time of the anaerobic ammonia oxidation reactor in the prior art, the methodThe invention provides a polyurethane filler for promoting rapid start and stable operation of anaerobic ammonia oxidation, and a preparation method and application thereof. The invention is prepared by mixing Na2SO3And mixing ferrous salt, hydroxylamine and a cross-linking agent, adding a polyurethane foaming raw material, and foaming to prepare the anaerobic ammonia oxidation filler.
In a first aspect of the invention there is provided a polyurethane filler comprising polyurethane foam, Na2SO3A ferrous salt, hydroxylamine and a crosslinking agent.
According to some embodiments of the invention, the polyurethane foam, Na2SO3The mass ratio of ferrous salt (calculated as Fe) to hydroxylamine is 150: 2-3: 1-2: 1-2.
According to some embodiments of the invention, the cross-linking agent comprises polyvinyl alcohol, sodium alginate and calcium chloride.
According to some embodiments of the invention, the mass ratio of polyvinyl alcohol, sodium alginate and calcium chloride is 1-15: 1.5-5: 1.
according to some embodiments of the invention, the Na2SO3The ratio of the total mass of ferrous salt (calculated as Fe) and hydroxylamine to the mass of the cross-linking agent is 1: 10-20.
According to the invention, the function of polyurethane foam for effectively attaching and trapping sludge is exerted, and Na passes through2SO3And Fe2+The slow release of the compound is carried out on the surface of the filler to maintain a reducing atmosphere, so that the surface of the filler is more suitable for the attachment and proliferation of the anaerobic ammonia oxidizing bacteria, and the attachment of the anaerobic ammonia oxidizing bacteria is selectively promoted; the rapid start of the anaerobic ammonia oxidation process is indirectly promoted by inhibiting the nitration reaction and promoting the nitrosation reaction through the slow release of the hydroxylamine. The hydrophilicity and the reducing atmosphere of the surface of the filler, the inhibition of the hydroxylamine on the nitration reaction and the like synergistically improve the starting efficiency of the anaerobic ammonia oxidation, and the method has wide practical value and prospect.
A second aspect of the invention provides a process for the preparation of a polyurethane filler according to the first aspect, comprising the steps of:
s1: mixing polyvinyl alcohol, sodium alginate and calcium chloride with water to obtain a cross-linking solution;
s2: mixing Na2SO3Mixing ferrous salt and hydroxylamine with the crosslinking solution to obtain a crosslinking mixed solution;
s3: providing a reaction liquid for preparing polyurethane foam;
s4: and mixing the crosslinking mixed solution with the reaction liquid for preparing the polyurethane foam to obtain the composite polyurethane foam.
According to other embodiments of the present invention, polyvinyl alcohol, sodium alginate, calcium chloride, Na2SO3And mixing ferrous salt, hydroxylamine and water to obtain a cross-linked mixed solution.
According to some embodiments of the invention, the method of making further comprises storing the syntactic polyurethane foam at-10-4 ℃, e.g., 0 ℃, to provide a slow release polyurethane filler.
According to some embodiments of the invention, the holding time is 30-60 h.
According to some embodiments of the present invention, the reaction liquid for preparing the polyurethane foam includes a polyester polyol, a polyisocyanate, a catalyst, a surfactant, a blowing agent, and water.
According to some embodiments of the invention, the catalyst is tetramethylethylenediamine.
According to some embodiments of the present invention, in the reaction liquid for preparing a polyurethane foam, the mass ratio of the polyester polyol, the polyisocyanate, the catalyst, the surfactant, the blowing agent and the water is 40 to 60: 40-60: 15-30: 30-40: 10-20: 100.
according to some specific embodiments of the present invention, the preparation method of the composite biological filler for promoting rapid start and stable operation of anaerobic ammonia oxidation comprises the following steps:
1) weighing polyvinyl alcohol, sodium alginate and calcium chloride, adding distilled water, and mixing to form a cross-linking solution;
2) mixing Na2SO3Adding ferrous salt and hydroxylamine into the crosslinking solution obtained in the step 1) to obtain a crosslinking mixed solution;
3) adding raw materials for preparing polyurethane foam into a mould, and stirring at a high speed;
4) adding the cross-linking mixed solution in the step 2) into the reaction solution in the step 3), and continuously stirring for 2-5S for foaming to obtain composite polyurethane foam;
5) and (3) placing the composite polyurethane foam obtained in the step 4) in a refrigerator, and storing for 30-60h at the temperature of-10-4 ℃ to obtain the slow-release polyurethane filler.
A third aspect of the invention provides the use of a polyurethane filler according to the first aspect or obtained according to the method of preparation of the second aspect in an anaerobic ammonia oxidation reaction.
According to some embodiments of the invention, the reaction is an anammox start-up reaction and/or a nitrosation-anammox integrated process start-up reaction.
The invention has the beneficial effects that:
(1)Fe2+can promote the rapid proliferation of the anammox bacteria, the ferrous salt is added in the invention to promote the rapid proliferation of the anammox bacteria, but in general, ferrous ions are extremely easy to oxidize and are extremely easy to be converted into Fe in a reactor3+，Fe3+The precipitate is generated through one-step hydrolysis, so that the bacteria in the common anaerobic ammonia oxidation reactor have Fe resistance2+Has very low utilization rate, Na in the invention2SO3The added ferrous ions are kept in sufficient concentration to promote the rapid growth of the anaerobic ammonium oxidation bacteria; and secondly, the reducing atmosphere on the surface of the filler is maintained, and the attachment and proliferation of the anaerobic ammonia oxidizing bacteria on the surface of the filler are promoted.
(2) The hydroxylamine is added to promote the nitrosation reaction, so that the nitrosation reaction is superior to the nitrification reaction, and the start of the anaerobic ammonia oxidation is indirectly promoted, and the function is mainly embodied in the start process of the nitrosation-anaerobic ammonia oxidation integrated reactor or process; on the other hand, the nitrifying bacteria can be prevented from being attached to the surface of the filler, and the competitive inhibition of the nitrifying bacteria on the anammox can be weakened.
(3) The main component of the filler is polyurethane, the polyurethane filler has the advantages of the traditional filler, and the surface of the polyurethane filler has certain cationic active groups, hydroxyl groups and other hydrophilic groups, so that the cationic active groups and the hydroxyl groups can be combined with microorganisms with negative charges in sewage to generate valence and bond combination, so that sludge can be more stably attached to the surface of the filler and is not easy to run off under the shearing action of water and air.
(4) The cross-linking agent is prepared by mixing polyvinyl alcohol, sodium alginate and calcium chloride, and has the advantage of being capable of being mixed with Na2SO3The ferrous salt and the hydroxylamine are crosslinked in the polyurethane foam, so that the polyurethane foam is slowly released, and the polyurethane foam is low in cost and easy to obtain.
(5) The invention adopts a foaming process adding method to mix polyurethane foam and Na2SO3The slow-release polyurethane filler is formed by combining ferrous salt and hydroxylamine, and the adhesion of attachments among foam gaps is more stable due to the mixed material added in the foaming process of polyurethane foam.
(7) The slow-release polyurethane filler has good overall flexibility, can be cut at will to adapt to reactors with different sizes and shapes, can improve the starting speed of the reactor, and enhances the shock resistance.
Drawings
FIG. 1 is a diagram of an apparatus for starting up a UASB anammox reactor in accordance with example 1 of the present invention, in which 1. a stirring apparatus; 2, UASB reactor; 3. a heating jacket; 4, electrode interface of pH and temperature; a UASB water inlet and distribution device; 6. an acid regulation pump; 7. an alkali conditioning pump; 8. a system water inlet pump; 9. a hot water pump; 10. a reflux pump; 11 a constant temperature water tank; 12. a water inlet of the three-phase separator; 13. a three-phase separator return outlet; 14. a water outlet of the three-phase separator; 15. a three-phase separator.
FIG. 2 is a diagram showing an apparatus of a UASB anammox start-up reactor in accordance with example 2 of the present invention, in which 1. a gas outlet of a three-phase separator; 2. a water outlet of the device; 3. a sampling port; probe interfaces such as pH, temperature, dissolved oxygen, etc.; 5. an aeration system: an air compressor, a gas flow regulation and control system, an aeration head and the like; 6. acid-base regulating part: an acid-containing pump and an alkali pump; 7. a water inlet pump; 8. a reflux pump; 9. a temperature control system.
Detailed Description
For easy understanding of the present invention, the present invention will be described in detail with reference to examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention.
The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
Example 1
Weighing 36 parts of polyvinyl alcohol, 24 parts of sodium alginate and 6 parts of calcium chloride according to parts by weight; weighing Na2SO31.5 parts of FeCl21 part each of (in terms of Fe) and hydroxylamine; adding the components into 200 parts of distilled water, stirring and dissolving to form a cross-linked mixed solution, and uniformly stirring.
Adding 50 parts of polyester polyol, 50 parts of polyisocyanate, 100 parts of water, 20 parts of tetramethylethylenediamine catalyst, 35 parts of surfactant and 15 parts of foaming agent into a container, stirring at a high speed for 2s, then adding the prepared cross-linked mixed solution in proportion to control the proportion of active ingredients in the formed polyurethane filler, continuously stirring for 2min, injecting into a mold for forming, and then placing into a refrigerator for storage for 48h at 0 ℃ to obtain the slow-release polyurethane filler.
Adopting a reactor device shown in figure 1, filling the prepared slow-release polyurethane filler into a UASB anaerobic ammonia oxidation start-up reactor, wherein the effective volume of the reactor is 1000ml, and the total filling volume accounts for 60 percent of the total volume of the reactor; taking sludge at the bottom of a settling tank in a domestic sewage treatment plant, standing and concentrating, removing supernatant, taking bottom concentrated sludge, and using a prepared inorganic salt solution (NaCl: 1000-1500 mg/L, KH)2PO4：10mg/L，CaCl2：5.6mg/L，MgSO4: 300mg/L) for 4 times, and standing for 1.5 hours after each time of elutriation to remove supernatant, so as to remove inorganic impurities and organic pollutants adsorbed on the surface of the sludge as far as possible. 600ml of elutriated and concentrated sludge is put into a UASB reactor, and stirred to ensure that the sewage is fully contacted and mixed with the filler.
Simulating wastewater (NH) by a peristaltic pump4 +-N and NO2 -N is 100mg/L) is fed into a UASB reactor, and effluent is dischargedAnd the effluent enters a three-phase separator from an upper outlet of the UASB, sewage sludge backflow is arranged at the bottom of the three-phase separator, and system effluent is discharged from an upper outlet of the three-phase separator. Adjusting the pump flow to enable the hydraulic retention time to be 8 hours, controlling the reflux ratio to be 4, controlling the internal temperature of the system to be 33 +/-2 ℃, controlling the pH to be 7.2-8.0, controlling the rotating speed of the stirring paddle to be 80r/min, sampling and monitoring indexes of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen and the like of inlet and outlet water of the system every day, wherein the ammonia nitrogen of the outlet water of the system at the initial stage is higher than that of the inlet water, and the ammonia nitrogen of the outlet water is lower than that of the inlet water by the 6 th day; by the 28 th day, the system shows denitrification capability, the total nitrogen removal rate reaches 7.8 percent, by the 72 th day, the ammonia nitrogen and nitrite nitrogen removal rates reach more than 95 percent, and the total nitrogen removal rate reaches 88 percent, so that the anaerobic ammonia oxidation system can be considered to be started successfully.
Comparative example 1
Adding 50 parts of polyester polyol, 50 parts of polyisocyanate, 100 parts of water, 20 parts of tetramethylethylenediamine catalyst, 35 parts of surfactant and 15 parts of foaming agent into a container, stirring at a high speed for 2s, injecting into a mold for molding, and then placing into a refrigerator for storage at 0 ℃ for 48h to obtain the slow-release polyurethane filler.
Filling the prepared blank polyurethane foam filler into a UASB anaerobic ammonia oxidation start-up reactor by adopting a reactor device shown in figure 1, wherein the effective volume of the reactor is 1000ml, and the total filling volume accounts for 60 percent of the total volume of the reactor; taking sludge at the bottom of a settling tank in a domestic sewage treatment plant, standing and concentrating, removing supernatant, taking bottom concentrated sludge, and using a prepared inorganic salt solution (NaCl: 1000-1500 mg/L, KH)2PO4：10mg/L，CaCl2：5.6mg/L，MgSO4: 300mg/L) for 4 times, and standing for 1.5 hours after each time of elutriation to remove supernatant, so as to remove inorganic impurities and organic pollutants adsorbed on the surface of the sludge as far as possible. 600ml of elutriated and concentrated sludge is put into a UASB reactor, and stirred to ensure that the sewage is fully contacted and mixed with the filler.
Simulating wastewater (NH) by a peristaltic pump4 +-N and NO2 --N) feeding the effluent into a UASB reactor, feeding the effluent into a three-phase separator from an upper outlet of the UASB reactor, setting sewage sludge reflux at the bottom of the three-phase separator, and discharging the effluent of the system from an upper outlet of the three-phase separatorAnd (6) discharging. Adjusting the pump flow to enable the hydraulic retention time to be 8 hours, controlling the reflux ratio to be 4, controlling the internal temperature of the system to be 33 +/-2 ℃, controlling the pH to be 7.2-8.0, controlling the rotating speed of the stirring paddle to be 80r/min, sampling and monitoring indexes of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen and the like of inlet and outlet water of the system every day, wherein the ammonia nitrogen of the outlet water of the system at the initial stage is higher than that of the inlet water, and the ammonia nitrogen of the outlet water is lower than that of the inlet water by the 6 th day; by the 40 th day, the system shows denitrification capability, the total nitrogen removal rate reaches 7.8 percent, and by the 72 th day, the ammonia nitrogen removal rate and the nitrite nitrogen removal rate are respectively 30 percent and 21 percent, which are far from the standard of successful start.
Comparative example 2
Weighing 36 parts of polyvinyl alcohol, 24 parts of sodium alginate and 6 parts of calcium chloride according to parts by weight; adding 200 parts of distilled water, stirring and dissolving to form a cross-linked mixed solution, and uniformly stirring.
Adding 50 parts of polyester polyol, 50 parts of polyisocyanate, 100 parts of water, 20 parts of tetramethylethylenediamine catalyst, 35 parts of surfactant and 15 parts of foaming agent into a container, stirring at a high speed for 2s, adding the prepared cross-linked mixed solution, continuously stirring for 2min, injecting into a mold for molding, and then placing into a refrigerator to store at 0 ℃ for 48h to obtain the comparative polyurethane filler.
Starting anaerobic ammonia oxidation reaction by using a comparative polyurethane filler 1 and adopting the same UASB reactor and the same operating conditions as those of the example 1, wherein the ammonia nitrogen of the effluent water of the initial system is higher than that of the influent water, and the ammonia nitrogen of the effluent water is lower than that of the influent water by the 6 th day; by the 42 th day, the system shows denitrification capability, the total nitrogen removal rate reaches 7.8%, and by the 72 th day, the ammonia nitrogen removal rate and the nitrite nitrogen removal rate are respectively 28% and 21%, and the filler effect is not substantially different from that of the comparative example 1.
Comparative example 3
Weighing 36 parts of polyvinyl alcohol, 24 parts of sodium alginate and 6 parts of calcium chloride according to parts by weight; weighing Na2SO31.5 parts of FeCl21 part (calculated as Fe); adding the components into 200 parts of distilled water, stirring and dissolving to form a cross-linked mixed solution, and uniformly stirring.
Adding 50 parts of polyester polyol, 50 parts of polyisocyanate, 100 parts of water, 20 parts of tetramethylethylenediamine catalyst, 35 parts of surfactant and 15 parts of foaming agent into a container, stirring at a high speed for 2s, adding the prepared cross-linked mixed solution, continuously stirring for 2min, injecting into a mold for molding, and then placing into a refrigerator to store at 0 ℃ for 48h to obtain the comparative polyurethane filler 1.
Starting an anaerobic ammonia oxidation reaction by adopting the same UASB reactor and the same operating conditions as those of the embodiment 1, wherein the ammonia nitrogen of the effluent water of the initial system is higher than that of the influent water, and the ammonia nitrogen of the effluent water is lower than that of the influent water by the 6 th day; by the day 43, the system shows denitrification capability, the total nitrogen removal rate reaches 8.0%, and by the day 72, the ammonia nitrogen removal rate and the nitrite nitrogen removal rate are respectively 45% and 38%, compared with the comparative example 1, the anaerobic ammonia oxidation effect is more obvious, but the anaerobic ammonia oxidation effect does not reach the standard of successful start, and the filling effect is obviously worse than that of the example 1.
Comparative example 4
Weighing 36 parts of polyvinyl alcohol, 24 parts of sodium alginate and 6 parts of calcium chloride according to parts by weight; weighing 1 part of hydroxylamine; adding the components into 200 parts of distilled water, stirring and dissolving to form a cross-linked mixed solution, and uniformly stirring.
Adding 50 parts of polyester polyol, 50 parts of polyisocyanate, 100 parts of water, 20 parts of tetramethylethylenediamine catalyst, 35 parts of surfactant and 15 parts of foaming agent into a container, stirring at a high speed for 2s, adding the prepared cross-linked mixed solution, continuously stirring for 2min, injecting into a mold for molding, and then placing into a refrigerator to store at 0 ℃ for 48h to obtain the comparative polyurethane filler 1.
Starting an anaerobic ammonia oxidation reaction by adopting the same UASB reactor and the same operating conditions as those of the embodiment 1, wherein the ammonia nitrogen of the effluent water of the initial system is higher than that of the influent water, and the ammonia nitrogen of the effluent water is lower than that of the influent water by 7 days; by the day 43, the system shows denitrification capability, the total nitrogen removal rate reaches 8.3%, and by the day 72, the ammonia nitrogen removal rate and the nitrite nitrogen removal rate are respectively 38% and 32%, compared with the comparative example 1, the anaerobic ammonia oxidation effect is more obvious, but the anaerobic ammonia oxidation effect does not reach the standard of successful start, and the filling effect is obviously worse than that of the example 1.
Example 2
The packing and reactor size and form were the same as in example 1, using the same packing and reactor configuration as shown in FIG. 2The reactor has the functions of aeration and dissolved oxygen control, and the inlet water contains NH4 +-N200 mg/L simulated water distribution, controlling the dissolved oxygen concentration in the reactor to be below 0.3mg/L, and the other operating conditions are the same as those in example 1, sampling and monitoring indexes such as ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in and out water of the system every day, wherein the total nitrogen of the effluent water of the system at the initial stage is higher than that of the influent water, the ammonia nitrogen of the effluent water is 120mg/L, the nitrite nitrogen is 61mg/L, the nitrate nitrogen concentration is 12mg/L, the total nitrogen of the effluent water is lower than that of the influent water, the maximum stage of the nitrate nitrogen concentration of the effluent water is 20mg/L on the 10 th day, the system shows denitrification capability on the 45 th day, the ammonia nitrogen of the effluent water is 30mg/L, the nitrite nitrogen is 132mg/L, the nitrate nitrogen is 8mg/L, the total nitrogen removal rate is 15%, and the ammonia nitrogen of the effluent water is 8mg/L, the nitrite nitrogen is 12mg/L, the nitrate nitrogen, Nitrate nitrogen is 18mg/L, the total nitrogen removal rate reaches 81%, and the nitrosation-anaerobic ammonia oxidation integrated process is basically started successfully.
Comparative example 5
The filler used was the blank polyurethane foam filler prepared in comparative example 1, and the other operating conditions and parameters were the same as in example 2. The indexes of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen and the like in and out of water of the system are sampled and monitored every day, the total nitrogen of the effluent of the system at the initial stage is higher than that of the influent water, the ammonia nitrogen of the effluent is 110mg/L, the nitrite nitrogen is 61mg/L, the nitrate nitrogen concentration is 25mg/L, the total nitrogen of the effluent is lower than that of the influent water, the maximum stage nitrogen concentration of the effluent is 56mg/L on the 15 th day, the effluent ammonia nitrogen is 38mg/L, the nitrite nitrogen is 120mg/L, the nitrate nitrogen is 28mg/L, the total nitrogen rate is only 7 percent on the 15 th day, the effluent ammonia nitrogen is 15mg/L, the nitrite nitrogen is 85mg/L, the nitrate nitrogen is 32mg/L on the 45 th day, the total nitrogen removal rate is about 34 percent, and the starting progress of the nitrosation-anaerobic ammonia oxidation integrated process is obviously laggard behind that of the embodiment 2.
Comparative example 6
The comparative polyurethane foam filler 1 prepared in comparative example 2 was used as the filler, and the other operating conditions and parameters were the same as those in example 2. Sampling and monitoring indexes such as ammonia nitrogen, nitrite nitrogen, nitrate nitrogen and the like of inlet and outlet water of the system every day, wherein the total nitrogen of the outlet water of the system is higher than that of the inlet water in the initial stage until the 5 th day, the ammonia nitrogen of the effluent is 107mg/L, the nitrite nitrogen is 62mg/L, the nitrate nitrogen concentration is 26mg/L, the total nitrogen of the effluent is lower than the total nitrogen of the influent, the maximum nitrate nitrogen concentration of the effluent reaches 58mg/L on the 17 th day, and when the effluent reaches the 45 th day, the ammonia nitrogen of the effluent is 36mg/L, the nitrite nitrogen is 115mg/L, the nitrate nitrogen is 34mg/L, the total nitrogen removal rate is 7.5%, the ammonia nitrogen of the effluent is 14mg/L, the nitrite nitrogen is 88mg/L, the nitrate nitrogen is 33mg/L and the total nitrogen removal rate is about 33% by 80 days, the starting progress of the nitrosation-anaerobic ammonia oxidation integrated process is obviously laggard compared with that of the embodiment 2, and the effect is not obviously different from that of the comparative example 3.
Example 3
Weighing 36 parts of polyvinyl alcohol, 24 parts of sodium alginate and 6 parts of calcium chloride according to parts by weight; weighing Na2SO30.5 part of FeCl2And hydroxylamine 0.5 parts each; adding the components into 200 parts of distilled water, stirring and dissolving to form a cross-linked mixed solution, and uniformly stirring.
Adding 50 parts of polyester polyol, 50 parts of polyisocyanate, 100 parts of water, 20 parts of tetramethylethylenediamine catalyst, 35 parts of surfactant and 15 parts of foaming agent into a container, stirring at a high speed for 2s, adding the prepared cross-linked mixed solution, continuously stirring for 2min, injecting into a mold for molding, and then placing into a refrigerator to store at 0 ℃ for 48h to obtain the slow-release polyurethane filler.
Starting an anaerobic ammonia oxidation reaction by adopting the same UASB reactor and the same operating conditions as those of the embodiment 1, wherein the ammonia nitrogen of the effluent water of the initial system is higher than that of the influent water, and the ammonia nitrogen of the effluent water is lower than that of the influent water by the 6 th day; by the 42 th day, the system shows denitrification capacity, the total nitrogen removal rate reaches 15%, by the 72 th day, the ammonia nitrogen removal rate and the nitrite nitrogen removal rate are 69% and 63%, respectively, the anaerobic ammonia oxidation start is nearly successful, but the filler effect is poorer than that of the embodiment 1.
Example 4
Weighing 36 parts of polyvinyl alcohol, 24 parts of sodium alginate and 6 parts of calcium chloride according to parts by weight; weighing Na2SO35 parts of FeCl2And 3 parts of hydroxylamine each; adding the components into 200 parts of distilled water, stirring and dissolving to form a cross-linked mixed solution, and uniformly stirring.
Adding 50 parts of polyester polyol, 50 parts of polyisocyanate, 100 parts of water, 20 parts of tetramethylethylenediamine catalyst, 35 parts of surfactant and 15 parts of foaming agent into a container, stirring at a high speed for 2s, adding the prepared cross-linked mixed solution, continuously stirring for 2min, injecting into a mold for molding, and then placing into a refrigerator to store at 0 ℃ for 48h to obtain the slow-release polyurethane filler.
Starting an anaerobic ammonia oxidation reaction by adopting the same UASB reactor and the same operating conditions as those of the embodiment 1, wherein the ammonia nitrogen of the effluent water of the initial system is higher than that of the influent water, and the ammonia nitrogen of the effluent water is lower than that of the influent water by the 6 th day; by the 42 th day, the system shows denitrification capability, the total nitrogen removal rate reaches 8.2%, and by the 72 th day, the ammonia nitrogen removal rate and the nitrite nitrogen removal rate are respectively 95% and 95%, the starting of the anaerobic ammonia oxidation process is successful, and the effect is not obviously improved compared with that of the embodiment 1.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A polyurethane filler is prepared from polyurethane foam and Na2SO3A ferrous salt, hydroxylamine and a crosslinking agent.
2. The polyurethane filler according to claim 1, wherein the polyurethane foam, Na2SO3The mass ratio of ferrous salt (calculated as Fe) to hydroxylamine is 150: 2-3: 1: 1-2.
3. The polyurethane filler according to claim 1 or 2, characterized in that the cross-linking agent comprises polyvinyl alcohol, sodium alginate and calcium chloride.
4. The polyurethane filler according to any one of claims 1-3, wherein the mass ratio of polyvinyl alcohol, sodium alginate and calcium chloride is 3-15: 1.5-5: 1.
5. the polyurethane filler of any one of claims 1-4, wherein the Na is2SO3The ratio of the total mass of ferrous salt (calculated as Fe) and hydroxylamine to the mass of the cross-linking agent is 1: 10-20.
6. A method of preparing a polyurethane filler according to any one of claims 1-5, comprising the steps of:
s1: mixing polyvinyl alcohol, sodium alginate and calcium chloride with water to obtain a cross-linking solution;
s2: mixing Na2SO3Mixing ferrous salt and hydroxylamine with the crosslinking solution to obtain a crosslinking mixed solution;
s3: providing a reaction liquid for preparing polyurethane foam;
s4: and mixing the crosslinking mixed solution with the reaction liquid for preparing the polyurethane foam to obtain the composite polyurethane foam.
7. The preparation method according to claim 6, further comprising storing the composite polyurethane foam at-10-4 ℃ for 30-60h, preferably 30-60h, to obtain the polyurethane filler.
8. The method according to claim 6 or 7, wherein the reaction liquid for preparing the polyurethane foam comprises polyester polyol, polyisocyanate, catalyst, surfactant, foaming agent and water, preferably, the catalyst is tetramethylethylenediamine.
9. The production method according to claim 8, wherein the reaction liquid for producing the polyurethane foam has a mass ratio of the polyester polyol, the polyisocyanate, the catalyst, the surfactant, the blowing agent and water of 40 to 60: 40-60: 15-30: 30-40: 10-20: 100.
10. use of a polyurethane filler according to any one of claims 1 to 5 or obtained by a method according to any one of claims 6 to 9 in an anammox reaction, in particular in an anammox start-up and/or a nitrosation-anammox integrated process start-up.
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CN117658320A (en) * 2024-01-24 2024-03-08 中国人民大学 Preparation method of sodium alginate-polyurethane filler fixed particle anaerobic ammonia oxidation sludge, product and application thereof

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JPH07126524A (en) * 1993-10-29 1995-05-16 Japan Synthetic Rubber Co Ltd Thermoplastic resin composition
CN103665848A (en) * 2013-11-28 2014-03-26 方万漂 Polyethylene and nylon 6 blending modified barrier material
CN103951039A (en) * 2014-04-04 2014-07-30 北京工业大学 Preparation and application of nitrifying bacteria immobilized bioactive filler based on polyurethane carrier
CN106745713A (en) * 2015-11-19 2017-05-31 中国石油化工股份有限公司 A kind of quick start method of anaerobic ammonia oxidation reactor
CN108017793A (en) * 2017-11-27 2018-05-11 兰州大学白银产业技术研究院 A kind of application being sustained in the preparation method and its chemical wastewater treatment of polyurethane mesh carrier

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JPH07126524A (en) * 1993-10-29 1995-05-16 Japan Synthetic Rubber Co Ltd Thermoplastic resin composition
CN103665848A (en) * 2013-11-28 2014-03-26 方万漂 Polyethylene and nylon 6 blending modified barrier material
CN103951039A (en) * 2014-04-04 2014-07-30 北京工业大学 Preparation and application of nitrifying bacteria immobilized bioactive filler based on polyurethane carrier
CN106745713A (en) * 2015-11-19 2017-05-31 中国石油化工股份有限公司 A kind of quick start method of anaerobic ammonia oxidation reactor
CN108017793A (en) * 2017-11-27 2018-05-11 兰州大学白银产业技术研究院 A kind of application being sustained in the preparation method and its chemical wastewater treatment of polyurethane mesh carrier

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117658320A (en) * 2024-01-24 2024-03-08 中国人民大学 Preparation method of sodium alginate-polyurethane filler fixed particle anaerobic ammonia oxidation sludge, product and application thereof

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