CN113462679A - Method for degrading polybrominated diphenyl ether flame retardant by utilizing biological sponge iron - Google Patents
Method for degrading polybrominated diphenyl ether flame retardant by utilizing biological sponge iron Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 182
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 91
- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 71
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
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- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 3
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- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- ARERIMFZYPFJAV-UHFFFAOYSA-N tetrabromodiphenyl ethers Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C(Br)=C1Br ARERIMFZYPFJAV-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
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- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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Abstract
The invention discloses a method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron, relating to the technical field of flame retardant degradation, and comprising the following steps of S1: feeding iron ore powder and inorganic binder bentonite into a moistening and grinding machine through a screw feeding rod for moistening and grinding, and then performing oxidation-reduction reaction to obtain a sponge iron pipe body, S2, preparing biological sponge iron: inoculating microbial strains into the interior of the sponge iron tube body, and activating and enriching the flame retardant S3: activating and enriching the polybrominated diphenyl ether flame retardant, and degrading the flame retardant S4: the biological sponge iron can degrade waste water or solid matters containing polybrominated diphenyl ethers or polybrominated diphenyl ether flame retardants, and has the advantages of low degradation cost, high degradation efficiency and good degradation effect.
Description
Technical Field
The invention relates to the technical field of flame retardant degradation, in particular to a method for degrading a polybrominated diphenyl ether flame retardant by utilizing biological sponge iron.
Background
The polybrominated diphenyl ethers include 209 homologs of tetrabromobiphenyl ether, pentabromide, hexabromide, octabromide, decabromide and the like. The commercial polybrominated diphenyl ethers are a group of diphenyl ether mixtures with different bromine atom numbers, and are therefore collectively referred to as polybrominated diphenyl ethers.
Polybrominated diphenyl ethers are a class of global organic pollutants that are widely present in the environment. Because of the characteristics of environmental persistence, long-distance transmission, bioaccumulation, toxic effect on organisms and human bodies and the like, the research on the environmental problems becomes a great hotspot of the current environmental science.
Polybrominated diphenyl ethers as a large class of flame retardant substances of brominated flame retardants have been increasingly widely applied to various consumer products due to the excellent flame retardant properties thereof. However, as the detection of PBDEs is continuously reported in environmental samples, the environmental problems caused by the compounds are also receiving more and more attention from people, particularly from environmental science.
The polybrominated diphenyl ethers are used as flame retardants and are added to composite materials in the manufacturing process of products so as to improve the fireproof performance of the products. Because polybrominated diphenyl ethers can release free radicals at high temperature, the combustion reaction is blocked. The decabromodiphenyl ether is a compound with the most bromine atoms in a polybrominated diphenyl ether family, and is low in price, excellent in performance and lowest in acute toxicity in all the brominated diphenyl ethers, so that the decabromodiphenyl ether is used most widely in the global range, and is used in products such as various electronic appliances, automatic control equipment, building materials, textiles, furniture and the like. According to statistics, the decabromodiphenyl oxide accounts for more than 75 percent of the total amount of the flame retardant.
In addition to the emission of the polybrominated diphenyl ethers to the surrounding environment in the form of dust by manufacturers, the main way of polluting the environment with polybrominated diphenyl ethers is to carry out incineration, crushing, landfill treatment and the like on electronic wastes containing the polybrominated diphenyl ethers. The residual amount in the soil increases year by year because polybrominated diphenyl ethers are quite stable in the environment and difficult to degrade. And polybrominated diphenyl ethers are insoluble in water and readily soluble in fat, and therefore, are easily absorbed by animals and gradually enriched in the food chain.
And (3) pollution path:
(1) the main method for directly contacting polybrominated diphenyl ethers is that production workers contact the polybrominated diphenyl ethers daily, and most of the dust is discharged out of the body. But the accumulation is gradually increased day by day.
(2) Trace amounts of polybrominated diphenyl ethers in the atmosphere, water, soil obtained via food can finally enter human food via the food chain. Therefore, the mode of exposure of most people to polybrominated diphenyl ethers is obtained by food.
The sponge iron is adopted to be matched with microorganisms to degrade the flame retardant of polybrominated diphenyl ethers, the effect is good, most of the existing polybrominated diphenyl ethers are degraded by photochemistry, but the degradation effect is poor, and the degradation efficiency is low.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for degrading a polybrominated diphenyl ether flame retardant by utilizing biological sponge iron, which comprises the following steps:
s1: preparation of sponge iron
Feeding iron ore powder and inorganic binder bentonite into a wet grinding machine through a spiral feeding rod for wet grinding, wherein the mass ratio of the iron ore powder to the inorganic binder bentonite is 5:3, placing the powder obtained after wet grinding, reducing coal and a desulfurizing agent into a mixer for mixing according to the mass ratio of 1:0.6:0.05, preparing the mixed powder into a hollow pipe after the mixing is finished, laying reducing coal powder with the thickness of 6-7cm at the bottom of a ceramic reaction tank, placing the hollow pipe into the ceramic reaction tank, sealing the top of the ceramic reaction tank with refractory soil, heating the ceramic reaction tank for oxidation-reduction reaction, and naturally cooling the ceramic reaction tank to room temperature after the oxidation-reduction reaction is finished to obtain a sponge iron pipe body;
s2: preparation of biological sponge iron
Adding a microbial strain carrier agent into a culture medium solution to prepare a mixed culture solution, stirring the mixed culture solution to uniformly mix the culture medium solution and the microbial strain carrier agent, then inoculating microbial strains into the mixed culture solution, wherein the inoculation amount of the microbial strains is 50g/L, performing shake culture at the ambient temperature of 30-40 ℃ for 60-80h to enable the microbial strain carrier agent to be attached to the surface of the strains, then removing the liquid, drying the solid at low temperature to obtain strain microspheres, and filling the obtained strain microspheres into the sponge iron tube body to obtain biological sponge iron;
s3: activation enrichment of flame retardant
Adding a surface active agent into the polybrominated diphenyl ether flame retardant, and then putting the flame retardant added with the surface active agent into a microwave reactor for microwave heating to activate and enrich polybrominated diphenyl ether substances;
s4: degradation of flame retardants
Preparing polybrominated diphenyl ether flame retardant, deionized water, normal hexane and normal hexane-acetone into a polybrominated diphenyl ether-containing solution according to the mass ratio of 3:50:20:5, then adding degradable polyelectrolyte and biological sponge iron into the polybrominated diphenyl ether-containing solution, wherein the addition amount of the degradable polyelectrolyte is 20g/L, the addition amount of the biological sponge iron is 50g/L, performing biodegradation culture at room temperature for 6-7 days, detecting the polybrominated diphenyl ether content in the degraded solution, filtering the solution after the polybrominated diphenyl ether in the degraded solution is completely degraded, and preparing the polybrominated diphenyl ether-containing solution next time according to the mass ratio of 70: 3.
Further, in the step S1, the length of the wet grinding is 30-40min, the rotating speed of the wet grinding machine is 80-90r/min, the particle size of the powder obtained after the wet grinding is 20-50um, and the wet grinding is more sufficient.
Further, the desulfurizing agent in the step S1 is prepared by mixing silicon, calcium and manganese according to the mass ratio of 3:2:1, and the desulfurizing effect is better.
Further, in the step S1, the heating temperature of the ceramic reaction tank in the oxidation-reduction reaction is 1000-1100 ℃, the reaction time is 13-20h, and the oxidation-reduction reaction is more thorough.
Further, the length of the sponge iron pipe body obtained in the step S1 is 3-5cm, the pipe diameter is 0.5-1cm, and the contact area with the solution is larger.
Further, the microbial strains inoculated in the mixed culture solution in the step S2 are prepared from Brevibacillus brevis and stenotrophomonas maltophilia according to the mass ratio of 1:2, and the effect of degrading the polybrominated diphenyl ether flame retardant is better.
Further, the concentration of the microbial strain carrier agent in the mixed culture solution prepared in the step S2 is 8mg/ml, which is more beneficial to the degradation of the polybrominated diphenyl ether flame retardant by the strain.
Furthermore, the microbial strain carrier agent is a mixture consisting of single-layer montmorillonite nanosheets and carbon fibers according to the weight ratio of 3:2, and has a better effect when used as a carrier of strains.
Further, the amount of the surfactant added in the step S3 is 1-3% of the mass of the polybrominated diphenyl ether flame retardant, and is used for activating the polybrominated diphenyl ether-enriched substance.
Further, the heating temperature of the microwave heating is 260-310 ℃, and the heating time is 2-3h, so that the activation and enrichment of the polybrominated diphenyl ether flame retardant are promoted.
The invention has the beneficial effects that:
(1) the biological sponge iron can degrade waste water or solid matters containing polybrominated diphenyl ethers or polybrominated diphenyl ether flame retardants, and has the advantages of low degradation cost, high degradation efficiency and good degradation effect.
(2) The invention does not introduce new pollutants in the degradation of the polybrominated diphenyl ether flame retardant and can not cause secondary pollution of waste water or solid matters.
Drawings
FIG. 1 is a schematic flow chart of the process for degrading polybrominated diphenyl ethers by using the biological sponge iron.
Detailed Description
Example 1
As shown in fig. 1, a method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron comprises the following steps:
s1: preparation of sponge iron
Feeding iron ore powder and inorganic binder bentonite into a wet grinding machine through a screw feeding rod for wet grinding, wherein the mass ratio of the iron ore powder to the inorganic binder bentonite is 5:3, the wet grinding time is 30min, the rotating speed of the wet grinding machine is 80r/min, the particle size of the powder obtained after wet grinding is 20-30um, the wet grinding is more sufficient, the powder obtained after wet grinding, reducing coal and a desulfurizing agent are placed into a mixer according to the mass ratio of 1:0.6:0.05 for mixing, the desulfurizing agent is prepared by mixing silicon, calcium and manganese according to the mass ratio of 3:2:1, the desulfurizing effect is better, after the mixing is completed, the mixed powder is made into a hollow pipe, reducing coal powder with the thickness of 6cm is paved at the bottom of a ceramic reaction tank, the hollow pipe is placed into the ceramic reaction tank, the top of the ceramic reaction tank is sealed by refractory soil, the ceramic reaction tank is heated for oxidation-reduction reaction, the heating temperature of the ceramic reaction tank in the oxidation-reduction reaction is 1000 ℃, the reaction time is 13h, the oxidation-reduction reaction is more thorough, the reaction is naturally cooled to room temperature along with the ceramic reaction tank after the oxidation-reduction reaction is completed, a sponge iron pipe body is obtained, the length of the obtained sponge iron pipe body is 3cm, the pipe diameter of the obtained sponge iron pipe body is 0.5cm, and the contact area of the obtained sponge iron pipe body and the solution is larger;
s2: preparation of biological sponge iron
Adding a microbial strain carrier agent into a culture medium solution to prepare a mixed culture solution, stirring the mixed culture solution to uniformly mix the culture medium solution and a microbial strain carrier agent, wherein the concentration of the microbial strain carrier agent in the prepared mixed culture solution is 8mg/ml, which is more favorable for degrading a polybrominated diphenyl ether flame retardant by strains, then inoculating the microbial strain into the mixed culture solution, wherein the inoculation amount of the microbial strain is 50g/L, the microbial strain inoculated by the mixed culture solution is prepared from brevibacillus brevis and stenotrophomonas maltophilia according to the mass ratio of 1:2, the effect of degrading the polybrominated diphenyl ether flame retardant is better, performing shake bed culture at the ambient temperature of 30 ℃ for 60 hours to ensure that the microbial strain carrier agent is attached to the surface of the strains, then removing the liquid, drying the solid at low temperature, and obtaining strain microspheres at the low-temperature drying temperature of 4 ℃, filling the interior of the sponge iron pipe body with the obtained strain microspheres to obtain biological sponge iron;
the microbial strain carrier agent is a mixture consisting of single-layer montmorillonite nanosheets and carbon fibers according to the weight ratio of 3:2, and has a better effect when being used as a carrier of a strain;
s3: activation enrichment of flame retardant
Adding a surface active agent into a polybrominated diphenyl ether flame retardant, wherein the addition amount of the surface active agent is 1 percent of the mass of the polybrominated diphenyl ether flame retardant, and the surface active agent is used for activating and enriching polybrominated diphenyl ether substances;
s4: degradation of flame retardants
Preparing polybrominated diphenyl ether flame retardant, deionized water, n-hexane and n-hexane-acetone into a polybrominated diphenyl ether-containing solution according to the mass ratio of 3:50:20:5, adding degradable polyelectrolyte and biological sponge iron into the polybrominated diphenyl ether-containing solution, detecting the polybrominated diphenyl ether content in the degraded solution after performing biodegradation culture for 6 days at room temperature, filtering the solution after completely degrading the polybrominated diphenyl ether in the degraded solution, and preparing the polybrominated diphenyl ether-containing solution next time by using the filtered solution and the polybrominated diphenyl ether flame retardant according to the mass ratio of 70: 3.
Example 2
As shown in fig. 1, a method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron comprises the following steps:
s1: preparation of sponge iron
Feeding iron ore powder and inorganic binder bentonite into a wet grinding machine through a screw feeding rod for wet grinding, wherein the mass ratio of the iron ore powder to the inorganic binder bentonite is 5:3, the wet grinding time is 35min, the rotating speed of the wet grinding machine is 85r/min, the particle size of the powder obtained after wet grinding is 30-40um, the wet grinding is more sufficient, the powder obtained after wet grinding, reducing coal and a desulfurizing agent are placed into a mixer according to the mass ratio of 1:0.6:0.05 for mixing, the desulfurizing agent is prepared by mixing silicon, calcium and manganese according to the mass ratio of 3:2:1, the desulfurizing effect is better, after the mixing is finished, the mixed powder is made into a hollow pipe, reducing coal powder with the thickness of 6.5cm is paved at the bottom of a ceramic reaction tank, the hollow pipe is placed into the ceramic reaction tank, the top of the ceramic reaction tank is sealed by using refractory soil, the ceramic reaction tank is heated for oxidation-reduction reaction, the heating temperature of the ceramic reaction tank in the oxidation-reduction reaction is 1050 ℃, the reaction time is 18h, the oxidation-reduction reaction is more thorough, the reaction is naturally cooled to room temperature along with the ceramic reaction tank after the oxidation-reduction reaction is completed, a sponge iron pipe body is obtained, the length of the obtained sponge iron pipe body is 4cm, the pipe diameter of the obtained sponge iron pipe body is 0.8cm, and the contact area of the obtained sponge iron pipe body and the solution is larger;
s2: preparation of biological sponge iron
Adding a microbial strain carrier agent into a culture medium solution to prepare a mixed culture solution, stirring the mixed culture solution to uniformly mix the culture medium solution and a microbial strain carrier agent, wherein the concentration of the microbial strain carrier agent in the prepared mixed culture solution is 8mg/ml, which is more favorable for degrading a polybrominated diphenyl ether flame retardant by strains, then inoculating the microbial strain into the mixed culture solution, wherein the inoculation amount of the microbial strain is 50g/L, the microbial strain inoculated by the mixed culture solution is prepared from brevibacillus brevis and stenotrophomonas maltophilia according to the mass ratio of 1:2, the effect of degrading the polybrominated diphenyl ether flame retardant is better, performing shake bed culture at the environment temperature of 35 ℃ for 65 hours to ensure that the microbial strain carrier agent is attached to the surface of the strains, then removing the liquid, performing low-temperature drying on the solid, and obtaining strain microspheres at the low-temperature drying temperature of 4 ℃, filling the interior of the sponge iron pipe body with the obtained strain microspheres to obtain biological sponge iron;
the microbial strain carrier agent is a mixture consisting of single-layer montmorillonite nanosheets and carbon fibers according to the weight ratio of 3:2, and has a better effect when being used as a carrier of a strain;
s3: activation enrichment of flame retardant
Adding a surface active agent into a polybrominated diphenyl ether flame retardant, wherein the addition amount of the surface active agent is 2% of the mass of the polybrominated diphenyl ether flame retardant, and the surface active agent is used for activating and enriching polybrominated diphenyl ether substances;
s4: degradation of flame retardants
Preparing polybrominated diphenyl ether flame retardant, deionized water, n-hexane and n-hexane-acetone into a polybrominated diphenyl ether-containing solution according to the mass ratio of 3:50:20:5, adding degradable polyelectrolyte and biological sponge iron into the polybrominated diphenyl ether-containing solution, detecting the polybrominated diphenyl ether content in the degraded solution after performing biodegradation culture for 6 days at room temperature, filtering the solution after completely degrading the polybrominated diphenyl ether in the degraded solution, and preparing the polybrominated diphenyl ether-containing solution next time by using the filtered solution and the polybrominated diphenyl ether flame retardant according to the mass ratio of 70: 3.
Example 3
As shown in fig. 1, a method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron comprises the following steps:
s1: preparation of sponge iron
Feeding iron ore powder and inorganic binder bentonite into a wet grinding machine through a screw feeding rod for wet grinding, wherein the mass ratio of the iron ore powder to the inorganic binder bentonite is 5:3, the wet grinding time is 40min, the rotating speed of the wet grinding machine is 90r/min, the particle size of powder obtained after wet grinding is 40-50um, the wet grinding is more sufficient, the powder obtained after wet grinding, reducing coal and a desulfurizing agent are placed into a mixer according to the mass ratio of 1:0.6:0.05 for mixing, the desulfurizing agent is prepared by mixing silicon, calcium and manganese according to the mass ratio of 3:2:1, the desulfurizing effect is better, the mixed powder is made into a hollow pipe after mixing is finished, reducing coal powder with the thickness of 7cm is paved at the bottom of a ceramic reaction tank, the hollow pipe is placed into the ceramic reaction tank, the top of the ceramic reaction tank is sealed by using refractory soil, the ceramic reaction tank is heated for oxidation-reduction reaction, the heating temperature of the ceramic reaction tank in the oxidation-reduction reaction is 1100 ℃, the reaction time is 20 hours, the oxidation-reduction reaction is more thorough, the reaction is naturally cooled to room temperature along with the ceramic reaction tank after the oxidation-reduction reaction is completed, a sponge iron pipe body is obtained, the length of the obtained sponge iron pipe body is 5cm, the pipe diameter of the obtained sponge iron pipe body is 1cm, and the contact area of the obtained sponge iron pipe body and the solution is larger;
s2: preparation of biological sponge iron
Adding a microbial strain carrier agent into a culture medium solution to prepare a mixed culture solution, stirring the mixed culture solution to uniformly mix the culture medium solution and a microbial strain carrier agent, wherein the concentration of the microbial strain carrier agent in the prepared mixed culture solution is 8mg/ml, which is more favorable for degrading a polybrominated diphenyl ether flame retardant by strains, then inoculating the microbial strain into the mixed culture solution, wherein the inoculation amount of the microbial strain is 50g/L, the microbial strain inoculated by the mixed culture solution is prepared from brevibacillus brevis and stenotrophomonas maltophilia according to the mass ratio of 1:2, the effect of degrading the polybrominated diphenyl ether flame retardant is better, performing shake bed culture at 40 ℃ for 80 hours to ensure that the microbial strain carrier agent is attached to the surface of the strains, then removing the liquid, performing low-temperature drying on the solid, and obtaining strain microspheres at the low-temperature drying temperature of 4 ℃, filling the interior of the sponge iron pipe body with the obtained strain microspheres to obtain biological sponge iron;
the microbial strain carrier agent is a mixture consisting of single-layer montmorillonite nanosheets and carbon fibers according to the weight ratio of 3:2, and has a better effect when being used as a carrier of a strain;
s3: activation enrichment of flame retardant
Adding a surface active agent into a polybrominated diphenyl ether flame retardant, wherein the addition amount of the surface active agent is 3% of the mass of the polybrominated diphenyl ether flame retardant, and the surface active agent is used for activating and enriching polybrominated diphenyl ether substances;
s4: degradation of flame retardants
Preparing polybrominated diphenyl ether flame retardant, deionized water, n-hexane and n-hexane-acetone into a polybrominated diphenyl ether-containing solution according to the mass ratio of 3:50:20:5, adding degradable polyelectrolyte and biological sponge iron into the polybrominated diphenyl ether-containing solution, detecting the polybrominated diphenyl ether content in the degraded solution after carrying out biodegradation culture for 7 days at room temperature, filtering the solution after the polybrominated diphenyl ether in the degraded solution is completely degraded, and preparing the polybrominated diphenyl ether-containing solution next time by using the filtered solution and the polybrominated diphenyl ether flame retardant according to the mass ratio of 70: 3.
Example 4
As shown in fig. 1, a method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron comprises the following steps:
s1: preparation of sponge iron
Feeding iron ore powder and inorganic binder bentonite into a wet grinding machine through a screw feeding rod for wet grinding, wherein the mass ratio of the iron ore powder to the inorganic binder bentonite is 5:3, the wet grinding time is 40min, the rotating speed of the wet grinding machine is 90r/min, the particle size of the powder obtained after wet grinding is 20-50um, the wet grinding is more sufficient, the powder obtained after wet grinding, reducing coal and a desulfurizing agent are placed into a mixer according to the mass ratio of 1:0.6:0.05 for mixing, the desulfurizing agent is prepared by mixing silicon, calcium and manganese according to the mass ratio of 3:2:1, the desulfurizing effect is better, the mixed powder is made into a hollow pipe after mixing is finished, reducing coal powder with the thickness of 7cm is paved at the bottom of a ceramic reaction tank, the hollow pipe is placed into the ceramic reaction tank, the top of the ceramic reaction tank is sealed by using refractory soil, the ceramic reaction tank is heated for oxidation-reduction reaction, the heating temperature of the ceramic reaction tank in the oxidation-reduction reaction is 1100 ℃, the reaction time is 20 hours, the oxidation-reduction reaction is more thorough, the reaction is naturally cooled to room temperature along with the ceramic reaction tank after the oxidation-reduction reaction is completed, a sponge iron pipe body is obtained, the length of the obtained sponge iron pipe body is 3cm, the pipe diameter of the obtained sponge iron pipe body is 0.5cm, and the contact area of the obtained sponge iron pipe body and the solution is larger;
s2: preparation of biological sponge iron
Adding a microbial strain carrier agent into a culture medium solution to prepare a mixed culture solution, stirring the mixed culture solution to uniformly mix the culture medium solution and a microbial strain carrier agent, wherein the concentration of the microbial strain carrier agent in the prepared mixed culture solution is 8mg/ml, which is more favorable for degrading a polybrominated diphenyl ether flame retardant by strains, then inoculating the microbial strain into the mixed culture solution, wherein the inoculation amount of the microbial strain is 50g/L, the microbial strain inoculated by the mixed culture solution is prepared from brevibacillus brevis and stenotrophomonas maltophilia according to the mass ratio of 1:2, the effect of degrading the polybrominated diphenyl ether flame retardant is better, performing shake bed culture at 40 ℃ for 80 hours to ensure that the microbial strain carrier agent is attached to the surface of the strains, then removing the liquid, performing low-temperature drying on the solid, and obtaining strain microspheres at the low-temperature drying temperature of 4 ℃, filling the interior of the sponge iron pipe body with the obtained strain microspheres to obtain biological sponge iron;
the microbial strain carrier agent is a mixture consisting of single-layer montmorillonite nanosheets and carbon fibers according to the weight ratio of 3:2, and has a better effect when being used as a carrier of a strain;
s3: activation enrichment of flame retardant
Adding a surface active agent into the polybrominated diphenyl ether flame retardant, wherein the addition amount of the surface active agent is 3% of the mass of the polybrominated diphenyl ether flame retardant, and the surface active agent is used for activating and enriching polybrominated diphenyl ether substances;
s4: degradation of flame retardants
Preparing polybrominated diphenyl ether flame retardant, deionized water, n-hexane and n-hexane-acetone into a polybrominated diphenyl ether-containing solution according to the mass ratio of 3:50:20:5, adding degradable polyelectrolyte and biological sponge iron into the polybrominated diphenyl ether-containing solution, detecting the polybrominated diphenyl ether content in the degraded solution after carrying out biodegradation culture for 7 days at room temperature, filtering the solution after the polybrominated diphenyl ether in the degraded solution is completely degraded, and preparing the polybrominated diphenyl ether-containing solution next time by using the filtered solution and the polybrominated diphenyl ether flame retardant according to the mass ratio of 70: 3.
The characteristics of Brevibacillus brevis and stenotrophomonas maltophilia:
brevibacillus brevis
Brevibacillus brevis is widely existed in plant rhizosphere soil, silt, rock, seawater and other environments. The discovery of Brevibacillus brevis and strong bacteriostatic activity thereof attract people to pay attention to Brevibacillus brevis, and the Brevibacillus brevis is considered as a potential biocontrol bacterium. The brevibacillus brevis has stronger protein secretion capability, and the secreted protein does not contain endotoxin. The brevibacillus brevis can synthesize and secrete a plurality of secondary metabolites and has strong bacteriostatic activity on a plurality of pathogenic bacteria.
The brevibacillus brevis can be used as a beneficial microorganism to kill or suppress the quantity of pathogenic organisms so as to control the occurrence of plant diseases.
Stenotrophomonas maltophilia
Stenotrophomonas maltophilia is a gram-negative bacterium of the genus xanthomonas that produces multiple flagella. It is widely present in water, soil, animals and plants in nature, and can also be detected from pharynx, oral cavity, phlegm and feces of normal human body. The bacteria can survive in almost any environment, have the capability of forming biofilms on various abiotic and biological surfaces, and have wide resistance to antibiotics, which has been classified as one of the multi-drug resistant bacteria for nosocomial infections by the world health organization.
Adsorption and degradation of stenotrophomonas maltophilia on cadmium ions
The stenotrophomonas maltophilia has a good adsorption effect on cadmium ions, the adsorption on cadmium is a process of first-speed and last-slow, the adsorption trend is gradually stable along with the prolonging of time, and the stable adsorption effect after 1 hour is 92.52%. Under the optimal adsorption condition that the mass concentration of the bacteria is 2.0g/L, the temperature is 25 ℃, and the pH value is 5, the adsorption effect is 93.73 percent best. Wherein the cell wall surface functional group C-H, N-H, O-H participates in the adsorption process as a main functional group.
Comparative example 1 to example 4, the content of polybrominated diphenyl ether substances in the solution was measured after 6 days of biodegradation culture, and the results are shown in Table 1:
table 1: examples 1-4 measurement results of the content of polybrominated diphenyl ethers in polybrominated diphenyl ether-containing solutions
As can be seen from the data in Table 1, in example 4, the content of polybrominated diphenyl ether substances in the solution was measured as the lowest polybrominated diphenyl ether content after 6 days of the biodegradation culture, and the duration of the biodegradation culture in example 4 was 7 days, and the content of polybrominated diphenyl ether substances in the polybrominated diphenyl ether-containing solution in example 4 was measured as 0mg/L after 7 days, which is sufficient to explain that example 4 is the most preferable example.
Claims (10)
1. A method for degrading polybrominated diphenyl ether flame retardant by utilizing biological sponge iron is characterized by comprising the following steps:
s1: preparation of sponge iron
Feeding iron ore powder and inorganic binder bentonite into a wet grinding machine through a spiral feeding rod for wet grinding, wherein the mass ratio of the iron ore powder to the inorganic binder bentonite is 5:3, placing the powder obtained after wet grinding, reducing coal and a desulfurizing agent into a mixer for mixing according to the mass ratio of 1:0.6:0.05, preparing the mixed powder into a hollow pipe after the mixing is finished, laying reducing coal powder with the thickness of 6-7cm at the bottom of a ceramic reaction tank, placing the hollow pipe into the ceramic reaction tank, sealing the top of the ceramic reaction tank with refractory soil, heating the ceramic reaction tank for oxidation-reduction reaction, and naturally cooling the ceramic reaction tank to room temperature after the oxidation-reduction reaction is finished to obtain a sponge iron pipe body;
s2: preparation of biological sponge iron
Adding a microbial strain carrier agent into a culture medium solution to prepare a mixed culture solution, stirring the mixed culture solution to uniformly mix the culture medium solution and the microbial strain carrier agent, then inoculating microbial strains into the mixed culture solution, wherein the inoculation amount of the microbial strains is 50g/L, performing shake culture at the ambient temperature of 30-40 ℃ for 60-80h to enable the microbial strain carrier agent to be attached to the surface of the strains, then removing the liquid, drying the solid at low temperature to obtain strain microspheres, and filling the obtained strain microspheres into the sponge iron tube body to obtain biological sponge iron;
s3: activation enrichment of flame retardant
Adding a surface active agent into the polybrominated diphenyl ether flame retardant, and then putting the flame retardant added with the surface active agent into a microwave reactor for microwave heating to activate and enrich polybrominated diphenyl ether substances;
s4: degradation of flame retardants
Preparing polybrominated diphenyl ether flame retardant, deionized water, normal hexane and normal hexane-acetone into a polybrominated diphenyl ether-containing solution according to the mass ratio of 3:50:20:5, then adding degradable polyelectrolyte and biological sponge iron into the polybrominated diphenyl ether-containing solution, wherein the addition amount of the degradable polyelectrolyte is 20g/L, the addition amount of the biological sponge iron is 50g/L, performing biodegradation culture at room temperature for 6-7 days, detecting the polybrominated diphenyl ether content in the degraded solution, filtering the solution after the polybrominated diphenyl ether in the degraded solution is completely degraded, and preparing the polybrominated diphenyl ether-containing solution next time according to the mass ratio of 70: 3.
2. The method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron as claimed in claim 1, wherein the duration of the wet grinding in step S1 is 30-40min, the rotating speed of the wet grinding machine is 80-90r/min, and the particle size of the obtained powder after the wet grinding is 20-50 um.
3. The method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron as claimed in claim 1, wherein the desulfurizing agent in the step S1 is prepared by mixing silicon, calcium and manganese according to a mass ratio of 3:2: 1.
4. The method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron as claimed in claim 1, wherein the heating temperature of the ceramic reaction tank in the redox reaction in step S1 is 1000-1100 ℃, and the reaction time is 13-20 h.
5. The method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron as claimed in claim 1, wherein the sponge iron tube obtained in the step S1 has a length of 3-5cm and a tube diameter of 0.5-1 cm.
6. The method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron as claimed in claim 1, wherein the microbial strain inoculated to the mixed culture solution in the step S2 is prepared from Brevibacillus brevis and stenotrophomonas maltophilia according to a mass ratio of 1: 2.
7. The method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron as claimed in claim 1, wherein the concentration of the microbial strain carrier in the mixed culture solution prepared in the step S2 is 8 mg/ml.
8. The method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron as claimed in claim 1, wherein the microbial strain carrier agent is a mixture of monolayer montmorillonite nanosheets and carbon fibers in a weight ratio of 3: 2.
9. The method for degrading polybrominated diphenyl ether flame retardant by using biological sponge iron as claimed in claim 1, wherein the amount of the surfactant added in step S3 is 1-3% by mass of the polybrominated diphenyl ether flame retardant.
10. The method for degrading polybrominated diphenyl ether flame retardant by using the biological sponge iron as claimed in claim 1, wherein the addition amount of the surfactant is 1-3% of the mass of the polybrominated diphenyl ether flame retardant.
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