WO2022100228A1 - 硫铁矿在污水处理中的应用方法 - Google Patents

硫铁矿在污水处理中的应用方法 Download PDF

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Publication number
WO2022100228A1
WO2022100228A1 PCT/CN2021/116013 CN2021116013W WO2022100228A1 WO 2022100228 A1 WO2022100228 A1 WO 2022100228A1 CN 2021116013 W CN2021116013 W CN 2021116013W WO 2022100228 A1 WO2022100228 A1 WO 2022100228A1
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pyrite
silane coupling
diaminoanthraquinone
parts
anthraquinone compound
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PCT/CN2021/116013
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English (en)
French (fr)
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严滨
李�雨
徐苏
叶茜
黄茵茵
刘斌
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厦门理工学院
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Publication of WO2022100228A1 publication Critical patent/WO2022100228A1/zh

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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
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention belongs to the technical field of sewage treatment, and relates to an application method of pyrite in sewage treatment.
  • Azo dyes, nitrates and other pollutants have become one of the important sources of water pollution, seriously affecting ecological epoxy and human health.
  • Chemical, physical and microbial methods have been reported to treat azo dyes, nitrates, etc., among which microbial methods are more efficient.
  • Anthraquinone compounds have been reported to promote and increase the rate of microbial degradation of azo dyes and nitrates, and the carriers include inorganic fillers, organic fillers, and the like. But researchers are still working on new materials to continue to improve the rate at which microorganisms degrade azo dyes and nitrates.
  • the purpose of the invention is to provide a new application method of pyrite in sewage treatment in order to overcome the defect that the degradation rate is relatively slow when the existing methods are used to degrade the azo dyes and nitrates in the sewage. Can significantly improve the degradation rate of azo dyes and nitrates.
  • the application method of pyrite in sewage treatment includes the following steps:
  • the surface of the pyrite is treated with a silane coupling agent to obtain the treated pyrite;
  • the surface of the treated pyrite is modified by chemically grafting an anthraquinone compound to obtain a modified pyrite;
  • the sewage contains one or both of nitrates and azo dyes.
  • the average particle size of the pyrite is 1-5000 ⁇ m. More preferably, the average particle size of the pyrite is 10-1000 ⁇ m, and even more preferably, the average particle size of the pyrite is 50-300 ⁇ m.
  • the method for treating the pyrite surface with silane coupling agent is as follows: dissolve 1 part by weight of silane coupling agent in 80 parts by weight of a mixed solvent of absolute ethanol and deionized water in a volume ratio of 90:10, adjust The pH is 4 to 5, stirring for 0.5 hours to obtain a silane treatment solution, 1 part by weight of pyrite is placed in 5 parts by weight of the silane treatment solution, the temperature is raised to a slight reflux, the reaction is slightly stirred for 2 hours, and washed with anhydrous ethanol for 3 and drying to obtain the treated pyrite.
  • There are many methods for treating pyrite surface with silane coupling agent and most of the methods conventionally applied to the surface treatment of inorganic fillers are suitable for pyrite.
  • the silane coupling agent is selected from epoxy silane coupling agent or mercapto silane coupling agent.
  • the epoxy silane coupling agent may be selected from 3-(2,3-glycidoxy)propyltrimethoxysilane, 3-(2,3-glycidoxy)propyltriethoxysilane, 3-(2,3-glycidoxy)propyltriethoxysilane, (2,3-glycidoxy)propylmethyldiethoxysilane, 3-(2,3-glycidoxy)propylmethyldimethoxysilane, 2-(3,4-ring Oxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane One or more of silane and 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane.
  • the mercaptosilane coupling agent may be selected from 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethyl One or more of oxysilanes.
  • the chemical method of grafting is the reaction of epoxy group with anthraquinone compound or the reaction of mercapto group with anthraquinone compound.
  • the silane coupling agent is selected from epoxy silane coupling agents
  • the anthraquinone compound is selected from amino-containing anthraquinone compounds.
  • the amino-containing anthraquinone compound is selected from 1-amino-2-bromo-4-hydroxyanthraquinone, 2-aminoanthraquinone, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, Aminoanthraquinone, 2,6-diaminoanthraquinone, 1,8-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1-amino-2-methylanthraquinone, 1,5-dihydroxy-4 , One or more of 8-diaminoanthraquinone and 1-aminoanthraquinone.
  • the silane coupling agent is selected from mercapto silane coupling agents
  • the anthraquinone compound is selected from vinyl-containing anthraquinone compounds.
  • the vinyl-containing anthraquinone compound is selected from 1-allyloxy-4-hydroxyanthraquinone-9,10-dione and 1-amino-4-allyloxyanthraquinone one or both.
  • the present invention utilizes the redox properties of pyrite and the ability to transfer electrons, and enhances the use of anthraquinone as a redox mediator to promote the degradation rate of nitrates and azo dyes by microorganisms, so that nitrates and azo dyes are improved. microbial degradation rate is faster.
  • Pyrite has a wide range of sources and low cost, and can better exert the ability of anthraquinone to degrade nitrates and azo dyes.
  • the present invention uses pyrite as a carrier to promote the degradation of nitrates and azo dyes by anthraquinone-promoting microorganisms, which has a different principle from the existing carriers.
  • the pyrite of the present invention can be reused after simple recovery treatment.
  • Silane treatment solution 1 Dissolve 1 part of 3-(2,3-glycidoxy)propyltrimethoxysilane in 80 parts of a mixed solvent of absolute ethanol and deionized water with a volume ratio of 90:10, adjust the pH to 4.5, and stir for 1 hour , Silane treatment solution 1 was obtained. 1 part of pyrite with an average particle size of 100 ⁇ m was placed in 5 parts of the above-mentioned silane treatment solution 1, the temperature was raised to a slight reflux, the reaction was slightly stirred for 2 hours, washed with absolute ethanol 3 times, and dried to obtain epoxy pyrite 1 .
  • silane treatment solution 3 1 part of 3-mercaptopropyltrimethoxysilane was dissolved in 100 parts of a mixed solvent of absolute ethanol and deionized water with a volume ratio of 85:15, adjusted to pH 4.0, and stirred for 1 hour to obtain silane treatment solution 3.
  • One part of pyrite with an average particle size of 450 ⁇ m was placed in 10 parts of the above-mentioned silane treatment solution 3, the temperature was raised to slight reflux, the reaction was slightly stirred for 2 hours, washed three times with absolute ethanol, and dried to obtain mercapto pyrite.
  • the tourmaline having an average particle diameter of 100 ⁇ m was treated with 3-(2,3-glycidoxy)propyltrimethoxysilane to obtain epoxy tourmaline.
  • Solid glass microspheres with an average particle size of 100 ⁇ m were treated with 3-(2,3-glycidoxy)propyltrimethoxysilane to obtain epoxy-based solid glass microspheres.
  • the talc powder with an average particle size of 100 ⁇ m was treated with 3-(2,3-glycidoxy)propyltrimethoxysilane to obtain epoxy-based talc powder.
  • 10 parts of epoxy talc, 2.3 parts of 2,6-diaminoanthraquinone, 160 parts of tetrahydrofuran and 0.7 part of 1-methylimidazole were mixed uniformly, stirred at room temperature for 5 hours, filtered, and the filtered solid was washed and dried to obtain Modified talc.
  • Degradation acceleration effect test on azo dyes 2 g of the sample to be tested and 2 g of pyrite with an average particle size of 100 ⁇ m were washed with physiological saline for 3 times, and then added to 200 ml of the azo dye-degrading strain GYZ (staphylococcus staphylococcus sp.) in 120 mg/L Acid Red B to conduct a decolorization test to determine the change in acid red B concentration with time. The results are shown in Table 1.
  • Test for the acceleration effect of nitrate degradation 2g of the sample to be tested and 2g of pyrite with an average particle size of 100 ⁇ m were washed with physiological saline for 3 times, and then added to 200ml of 150mg/L nitrate containing denitrifying microorganisms in logarithmic growth phase. Tests were carried out in wastewater to determine the change in nitrate concentration over time. The results are shown in Table 2.
  • the chemically grafted anthraquinone compound of the pyrite of the present invention has a good effect in promoting the microbial degradation of azo dyes and nitrates.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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)

Abstract

本发明属于污水处理技术领域，具体是硫铁矿在污水处理中的应用方法，硫铁矿表面经过硅烷处理后获得环氧基或者巯基基团，再与相应的蒽醌化合物反应，硫铁矿表面化学接枝蒽醌化合物。本发明利用了硫铁矿氧化还原的性质，提升了蒽醌化合物促进偶氮染料、硝酸盐生物降解的速率，具有较好的污水处理效果。

Description

硫铁矿在污水处理中的应用方法 技术领域
本发明属于污水处理技术领域，涉及硫铁矿在污水处理中的应用方法。
背景技术
偶氮染料、硝酸盐等污染物已成为水体污染的重要污染源之一，严重影响到生态环氧和人体健康。已报道有化学、物理以及微生物的方法处理偶氮染料、硝酸盐等，其中微生物法效率较高。蒽醌化合物已报道用于促进提升微生物降解偶氮染料、硝酸盐的速率，而且载体有无机填料、有机填料等。但研究者仍然在研究新的材料以继续提升微生物降解偶氮染料、硝酸盐的速率。
发明内容
发明的目的是为了克服采用现有的方法对污水中的偶氮染料和硝酸盐进行降解时降解速率较慢的缺陷，而提供一种新的硫铁矿在污水处理中的应用方法，该方法能够显著提高偶氮染料和硝酸盐的降解速率。
本发明的技术方案如下：
硫铁矿在污水处理中的应用方法，包括以下步骤：
S1、硫铁矿表面经过硅烷偶联剂处理，获得处理的硫铁矿；
S2、处理的硫铁矿表面通过化学方法接枝蒽醌化合物进行改性，获得改性的硫铁矿；
S3、将改性的硫铁矿放置在污水中对所述污水进行处理。
在优选的方案中，所述污水含有硝酸盐和偶氮染料中的一种或两种。
在优选的方案中，所述硫铁矿的平均粒径为1～5000μm。更优选的，所述硫铁矿的平均粒径为10～1000μm，再优选的，所述硫铁矿的平均粒径为50～300μm。
在优选的方案中，硫铁矿表面硅烷偶联剂处理的方法为：将1重量份硅烷偶联剂溶于80重量份体积比90:10的无水乙醇和去离子水混合溶剂中，调节pH为4～5，搅拌0.5小时，获得硅烷处理液，将1重量份硫铁矿置于5重量份所述硅烷处理液中，升温至微回流，轻微搅拌反应2小时，无水乙醇洗涤3次，干燥，获得处理的硫铁矿。硫铁矿表面硅烷偶联剂处理的方法较多，常规应用于无机填料表面处理的方法大部分适合于硫铁矿。
在更优选的方案中，所述硅烷偶联剂选自环氧基硅烷偶联剂或巯基硅烷偶联剂。
环氧基硅烷偶联剂可以选自3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-(2,3环氧丙氧)丙基三乙氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二乙氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、2-(3,4-环氧环己基)乙基三乙氧基硅烷、2-(3,4-环氧环己基)乙基甲基二乙氧基硅烷和2-(3,4-环氧环己基)乙基甲基二甲氧基硅烷中的一种或几种。
巯基硅烷偶联剂可以选自3-巯基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、3-巯基丙基甲基二甲氧硅烷和3-巯基丙基甲基二乙氧基硅烷中的一种或几种。
在进一步优选的方案中，所述化学方法接枝为环氧基与蒽醌化合物反应或者巯基与蒽醌化合物反应。
在更进一步优选的方案中，所述硅烷偶联剂选自环氧基硅烷偶联剂，所述蒽醌化合物选自含氨基蒽醌化合物。
再进一步优选的方案中，所述含氨基蒽醌化合物选自1-氨基-2-溴-4-羟基蒽醌、2-氨基蒽醌、1,2-二氨基蒽醌、1,4-二氨基蒽醌、2,6-二氨基蒽醌、1,8-二氨基蒽醌、1,5-二氨基蒽醌、1-氨基-2-甲基蒽醌、1,5-二羟基-4,8-二氨基蒽醌和1-氨基蒽醌中的一种或几种。
在更进一步优选的方案中，所述硅烷偶联剂选自巯基硅烷偶联剂，所述蒽醌化合物选自含乙烯基蒽醌化合物。
再进一步优选的方案中，所述含乙烯基蒽醌化合物选自1-烯丙氧基-4-羟基蒽醌-9,10-二酮和1-氨基-4-烯丙氧基蒽醌中的一种或两种。
本发明的有益效果是：
(1)本发明利用硫铁矿的氧化还原性能、具有转移电子的能力，提升了蒽醌作为氧化还原介体促进提升微生物对硝酸盐和偶氮染料的降解速率，使得硝酸盐和偶氮染料的微生物降解速率更快。
(2)硫铁矿来源广泛、成本低，能更好的发挥蒽醌对硝酸盐和偶氮染料的降解能力。
(3)本发明采用硫铁矿作为载体促进蒽醌提升微生物对硝酸盐和偶氮染料的降解与现有的载体具有不一样的原理。
(4)本发明的硫铁矿经过简单的回收处理后可重新使用。
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。
如无特别指明，以下各实施例中所述份数为重量份数。
实施例1
将1份3-(2,3-环氧丙氧)丙基三甲氧基硅烷溶于80份体积比90:10的无水乙醇和去离子水混合溶剂中，调节pH为4.5，搅拌1小时，获得硅烷处理液1。将1份平均粒径100μm的硫铁矿置于5份上述硅烷处理液1中，升温至微回流，轻微搅拌反应2小时，无水乙醇洗涤3次，干燥，获得环氧基硫铁矿1。
实施例2
将1份2-(3,4-环氧环己基)乙基三甲氧基硅烷溶于100份体积比85:15的无水乙醇和去离子水混合溶剂中，调节pH为4.0，搅拌0.5小时，获得硅烷处理液2。将1份平均粒径300μm的硫铁矿置于10份上述硅烷处理液2中，升温至微回流，轻微搅拌反应2小时，无水乙醇洗涤3次，干燥，获得环氧基硫铁矿2。
实施例3
将1份3-巯基丙基三甲氧基硅烷溶于100份体积比85:15的无水乙醇和去离子水混合溶剂中，调节pH为4.0，搅拌1小时，获得硅烷处理液3。将1份 平均粒径450μm的硫铁矿置于10份上述硅烷处理液3中，升温至微回流，轻微搅拌反应2小时，无水乙醇洗涤3次，干燥，获得巯基硫铁矿。
实施例4
将10份实施例1中获得的环氧基硫铁矿1、2份2-氨基蒽醌、200份四氢呋喃和0.6份2-甲基咪唑混合均匀，室温下搅拌6小时，过滤，滤出固体清洗、干燥，获得改性硫铁矿1。
实施例5
将10份实施例1中获得的环氧基硫铁矿1、3份1,4-二氨基蒽醌、200份四氢呋喃和0.4份2-甲基咪唑混合均匀，室温下搅拌8小时，过滤，滤出固体清洗、干燥，获得改性硫铁矿2。
实施例6
将10份实施例2中获得的环氧基硫铁矿2、2.3份2,6-二氨基蒽醌、160份四氢呋喃和0.7份1-甲基咪唑混合均匀，室温下搅拌5小时，过滤，滤出固体清洗、干燥，获得改性硫铁矿3。
实施例7
将10份实施例2中获得的环氧基硫铁矿2、2.7份1-氨基蒽醌、160份无水乙醇和0.8份1-甲基咪唑混合均匀，室温下搅拌4小时，过滤，滤出固体清洗、干燥，获得改性硫铁矿4。
实施例8
将10份实施例2中获得的环氧基硫铁矿2、1.4份1-氨基-2-甲基蒽醌、180份无水乙醇和0.7份1-甲基咪唑混合均匀，室温下搅拌7小时，过滤，滤出固体清洗、干燥，获得改性硫铁矿5。
实施例9
将10份实施例3中获得的巯基硫铁矿、3.2份1-烯丙氧基-4-羟基蒽醌-9,10-二酮、230份四氢呋喃和0.01份安息香双甲醚混合均匀，搅拌下在主波长365nm、强度5mW/cm 2的紫外光下照射4min，撤除紫外光，过滤，滤出固体清洗、干燥，获得改性硫铁矿6。
实施例10
将10份实施例3中获得的巯基硫铁矿、2.2份1-氨基-4-烯丙氧基蒽醌、200份四氢呋喃和0.01份安息香双甲醚混合均匀，搅拌下在主波长365nm、强度5mW/cm 2的紫外光下照射3.5min，撤除紫外光，过滤，滤出固体清洗、干燥，获得改性硫铁矿7。
对比例1
平均粒径100μm的电气石用3-(2,3-环氧丙氧)丙基三甲氧基硅烷处理后获得环氧基电气石。将10份环氧基电气石、2.3份2,6-二氨基蒽醌、160份四氢呋喃和0.7份1-甲基咪唑混合均匀，室温下搅拌5小时，过滤，滤出固体清洗、干燥，获得改性电气石。
对比例2
平均粒径100μm的实心玻璃微球用3-(2,3-环氧丙氧)丙基三甲氧基硅烷处理后获得环氧基实心玻璃微球。将10份环氧基实心玻璃微球、2.3份2,6-二氨基蒽醌、160份四氢呋喃和0.7份1-甲基咪唑混合均匀，室温下搅拌5小时，过滤，滤出固体清洗、干燥，获得改性实心玻璃微球。
对比例3
平均粒径100μm的滑石粉用3-(2,3-环氧丙氧)丙基三甲氧基硅烷处理后获得环氧基滑石粉。将10份环氧基滑石粉、2.3份2,6-二氨基蒽醌、160份四氢呋喃和0.7份1-甲基咪唑混合均匀，室温下搅拌5小时，过滤，滤出固体清洗、干燥，获得改性滑石粉。
应用对比
对偶氮染料的降解加速效果测试：分别将2g待测样品和2g平均粒径100μm的硫铁矿用生理盐水冲洗3次后，加入到200ml含对数生长期的偶氮染料降解菌株GYZ(staphylococcus sp.)的120mg/L的酸性红B中进行脱色测试，测定酸性红B浓度随时间的变化。结果如表1所示。
表1
Figure PCTCN2021116013-appb-000001
从表1的结果可知，本发明的硫铁矿化学接枝蒽醌化合物后对偶氮染料具有较好的促进提升微生物降解速率的效果。
对硝酸盐降解加速效果测试：分别将2g待测样品和2g平均粒径100μm的硫铁矿用生理盐水冲洗3次后，加入到200ml含对数生长期反硝化微生物的150mg/L的硝酸盐废水中进行测试，测定硝酸盐浓度随时间的变化。结果如表2所示。
表2
Figure PCTCN2021116013-appb-000002
Figure PCTCN2021116013-appb-000003
从表2的结果可知，本发明的硫铁矿化学接枝蒽醌化合物后对硝酸盐具有较好的促进提升微生物降解速率的效果。
稳定性测试：分别将2g待测样品用生理盐水冲洗3次后，加入到200ml含对数生长期的偶氮染料降解菌株GYZ(staphylococcus sp.)的120mg/L的酸性红B中进行脱色测试，测定6小时后酸性红B的浓度。再将待测样品用清水和无水乙醇清洗干燥后再按上述方法用酸性红B进行脱色测试6小时，如此反复测试12次。结果如表3所示。
表3
Figure PCTCN2021116013-appb-000004
表3结果显示，本发明的硫铁矿化学接枝蒽醌化合物后在促进提升偶氮染料的微生物降解的速率上具有较好的稳定性。
综上所述，本发明的硫铁矿化学接枝蒽醌化合物后在促进提升偶氮染料和硝酸盐的微生物降解上具有较好的效果。
如上所述，显示和描述了本发明的基本原理、主要特征和优点。本领域技术人员应该了解本发明不受上述实施例的限制，上述实施例仅为本发明的较佳实施例而已，不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。本发明要求保护范围由所附的权利要求书及其等同物界定。

Claims (6)

  1. 硫铁矿在污水处理中的应用方法，其特征在于，包括以下步骤：
    S1、所述硫铁矿表面经过硅烷偶联剂处理，获得处理的硫铁矿；
    S2、所述处理的硫铁矿表面通过化学方法接枝蒽醌化合物进行改性，获得改性的硫铁矿；所述化学方法接枝为环氧基与蒽醌化合物反应或者巯基与蒽醌化合物反应；所述硅烷偶联剂选自环氧基硅烷偶联剂且所述蒽醌化合物选自含氨基蒽醌化合物，或者，所述硅烷偶联剂选自巯基硅烷偶联剂且所述蒽醌化合物选自含乙烯基蒽醌化合物；
    S3、将所述改性的硫铁矿放置在所述污水中对所述污水进行处理。
  2. 根据权利要求1所述的应用方法，其特征在于，所述污水含有硝酸盐和偶氮染料中的一种或两种。
  3. 根据权利要求1所述的应用方法，其特征在于，所述硫铁矿的平均粒径为1～5000μm。
  4. 根据权利要求1所述的应用方法，其特征在于，步骤S1中硫铁矿表面硅烷偶联剂处理的方法为：将1重量份所述硅烷偶联剂溶于80重量份体积比90:10的无水乙醇和去离子水混合溶剂中，调节pH为4～5，搅拌0.5小时，获得硅烷处理液，将1重量份所述硫铁矿置于5重量份所述硅烷处理液中，升温至微回流，轻微搅拌反应2小时，无水乙醇洗涤3次，干燥，获得所述处理的硫铁矿。
  5. 根据权利要求1所述的应用方法，其特征在于，所述含氨基蒽醌化合物选自1-氨基-2-溴-4-羟基蒽醌、2-氨基蒽醌、1,2-二氨基蒽醌、1,4-二氨基蒽醌、2,6-二氨基蒽醌、1,8-二氨基蒽醌、1,5-二氨基蒽醌、1-氨基-2-甲基蒽醌、1,5-二羟基-4,8-二氨基蒽醌和1-氨基蒽醌中的一种或几种。
  6. 根据权利要求1所述的应用方法，其特征在于，所述含乙烯基蒽醌化合物选自1-烯丙氧基-4-羟基蒽醌-9,10-二酮和1-氨基-4-烯丙氧基蒽醌中的一种或两种。
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