CN114853129A - In-situ composite aluminum ferrite water treatment agent and preparation method and application method thereof - Google Patents

In-situ composite aluminum ferrite water treatment agent and preparation method and application method thereof Download PDF

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CN114853129A
CN114853129A CN202210565095.6A CN202210565095A CN114853129A CN 114853129 A CN114853129 A CN 114853129A CN 202210565095 A CN202210565095 A CN 202210565095A CN 114853129 A CN114853129 A CN 114853129A
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water treatment
treatment agent
situ composite
composite aluminum
aluminum ferrite
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CN114853129B (en
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韩晓刚
顾玲玲
蔡建刚
闵建军
顾一飞
蒋晓春
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Changzhou Qingliu Environmental Protection Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention relates to an in-situ composite aluminum ferrite water treatment agent, a preparation method and an application method thereof, and the in-situ composite aluminum ferrite water treatment agent comprises the following steps: in the presence of Fe 3+ Adding an insoluble aluminum source into the aqueous solution, and pulping uniformly to obtain a mixed material; then adding alkali, heating to 50-85 ℃, uniformly dissolving the mixed material, continuously stirring, and keeping the temperature for at least 30min to obtain a suspension; then adding a chlorine-containing oxidant to carry out oxidation reaction to obtain the in-situ composite aluminum ferrite water treatment agent. The in-situ compounded aluminum ferrite water treatment agent has better flocculation performance and storage stability, and also has better bactericidal performance.

Description

In-situ composite aluminum ferrite water treatment agent and preparation method and application method thereof
Technical Field
The invention relates to the technical field of water treatment agents, and particularly relates to an in-situ composite aluminum ferrite water treatment agent and a preparation method and an application method thereof.
Background
With the continuous development of social industrialization and urbanization, a difficult and important task of environmental protection workers is sewage purification. In the aspects of sewage treatment, waste water treatment, water purification and the like, various flocculants are required to be used for removing impurities in water and settling and removing the impurities by water-insoluble dispersed substances. The flocculation sedimentation method has the advantages of economy, convenience and high efficiency in the water treatment technology, and is often applied to the aspects of a preposed unit of biochemical treatment, sludge dewatering, high-turbidity water supply and the like in the water treatment process. After the flocculating agent is added into the wastewater, pollutants in the wastewater are aggregated to form large particles (alum flowers) to be removed by sedimentation. Flocculant removal 10 -3 -10 -6 mm suspended particles, metal ions, oil substances, pigments and other organic and inorganic substances, and the commonly used flocculating agents can be divided into inorganic flocculating agents, organic flocculating agents, microbial flocculating agents, composite flocculating agents and the like.
The inorganic flocculant includes inorganic low molecular flocculant, aluminum salt system and iron salt system. Common aluminum salts include aluminum sulfate, alum, sodium aluminate, aluminum chloride, etc.; iron salts commonly used are ferric sulfate, ferric chloride, ferrous sulfate, and the like. Sodium aluminate and sodium ferrate are both alkaline water treatment agents. Sodium ferrate has poor stability. Although the sodium aluminate can solve the problem of pH value adjustment in the weakly acidic water treatment process, the flocculation alum floc of the sodium aluminate used in the water treatment process is not large, and the sedimentation performance is not good.
Therefore, in order to solve the problems of poor stability of ferrate and poor flocculation performance of sodium aluminate, the sodium ferrate and the sodium aluminate are synthesized in situ, so that the problem of water control effect in the water treatment process can be effectively solved.
Disclosure of Invention
In order to solve the problems of poor stability of ferrate and poor flocculation performance of sodium aluminate, an in-situ composite aluminum ferrite water treatment agent, a preparation method and an application method thereof are provided. The in-situ composite aluminum ferrite medicament can overcome the defects of small aluminums alum floc, difficult precipitation and single function of the traditional water treatment agent sodium aluminate in the water treatment process, and simultaneously has better storage stability of the product.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of an in-situ composite aluminum ferrite water treatment agent comprises the following steps:
in the presence of Fe 3+ Adding an insoluble aluminum source into the aqueous solution, and pulping uniformly to obtain a mixed material; then adding alkali, heating to 50-85 ℃, uniformly dissolving the mixed material, continuously stirring, and keeping the temperature for at least 30min to obtain a suspension; then adding a chlorine-containing oxidant to carry out oxidation reaction to obtain the in-situ composite aluminum ferrite water treatment agent.
Further, the insoluble aluminum source is aluminum hydroxide and/or pseudo-boehmite; said Fe-containing 3+ The water solution is one or more of ferric chloride (III) water solution and ferric sulfate (III) water solution; the alkali is sodium hydroxide and/or potassium hydroxide; the chlorine-containing oxidizing agent is one or more of sodium hypochlorite, potassium hypochlorite, sodium chlorate and potassium chlorate, preferably sodium hypochlorite and/or potassium hypochlorite, and the oxidizing agent is preferably hypochlorite because chlorate is relatively stable and cannot rapidly exert oxidizing property in a strong alkaline environment.
Further, the Fe content 3+ Fe in aqueous solution 3+ The content of (A) is more than 0.5 mol/L; said Fe-containing 3+ Fe in aqueous solution 3+ The mol ratio of the insoluble aluminum source to the alkali to the chlorine-containing oxidant is (1-2.5) to (0.3-1.2) to (1-3.5) to (0.1-5).
Further, the heating temperature is 70-80 ℃, and the heat preservation time is 1-2 h.
Further, the in-situ composite aluminum ferrite water treatment agent is in a liquid state.
On the other hand, the invention provides the in-situ composite aluminum ferrite water treatment agent prepared by the preparation method, wherein the content of alumina in the composite aluminum ferrite water treatment agent is more than or equal to 8 wt%, and Fe 6+ The compound content is more than or equal to 1.5 wt%, and the causticization coefficient is at least 2.
The third aspect of the invention provides an application method of the in-situ composite aluminum ferrite water treatment agent prepared by the preparation method, wherein the in-situ composite aluminum ferrite water treatment agent is added into water to be treated, and impurities in the water are flocculated and settled by stirring; the dosage of the in-situ composite aluminum ferrite water treatment agent in the water to be treated is less than 50 mg/L.
Further, the water to be treated is sewage or wastewater.
The beneficial technical effects are as follows: adding aluminum hydroxide and alkali such as sodium hydroxide into Fe (III) solution, heating to dissolve insoluble substances, carrying out heat preservation reaction, forming a complex by aluminate radicals and iron (III) in the heat preservation process to obtain suspension, and adding an oxidant to oxidize Fe (III) in situ to Fe (VI) so as to finally obtain the in-situ composite aluminum ferrite water treatment agent. The in-situ compounded aluminum ferrite water treatment agent has better flocculation performance and storage stability, and also has better bactericidal performance.
Drawings
FIG. 1 is an XRD pattern of an in-situ compounded aluminum ferrite water treatment agent Fe (VI) -SA of example 1 and a conventional water treatment agent sodium aluminate SA of comparative example 1, wherein A represents a product of comparative example 1 and B represents a product of example 1. The above XRD test shows that the materials are all solid, and the product of example 1 is dried and then detected.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement proposed by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
A preparation method of an in-situ composite aluminum ferrite water treatment agent comprises the following steps:
adding 200g (1.2330mol) of ferric chloride (III) into 300g of water, stirring uniformly, adding 39g (0.5mol) of aluminum hydroxide, pulping uniformly to obtain a mixed material, then adding 40g (1mol) of sodium hydroxide, heating to 75 ℃ to uniformly dissolve insoluble substances in the mixed material, and keeping the temperature for 1 h; and then adding 10g (0.1343mol) of sodium hypochlorite to turn the material into yellow brown, and continuously stirring until the material becomes a mauve bright solution to obtain the in-situ composite sodium aluminoferrite water treatment agent, wherein the product name is Fe (VI) -SA.
The liquid product of this example is stable for at least 3 months at temperatures no higher than 40 ℃ without sediment.
Example 2
A preparation method of an in-situ composite aluminum ferrite water treatment agent comprises the following steps:
adding 200g (1.2330mol) of ferric chloride (III) into 300g of water, stirring uniformly, adding 78g (1mol) of aluminum hydroxide, pulping uniformly to obtain a mixed material, then adding 120g (3mol) of sodium hydroxide, heating to 80 ℃ to uniformly dissolve insoluble substances in the mixed material, and keeping the temperature for 1.5 h; and then adding 45g (0.4970mol) of potassium hypochlorite to turn the material into yellow brown, and continuously stirring until the material becomes a mauve bright solution, thus obtaining the in-situ composite sodium aluminoferrite water treatment agent, wherein the product name is Fe (VI) -SA.
The liquid product of this example is stable for at least 3 months at temperatures no higher than 40 ℃ without sediment.
Example 3
A preparation method of an in-situ composite aluminum ferrite water treatment agent comprises the following steps:
adding 400g (2.4660mol) of ferric chloride (III) into 300g of water, stirring uniformly, adding 102g (1mol) of pseudo-boehmite, pulping uniformly to obtain a mixed material, then adding 100g (2.5mol) of sodium hydroxide, heating to 70 ℃ to uniformly dissolve insoluble substances in the mixed material, and keeping the temperature for 2 hours; and adding 74.5g (1mol) of sodium hypochlorite to change the material into yellow brown, and continuously stirring until the material becomes a mauve bright solution to obtain the in-situ composite sodium aluminoferrite water treatment agent, wherein the product name is Fe (VI) -SA.
The liquid product of this example is stable for at least 3 months at temperatures no higher than 40 ℃ without sediment.
Comparative example 1
The comparative example is a commercial sodium aluminate SA product of the traditional water treatment agent, and is provided by a Zibo river water purification material factory. Sodium aluminate has traditionally been a solid product which is dissolved in deionized water to give a 50 wt% sodium aluminate solution, and precipitation is observed after storage for 1 day at temperatures not higher than 40 ℃.
Comparative example 2
This comparative example is a commercial solid product of sodium ferrate. After the suspension is dissolved in deionized water to prepare a 10 wt% solution and placed at room temperature for 3 days, the purple red color of the suspension is completely faded and becomes a soil yellow suspension. This is Fe 6+ Reduction to Fe 3+ After iron ion, Fe (OH) is formed 3 Caused by precipitation.
Specific substance contents and parameters in the in-situ composite sodium aluminoferrite water treatment agent Fe (VI) -SA and the comparative sodium aluminate SA in the examples are searched, and the specific parameters are shown in Table 1.
TABLE 1 parameters of Fe (VI) -SA for examples and SA for comparative examples
Figure BDA0003657626210000041
As can be seen from Table 1, the causticization coefficient of the in-situ composite sodium aluminoferrite water treatment agent Fe (VI) -SA is higher and is more than 2.
The XRD patterns of the Fe (VI) -SA of the product of example 1 and the SA of the comparative example 1 are shown in figure 1, and as can be seen from figure 1, the diffraction peak of Fe (VI) appears in the product of example 1, which proves that Fe (VI) is compounded into the sodium aluminate crystals in situ. The products of example 2 and example 3 were also examined and the peak positions were essentially the same.
The storage stability at 38 ℃ of the product of example 1 and of the product of comparative example 2 is shown in Table 2.
TABLE 2 storage stability at 38 ℃ of the product Fe (VI) -SA of example 1 and of the product of comparative example 2
Figure BDA0003657626210000042
Figure BDA0003657626210000051
As can be seen from Table 2, the in-situ composite sodium aluminoferrite water treatment agent formed by in-situ compounding of high-valence iron in the process of preparing sodium aluminate has high storage stability at 38 ℃, and the effective substance Fe 6+ The content is reduced slightly, and the product can be stored for more than 3 months.
Application example 1
The Fe (VI) -SA product obtained in the above example and the comparative product are applied to sewage treatment by adding the Fe (VI) -SA product obtained in the above example and the water treatment agent obtained in the comparative product into water to be treated, and the impurities in the water are flocculated and settled by stirring in a coagulation way.
By COD Mn The data characterize the cleaning effect of the water treatment agent and the results are shown in table 3.
TABLE 3 effluent COD of treated wastewater of Fe (VI) -SA product obtained in example and COD of treated wastewater of comparative example 1 at different dosages Mn The result of the detection
Figure BDA0003657626210000052
As can be seen from Table 3, the product of the invention, sodium aluminate, which is obtained by compounding high-valence iron in situ, has better purification effect, and COD removal effect is better than that of sodium aluminate.
The coagulation effect of the water treatment agent was characterized by the residual turbidity and the results are shown in table 4.
Table 4 results of residual turbidity detection of effluent after sewage treatment by using Fe (VI) -SA as product in example and product in comparative example 1 at different adding amounts
Figure BDA0003657626210000053
As can be seen from Table 4, the product of the invention, sodium aluminate obtained by in-situ compounding high-valence iron, has better coagulation effect and better sedimentation performance compared with sodium aluminate.
The bactericidal effect of the products of the examples of the invention was also evaluated and the results are shown in table 5.
TABLE 5 bactericidal Effect of the product Fe (VI) -SA of example 1 on wastewater at different dosages
Figure BDA0003657626210000061
As can be seen from Table 5, the sodium aluminate obtained by compounding the high-valence iron in situ according to the invention has a certain bactericidal property in addition to a good coagulation effect and a good COD removal effect.
The reason why the sodium aluminate product of the in-situ composite high-valence iron has better coagulation and COD removal effects is probably that a certain form of bonding effect is generated between Fe (VI) and Al ion hydrolysate in Fe (VI) -SA to generate a polymerization product, and Fe (VI) has a polymerization effect on Al polymer, so that the water purification effect of the product is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (8)

1. A preparation method of an in-situ composite aluminum ferrite water treatment agent is characterized by comprising the following steps:
in the presence of Fe 3+ Adding an insoluble aluminum source into the aqueous solution, and pulping uniformly to obtain a mixed material; then adding alkali, heating to 50-85 ℃, uniformly dissolving the mixed material, continuously stirring, and keeping the temperature for at least 30min to obtain a suspension; then adding a chlorine-containing oxidant to carry out oxidation reaction to obtain the in-situ composite aluminum ferrite water treatment agent.
2. The method for preparing the in-situ composite aluminum ferrite water treatment agent as claimed in claim 1, wherein the insoluble aluminum source is aluminum hydroxide and/or pseudo-boehmite; said Fe-containing 3+ The water solution is one or more of ferric chloride (III) water solution and ferric sulfate (III) water solution; the alkali is sodium hydroxide and/or potassium hydroxide; the chlorine-containing oxidant is one or more of sodium hypochlorite, potassium hypochlorite, sodium chlorate and potassium chlorate.
3. The method for preparing the in-situ composite aluminum ferrite water treatment agent according to claim 1, wherein the Fe-containing water treatment agent is prepared by a method comprising the following steps of 3+ Fe in aqueous solution 3+ The content of (A) is more than 0.5 mol/L; said Fe-containing 3+ Fe in aqueous solution 3+ The mol ratio of the insoluble aluminum source to the alkali to the chlorine-containing oxidant is (1-2.5) to (0.3-1.2) to (1-3.5) to (0.1-5).
4. The method for preparing the in-situ composite aluminum ferrite water treatment agent according to claim 1, wherein the heating temperature is 70-80 ℃, and the heat preservation time is 1-2 h.
5. The method for preparing the in-situ composite aluminum ferrite water treatment agent according to claim 1, wherein the in-situ composite aluminum ferrite water treatment agent is in a liquid state.
6. The in-situ composite aluminum ferrite water treatment agent prepared by the preparation method of any one of claims 1 to 5, wherein the content of alumina in the composite aluminum ferrite water treatment agent is more than or equal to 8 wt%, and Fe 6+ The compound content is more than or equal to 1.5 wt%, and the causticization coefficient is at least 2.
7. The application method of the in-situ composite aluminum ferrite water treatment agent prepared by the preparation method according to any one of claims 1 to 5, which is characterized in that the in-situ composite aluminum ferrite water treatment agent is added into water to be treated, and impurities in the water are flocculated and settled by stirring; the dosage of the in-situ composite aluminum ferrite water treatment agent in the water to be treated is less than 50 mg/L.
8. The method of use according to claim 7, wherein the water to be treated is sewage or wastewater.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1172078A (en) * 1997-08-18 1998-02-04 中国科学院生态环境研究中心 Electrochemical method for preparing multifunctional compound high iron-aluminium flocculating agent
CN104445557A (en) * 2014-12-12 2015-03-25 上海市政工程设计研究总院（集团）有限公司 Application of ferrate compound agent in treatment of low-temperature low-turbidity water
CN108190965A (en) * 2018-04-08 2018-06-22 福建省爱心环境科技有限公司 A kind of preparation method of Na2Fe04 solution
CN110550713A (en) * 2019-09-05 2019-12-10 新疆水处理工程技术研究中心有限公司 Composite efficient COD (chemical oxygen demand) remover
CN113880123A (en) * 2021-09-18 2022-01-04 常州清流环保科技有限公司 Efficient composite water purifying agent and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1172078A (en) * 1997-08-18 1998-02-04 中国科学院生态环境研究中心 Electrochemical method for preparing multifunctional compound high iron-aluminium flocculating agent
CN104445557A (en) * 2014-12-12 2015-03-25 上海市政工程设计研究总院（集团）有限公司 Application of ferrate compound agent in treatment of low-temperature low-turbidity water
CN108190965A (en) * 2018-04-08 2018-06-22 福建省爱心环境科技有限公司 A kind of preparation method of Na2Fe04 solution
CN110550713A (en) * 2019-09-05 2019-12-10 新疆水处理工程技术研究中心有限公司 Composite efficient COD (chemical oxygen demand) remover
CN113880123A (en) * 2021-09-18 2022-01-04 常州清流环保科技有限公司 Efficient composite water purifying agent and preparation method and application thereof

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