CN111039371A - Natural organic composite flocculant and preparation method and application thereof - Google Patents
Natural organic composite flocculant and preparation method and application thereof Download PDFInfo
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- CN111039371A CN111039371A CN201911336797.1A CN201911336797A CN111039371A CN 111039371 A CN111039371 A CN 111039371A CN 201911336797 A CN201911336797 A CN 201911336797A CN 111039371 A CN111039371 A CN 111039371A
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
Abstract
The invention discloses a natural organic composite flocculant and a preparation method and application thereof. The natural organic compound flocculant comprises 5-25 wt% of modified chitosan, 5-40 wt% of steel slag, 10-25 wt% of modified starch, 5-20 wt% of potassium oxide, 5-10 wt% of calcium carbonate, 15-20 wt% of ceramic powder and 10-15 wt% of guar gum compound, wherein the total weight of the natural organic compound flocculant is 100 wt%. The invention also provides a preparation method of the natural organic compound flocculant and application of the natural organic compound flocculant in sewage coagulating sedimentation treatment. The natural organic compound flocculant provided by the invention can effectively remove pollutants in wastewater through the actions of adsorption, flocculation and the like, so as to achieve the purpose of purifying water.
Description
Technical Field
The invention relates to the technical field of sewage flocculation treatment. More particularly, relates to a natural organic composite flocculant, a preparation method and application thereof.
Background
Flocculation is an indispensable process in water treatment, and flocculants play a decisive role in the flocculation process. Typical flocculants include inorganic flocculants, organic flocculants, and complex flocculants. Inorganic flocculants commonly used at present include aluminum salt, iron salt and the like, and organic flocculants commonly used include polyacrylamide, lignin, chitosan, starch and the like. The combined use of aluminum salts and polyacrylamide is most common in flocculation. However, recent studies have shown that aluminum salts have some toxicity to human bodies and are likely to cause alzheimer's disease, and that residues of polyacrylamide can generate acrylamide monomers, which are biologically neurotoxic. The corrosive and color properties of iron salts limit their applicability.
In recent years, natural organic polymeric flocculants have been widely developed to replace aluminum salts and polyacrylamides, and modification studies of natural organic macromolecular substances such as lignin, chitosan, starch and the like have been carried out. The modified natural organic flocculant has flocculation capacity no weaker than that of polyacrylamide and no biological toxicity. They generally have extremely high manufacturing costs, are economically inefficient to popularize, and have limited adsorption capacity.
The composite flocculant can effectively avoid the defects of natural organic flocculants. The organic natural flocculant is combined with other compounds through a specific manufacturing process, so that the cost of the flocculant can be reduced, and the applicability, the adsorption capacity and the flocculation capacity of the flocculant can be improved.
Based on the reasons, the invention provides a natural organic composite flocculant and a preparation method and application thereof, which can reduce the manufacturing cost of the flocculant while ensuring and even improving the pollutant removal capacity of the flocculant.
Disclosure of Invention
The first purpose of the invention is to provide a natural organic composite flocculant.
The second purpose of the invention is to provide a preparation method of the natural organic compound flocculant.
The third purpose of the invention is to provide the application of the natural organic compound flocculant.
In order to achieve the purpose, the invention adopts the following technical scheme:
a natural organic composite flocculant, wherein the natural organic composite flocculant accounts for 100 wt% of the total weight of the natural organic composite flocculant, and comprises:
in the natural organic compound flocculant, the modified chitosan is a natural organic polymer flocculant, a large number of acylamino and hydroxyl groups exist in chitosan molecules, the flocculant has good adsorption and flocculation capacities, the raw materials are completely taken from the nature, the modified chitosan is soluble in water, and the flocculation capacity is greatly enhanced;
the modified starch and the modified chitosan have similar functions, and the modified starch and the modified chitosan are used together, so that the application range of the medicament can be greatly improved, and the effectiveness of the flocculating agent on different pollutants is improved;
the potassium oxide can adjust the pH value of the sewage and create proper pH value for the use of the flocculating agent;
the guar gum compound is a thickening agent and can improve the flocculation capacity of the flocculating agent;
the steel slag has higher adsorption capacity and can adsorb pollutants in the wastewater;
the calcium carbonate can improve the compactness of the floc, so that the floc is not easy to break after being formed;
the ceramic powder can enable flocs to be rapidly separated from water and agglomerated, enables the flocs not to be broken easily, can effectively form compact and unbreakable flocs with low water content by being matched with calcium carbonate for use, and can be rapidly settled.
The components are matched with each other and have synergistic effect, so that the composite can be used for various waste water, and the lack of any component or the change of the content of any component can cause the composite to be weakened in different degrees in the treatment of different waste water.
Preferably, the modified chitosan comprises one or more of 2-hydroxypropyl trimethyl ammonium chloride chitosan, carboxymethyl chitosan and sodium xanthate chitosan.
Preferably, the modified starch is acrylamide graft copolymerization modified starch.
Preferably, the steel slag is waste slag generated in the steel-making process of a steel plant.
Preferably, the guar based compound comprises guar and/or guar copolymers.
Preferably, the mesh number of the modified chitosan is not less than 100 meshes.
Preferably, the mesh number of the steel slag is not less than 400 meshes.
Preferably, the mesh number of the modified starch is not less than 100 meshes.
Preferably, the mesh number of the ceramic powder is not less than 400 meshes.
Preferably, the mesh number of the calcium carbonate is not less than 400 meshes.
Preferably, the mesh number of the guar gum compound is 100 meshes.
Preferably, the mesh number ratio of the modified chitosan, the steel slag, the modified starch, the ceramic powder, the calcium carbonate and the guar gum compound is 100:400:100:400:400:100, and the mesh number of the potassium oxide is not limited.
As another aspect of the present invention, the present invention also provides a preparation method of the above natural organic composite flocculant, which comprises the following steps:
and uniformly mixing the modified chitosan, the steel slag, the modified starch, the potassium oxide, the calcium carbonate, the ceramic powder and the guar gum compound to obtain the natural organic composite flocculant.
Preferably, the mixing uniformity of the modified chitosan, the steel slag, the modified starch, the potassium oxide, the calcium carbonate, the ceramic powder and the guar gum compound is more than 98%.
In the steps, the mixing is a conventional technical means in the field, and the stirring can be carried out in the mixing process, so that the components are more fully mixed, and local agglomeration is prevented; furthermore, it is to be understood that the above mixing step is carried out at room temperature; in addition, the adding sequence of the components is not specifically required in the mixing process, and the adding sequence of the raw materials can be reasonably adjusted by a person skilled in the art according to the field operation requirement.
As another aspect of the invention, the invention also provides an application of the natural organic compound flocculant in sewage coagulating sedimentation treatment.
In addition, unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
The invention has the following beneficial effects:
the natural organic compound flocculant provided by the invention can effectively remove pollutants in wastewater through the actions of adsorption, flocculation and the like, so as to achieve the purpose of purifying water.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the invention, the preparation method is a conventional method if no special description is provided; the starting materials used are commercially available from published sources unless otherwise specified.
Example 1
This example provides a natural organic composite flocculant, where the natural organic composite flocculant includes, based on 100 wt% of the total weight of the natural organic composite flocculant:
the embodiment also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding steel slag, calcium carbonate and ceramic powder into 400-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, ceramic powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches more than 98%.
Example 2
This example provides a natural organic composite flocculant, where the natural organic composite flocculant includes, based on 100 wt% of the total weight of the natural organic composite flocculant:
the embodiment also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding steel slag, calcium carbonate and ceramic powder into 400-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, ceramic powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches more than 98%.
Example 3
This example provides a natural organic composite flocculant, where the natural organic composite flocculant includes, based on 100 wt% of the total weight of the natural organic composite flocculant:
the embodiment also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding steel slag, calcium carbonate and ceramic powder into 400-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, ceramic powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches more than 98%.
Comparative example 1
The comparative example provides a natural organic composite flocculant, wherein the natural organic composite flocculant comprises, based on 100 wt% of the total weight of the natural organic composite flocculant:
the comparative example also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding sodium chloride, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding steel slag, calcium carbonate and ceramic powder into 400-mesh powder;
2) and (2) at room temperature, proportionally putting sodium chloride powder, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, ceramic powder and guar gum powder into a mixer for stirring, and obtaining the natural organic compound flocculant when the mixing uniformity reaches more than 98%.
Comparative example 2
The comparative example provides a natural organic composite flocculant, wherein the natural organic composite flocculant comprises, based on 100 wt% of the total weight of the natural organic composite flocculant:
the comparative example also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding sodium chloride, calcium carbonate and ceramic powder into 400-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, sodium chloride powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, ceramic powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches more than 98%.
Comparative example 3
The comparative example provides a natural organic composite flocculant, wherein the natural organic composite flocculant comprises, based on 100 wt% of the total weight of the natural organic composite flocculant:
the comparative example also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding steel slag, sodium chloride and ceramic powder into 400-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, sodium chloride powder, ceramic powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches more than 98%.
Comparative example 4
The comparative example provides a natural organic composite flocculant, wherein the natural organic composite flocculant comprises, based on 100 wt% of the total weight of the natural organic composite flocculant:
the comparative example also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding steel slag, calcium carbonate and sodium chloride into 400-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, sodium chloride powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches more than 98%.
Comparative example 5
The comparative example provides a natural organic composite flocculant, wherein the natural organic composite flocculant comprises, based on 100 wt% of the total weight of the natural organic composite flocculant:
the comparative example also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 400-mesh powder at room temperature, and respectively grinding steel slag, calcium carbonate and ceramic powder into 400-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, ceramic powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches more than 98%.
Comparative example 6
The comparative example provides a natural organic composite flocculant, wherein the natural organic composite flocculant comprises, based on 100 wt% of the total weight of the natural organic composite flocculant:
the comparative example also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding steel slag, calcium carbonate and ceramic powder into 400-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, ceramic powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches 90%.
Comparative example 7
The comparative example provides a natural organic composite flocculant, wherein the natural organic composite flocculant comprises, based on 100 wt% of the total weight of the natural organic composite flocculant:
the embodiment also provides a preparation method of the natural organic composite flocculant, which comprises the following steps:
1) respectively grinding 2-hydroxypropyl trimethyl ammonium chloride chitosan, acrylamide graft copolymerization modified starch and guar gum into 100-mesh powder at room temperature, and respectively grinding steel slag, calcium carbonate and ceramic powder into 1000-mesh powder;
2) and (2) putting chitosan powder of 2-hydroxypropyl trimethyl ammonium chloride, steel slag powder, acrylamide graft copolymerization modified starch powder, potassium oxide, calcium carbonate powder, ceramic powder and guar gum powder into a mixer at room temperature in proportion, and stirring to obtain the natural organic composite flocculant when the mixing uniformity reaches more than 98%.
Test example 1
The test example provides an application of a natural organic composite flocculant in the treatment of turbid circulating water in the metallurgical industry, which comprises the following steps:
the natural organic composite flocculant prepared in example 1, the natural organic composite flocculant prepared in comparative example 1 and the dirty ring wastewater of a certain steel plant are respectively mixed and stirred in a beaker to carry out a beaker experiment.
The experimental results show that: the content of suspended matters in raw water of the turbid circulating wastewater of a certain steel plant is 391.1 mg/L; in this test example, the flocculants of example 1 and comparative example 1 were added to turbid circulating water raw water in amounts of 0.1mg/L, 0.2mg/L, 0.3mg/L, 0.4mg/L, 0.5mg/L, 0.7mg/L and 1mg/L, respectively, and the respective solutions were stirred for 10 minutes and then left to stand for 2 minutes to conduct tests. The concentration of the effluent suspension is shown in table 1. As can be seen from the table, the flocculant of example 1 had reduced the concentration of suspended solids in the effluent to below 20mg/L after being added in an amount of 0.3mg/L, and stabilized the concentration of suspended solids to below 10mg/L after being added in an amount of 0.5mg/L and above; whereas the flocculant of comparative example 1 was largely ineffective due to the absence of chitosan, the best treatment still remained at a suspended particulate concentration of 45.1 mg/L. The result proves that the flocculant of the embodiment 1 of the invention effectively removes suspended particles in wastewater, and the 2-hydroxypropyl trimethyl ammonium chloride chitosan plays a crucial role.
TABLE 1 results of treatment of turbid waste water
Test example 2
The experimental example provides an application of a natural organic composite flocculant in mercury-containing wastewater treatment, which comprises the following steps:
the natural organic composite flocculant prepared in example 2, the natural organic composite flocculant prepared in comparative example 2 and mercury-containing wastewater of a certain chemical plant are mixed and stirred in beakers respectively, and a beaker experiment is carried out.
The experimental results show that: the content of mercury in raw water of mercury-containing wastewater of a certain chemical plant is 194.1 mg/L; the test was carried out in the present application examples by stirring the mixture at 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 7mg/L and 9mg/L for 20 min. The concentration of the residual mercury after the addition is shown in Table 2. As can be seen, when the adding amount of the flocculating agent in the embodiment 2 is 7mg/L, the mercury in the wastewater is effectively removed, and the content of the residual mercury in the wastewater is only 0.52 mg/L; the flocculant of the comparative example is superior to steel slag lacking the key adsorption effect, and the mercury removal capacity is greatly weakened.
TABLE 2 results of treatment of wastewater containing mercury
Test example 3
The experimental example provides an application of a natural organic composite flocculant in black and odorous water treatment engineering, which comprises the following steps:
the natural organic composite flocculant prepared in example 3, comparative example 4, comparative example 5, comparative example 6 and comparative example 7 and the black and odorous river sewage obtained from a river are respectively mixed and stirred in a beaker to carry out a beaker experiment.
The experimental results show that: in this test example, the flocculants of example 3, comparative example 4, comparative example 5, comparative example 6 and comparative example 7 were added to the sewage of the black and odorous water body in an amount of 2mg/L, followed by stirring for 2min and then standing for 10min each to conduct a test. The addition effect is shown in Table 3. Therefore, when the flocculant of the embodiment 3 of the invention is applied to the purification of black and odorous riverways, COD, BOD, total phosphorus, total nitrogen and the like in the water body are effectively removed; comparative example 3 the treatment effect on the black and odorous water body is close to that of example 3, but the flocculant lacks calcium carbonate, so that the generated sludge is not compact enough, the sludge is loose, the sludge is easy to break in the actual use process, and the settling time and the effluent turbidity are increased; the treatment effect of comparative example 4 is also good, but the sedimentation rate of the flocs is caused due to the lack of the ceramic powder; in comparative example 5, the specific surface area of the flocculant is reduced and the flocculation capacity of the flocculant is reduced due to the fact that the particles of the 2-hydroxypropyl trimethyl ammonium chloride chitosan, the acrylamide graft copolymerization modified starch and the guar gum after grinding are large; in comparative example 6, the flocculant was not uniformly distributed in water due to the low degree of mixing of the flocculant, resulting in a decrease in flocculation ability; in comparative example 7, the steel slag, calcium carbonate and ceramic powder have larger particles, so that the specific surface area is reduced, the adsorption capacity is reduced, and the residual COD and BOD of effluent are higher.
TABLE 3 treatment results of black and odorous water
In conclusion, the components of the natural organic compound flocculant are matched with each other and have synergistic effect, so that the effect of flocculating the pollutants in the sewage is optimal; wherein, the lack of chitosan causes the sedimentation capability of the flocculant to suspended matters to be seriously reduced; the lack of steel slag causes the serious reduction of the adsorption capacity of the flocculant to heavy metal ions in the sewage; in the absence of calcium carbonate or ceramic powder, the quality of flocs is reduced, which is not favorable for clarification and sludge treatment.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. The natural organic composite flocculant is characterized by comprising the following components in percentage by weight of 100 percent of the total weight of the natural organic composite flocculant:
2. the natural organic composite flocculant according to claim 1, wherein the modified chitosan comprises one or more of 2-hydroxypropyltrimethyl ammonium chloride chitosan, carboxymethyl chitosan, and sodium xanthate chitosan.
3. The natural organic composite flocculant according to claim 1, wherein the modified starch is acrylamide graft copolymer modified starch.
4. The natural organic composite flocculant of claim 1, wherein the steel slag is waste slag generated in a steel-making process of a steel plant.
5. The natural organic composite flocculant according to claim 1, wherein the guar-based compound comprises guar and/or a guar copolymer.
6. The natural organic composite flocculant according to claim 1, wherein the modified chitosan has a mesh number of not less than 100 meshes; the mesh number of the steel slag is not less than 400 meshes; the mesh number of the modified starch is not less than 100 meshes; the mesh number of the ceramic powder is not less than 400 meshes; the mesh number of the calcium carbonate is not less than 400 meshes; the mesh number of the guar gum compound is 100 meshes.
7. The natural organic composite flocculant according to claim 1, wherein the mesh ratio of the modified chitosan, the steel slag, the modified starch, the ceramic powder, the calcium carbonate and the guar gum compound is 100:400:100:400:400: 100.
8. A preparation method of the natural organic compound flocculant according to any one of claims 1 to 7, characterized by comprising the following steps:
and uniformly mixing the modified chitosan, the steel slag, the modified starch, the potassium oxide, the calcium carbonate, the ceramic powder and the guar gum compound to obtain the natural organic composite flocculant.
9. The method for preparing the natural organic compound flocculant according to claim 8, wherein the mixing uniformity of the modified chitosan, the steel slag, the modified starch, the potassium oxide, the calcium carbonate, the ceramic powder and the guar gum compound is more than 98%.
10. The application of the natural organic compound flocculant according to any one of claims 1 to 7 in sewage coagulating sedimentation treatment.
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| CN109942060A (en) * | 2019-03-20 | 2019-06-28 | 马晶乐 | A kind of sewage treatment drug of mineral base flocks |
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| US20060231499A1 (en) * | 2005-04-18 | 2006-10-19 | Ken Brummett | Methods and compositions for wastewater treatment |
| CN104903252A (en) * | 2013-04-18 | 2015-09-09 | 北京东方协和医药生物技术有限公司 | A composition for treating waste water |
| CN105502617A (en) * | 2016-01-27 | 2016-04-20 | 江南大学 | Guar gum-chitosan natural flocculant and preparing method thereof |
| CN109179616A (en) * | 2018-11-07 | 2019-01-11 | 中冶京诚工程技术有限公司 | A kind of efficient flocculant of natural degradable and the preparation method and application thereof |
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