CN111573801B - Organic composite aluminum sulfate water treatment agent and preparation method thereof - Google Patents
Organic composite aluminum sulfate water treatment agent and preparation method thereof Download PDFInfo
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Abstract
The invention provides an organic composite aluminum sulfate water treatment agent and a preparation method thereof, wherein printing and dyeing sludge is used as a raw material, aluminum sulfate is prepared after calcination and acid leaching, and then the aluminum sulfate is compounded with modified starch and modified chitosan to prepare the water treatment agent. The invention effectively utilizes the printing and dyeing sludge, improves the utilization rate of the sludge, and improves the solubility and flocculation performance of the water treatment agent by introducing natural high molecular substances.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an organic composite aluminum sulfate water treatment agent and a preparation method thereof.
Background
Water is a source of life, and the sustainable utilization of water resources is one of the most important problems in the continuous utilization of natural resources. With the rapid development of industry and the continuous improvement of rural urbanization level, the contradiction between supply and demand of water resources becomes more and more prominent, and the method becomes one of strategic problems in the world. The treatment of domestic water, municipal sewage and industrial wastewater has become one of the great challenges facing the world. The flocculation precipitation method is the most economic and widely applied treatment method, a flocculating agent is selected as the core of the flocculation precipitation method, an inorganic polymeric flocculating agent has excellent flocculation performance, is used as a mainstream water treatment flocculating agent nowadays, and is widely applied to various links of water supply, municipal sewage, industrial wastewater and the like. The inorganic polymeric flocculant has multi-channel complex ions, can effectively adsorb colloid particles, promotes colloid agglomeration through the actions of crosslinking, bridging, adhesion and the like, can neutralize suspended matters and charges on the surfaces of the colloid particles, reduces the potential, generates physical and chemical changes, causes the mutual attraction between the colloid particles to cause colloid instability, thereby promoting the collision between the colloid particles and forming floc settlement.
The aluminum salt coagulant is used in water treatment in a small amount, generates a small amount of sludge and is the most widely used coagulant in China. However, the aluminum salt has poor adsorption and bridging capacity, the hydrolysis reaction is not stable, and when the aluminum salt is used for treating a large amount of wastewater, the dosage is large, and residual Al is remained 3+ Increase the amount of the waste water and easily cause secondary pollution. Meanwhile, in recent years, the cost of producing aluminum salt by using aluminum hydroxide and aluminum chloride as raw materials is greatly increased due to the rising price of aluminum-containing materials such as aluminum scraps, aluminum ash and the like, so that research on preparing an aluminum salt flocculating agent by using novel raw materials, improving the flocculation effect of aluminum salt and reducing secondary pollution becomes an important industrial research point.
Disclosure of Invention
Aiming at the defects of high preparation cost, poor flocculation effect and easy secondary pollution of the existing aluminum salt flocculant, the invention provides the organic composite aluminum sulfate water treatment agent and the preparation method thereof.
The invention is realized by the following technical scheme:
an organic composite aluminum sulfate water treatment agent is mainly prepared from the following components: printing and dyeing sludge, sulfuric acid, modified starch, modified chitosan and glacial acetic acid.
The preparation method of the organic composite aluminum sulfate water treatment agent comprises the following steps:
(1) Spreading the printing and dyeing sludge into a thin layer of 2-3 cm, naturally drying in the air, then smashing, burning for 2 hours at 500-600 ℃, and grinding and sieving by a 100-mesh sieve to obtain sludge powder;
(2) Dissolving sludge powder in water according to a liquid-solid ratio of (4-5) mL/g, adding 1mol/L sulfuric acid into the sludge powder according to the ratio of the sludge powder to the sulfuric acid =1g (0.8-1) mL, leaching for 3h at normal temperature by oscillation, standing for 30min, and taking an upper layer solution to obtain a leaching solution;
(3) Adding 12-18 mol/L sulfuric acid solution into the leachate to adjust the pH value to 2-3, reacting until no precipitate is generated, keeping the temperature for 1-2 h at 40-60 ℃, removing the precipitate, and taking supernatant to obtain aluminum sulfate solution;
(4) Taking an aluminum sulfate solution, adding a biomass mixed solution with the mass of 2-8% of that of the aluminum sulfate solution under the stirring condition, and quickly stirring and reacting for 2-3 hours until the aluminum sulfate solution is completely dissolved to obtain the composite aluminum sulfate water treatment agent.
The preparation method of the biomass mixed solution comprises the following steps:
dissolving modified starch in distilled water according to the solid-to-liquid ratio of 1.5;
the modified starch is acrylamide modified starch, and the modified chitosan is etherified modified chitosan.
The invention takes the printing and dyeing sludge as a raw material, prepares the aluminum sulfate by calcining and acid leaching, and compounds the aluminum sulfate with the modified starch and the modified chitosan to improve the bridging capacity of the product, thereby improving the flocculation capacity of the product. The printing and dyeing sludge contains a large amount of aluminum, the main components of the printing and dyeing sludge are aluminum oxide and ferric oxide after high-temperature calcination, organic matters in the sludge are removed simultaneously, the aluminum is enriched, the aluminum is leached by sulfuric acid, the leached aluminum reacts to form aluminum sulfate after the concentrated sulfuric acid reaction, and finally the aluminum sulfate is compounded with modified starch and modified chitosan to obtain the water treatment agent, so that the bridging capacity of the water treatment agent is improved, and the flocculation effect is improved.
The calcination is mainly used for removing organic matters and moisture in the printing and dyeing sludge, so that aluminum and iron are enriched, the aluminum and iron content is increased along with the temperature rise, the calcination cost is increased along with the increase, and the calcination temperature is preferably 500-600 ℃; the sulfuric acid is used as leaching acid, the aluminum in the calcined sludge can be maximally leached, the sulfuric acid is relatively low in cost, and the leachate is mainly Al 3+ 、Al(OH) 2+ 、Al(OH) 2 + 、Al 2 O 3 、Al(OH) 3 And the subsequent preparation efficiency of the aluminum sulfate is improved. The larger the adding amount of the sulfuric acid is, the higher the leaching rate of the aluminum is, but the acidity of the solution is increased, so that a large amount of precipitates are generated to take away aluminum ions, and the aluminum content of the finally prepared product is reduced. As the reaction temperature rises, the solid-liquid mixture is more viscous, which causes difficulty in solid-liquid separation, part of aluminum ions are trapped on filter paper, which causes reduction of aluminum leaching rate, and the reaction cost is increased by raising the temperature, so leaching is carried out at normal temperature. The solid-liquid ratio is increased to facilitate the stirring, but the aluminum metal content in the leachate is reduced, so that the subsequent preparation efficiency of the aluminum sulfate is reduced, and the liquid-solid ratio is optimally selected to be (4-5) mL/g by comprehensively considering that the reaction ensures that the sludge particles are fully contacted with the acid solution and the coagulation efficiency is high.
As a further improvement of the invention, the preparation method of the acrylamide modified starch comprises the following steps:
dissolving corn starch in water with equal mass, gelatinizing for 30min at 90 ℃, heating to 120 ℃, introducing nitrogen for 30min to obtain a reaction solution, then adding ammonium sulfate into the reaction solution, adding 2mol/L acrylamide solution, reacting for 5h, washing with acetone, and drying to obtain acrylamide modified starch;
the adding amount of the ammonium sulfate is 0.5 to 1 percent of the mass of the reaction liquid; the mass ratio of the acrylamide solution to the starch is (1-3) to 1.
As a further improvement of the invention, the preparation method of the etherified modified chitosan comprises the following steps:
dissolving chitosan in a mixed solution of sodium hydroxide and isopropanol according to 0.25g/mL, stirring and heating to 50 ℃, keeping the temperature constant for 2 hours, then adding a 35% by mass 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, heating to 50-80 ℃, reacting at constant temperature for 6-12 hours, after the reaction is finished, adjusting the pH to 7.0 by using dilute hydrochloric acid, then carrying out suction filtration, soaking and washing filter residues by using acetone, then carrying out suction filtration, soaking and washing the obtained secondary filter residues by using absolute ethyl alcohol, then carrying out suction filtration, and drying the obtained tertiary filter residues in a 70 ℃ vacuum drying oven to obtain etherified modified chitosan;
the molar ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution to the chitosan solution is (3-5) to 1;
the mass fraction ratio of the sodium hydroxide solution to the isopropanol is 30%, and the volume ratio of the sodium hydroxide solution to the isopropanol is 1.
The acrylamide modified starch has larger specific surface area, carries a plurality of active groups on the surface, has good water solubility, and improves the bridging capacity of the water treatment agent; the etherified and modified chitosan introduces functional group quaternary ammonium cation, weakens the acting force of hydrogen bond, thereby increasing the solubility of the chitosan, improving the adsorption bridging and charge neutralization between the chitosan modifier and particles, and enhancing the flocculation effect; the surface active groups of the acrylamide modified starch can be better crosslinked with etherified modified chitosan, the charge neutralization effect of aluminum sulfate is further improved under the action of quaternary ammonium cations, the influence of the pH value of sewage on a water treatment agent is reduced, the application range of the agent is improved, and the flocculation effect of the water treatment agent is further improved. The water treatment agent is prepared by modifying and compounding natural high molecular substance starch and chitosan, has good water solubility, reduces the using amount of aluminum sulfate without reducing the flocculation effect, reduces the residual amount of aluminum ions after water treatment, has beneficial degradation performance and avoids secondary pollution.
The starch semi-rigid hydrophilic chain skeleton is matched with flexible polyacrylamide with excellent application performance to form rigid and flexible mutual aid reticular macromolecules, so that the starch semi-rigid hydrophilic chain skeleton has a good net-catching effect, and the quaternary ammonium salt cationic starch has good water solubility and can play a role of a charge neutralization adsorption bridge frame with particles in water, so that the particles in a system are destabilized and flocculated, and the advantages of the particles and the water are combined to achieve a better flocculation effect. When the amount of acrylamide added is small, the polyacrylamide chain segment grafted onto the starch chain is short, the extensibility is poor, the net-capturing effect on suspended particles is limited, and the flocculation effect is further influenced. When the addition amount of acrylamide is large, the polyacrylamide chain segment grafted to the starch chain is long, and after the polyacrylamide chain segment is crosslinked with the etherified modified chitosan, the polyacrylamide chain can wrap cationic groups, so that the neutralization and destabilization effects of the polyacrylamide chain are influenced, and the flocculation effect is further influenced. In general, the mass ratio of the acrylamide solution to the starch is preferably (1-3): 1.
The substitution degree of the etherified modified chitosan is increased along with the increase of the adding amount of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, when the adding amount exceeds a certain amount, the relative amount of amino groups available for substitution is relatively reduced, and the redundant 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is not easy to substitute due to the increase of steric hindrance, so that the reaction efficiency is reduced. In general, the molar ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution to the chitosan solution is (3-5): 1 is most suitable. Along with the extension of the reaction time, the chitosan particles fully expand in the reaction, the probability of mutual collision between reactants is improved, and the reaction is fully carried out. The substitution degree is increased, when the reaction time reaches a certain time, the reaction time is increased, the chitosan is sticky, the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is not easy to permeate into the chitosan particles, and the reaction efficiency is reduced; on the other hand, as the reaction time is prolonged, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is hydrolyzed, and the hydrolysis speed is increased as the reaction time is prolonged, so that the reaction efficiency and the substitution degree of etherified chitosan are reduced. Along with the extension of the reaction time, more quaternary ammonium groups enter the chitosan molecules, so that the product has stronger positive charge and is more beneficial to flocculation, the adsorption rate firstly shows a growing trend, and after the reaction time exceeds 10 hours, the viscosity of the product aqueous solution is increased, the flocculation precipitation is hindered, and the flocculation performance is reduced. The reaction time is preferably 6 to 12 hours in comprehensive consideration.
The invention has the beneficial effects that:
1. the invention takes the printing and dyeing sludge as the raw material to prepare the aluminum sulfate, and prepares the water treatment medicament by compounding with the modified starch and the modified chitosan, thereby reducing the cost of the raw material and effectively utilizing the sludge.
2. The water treatment agent is prepared from the acrylamide modified starch and the etherified modified chitosan composite aluminum sulfate, so that the bridging capacity and the dissolving performance of the water treatment agent are improved, and the flocculation effect of the water treatment agent is improved.
3. The water treatment agent prepared by the invention introduces natural substances to increase flocculation capacity and dissolution performance, reduces the residual quantity of aluminum ions after water treatment, avoids secondary pollution, simultaneously introduces natural polymers to ensure that the water treatment agent has better degradation performance, and reduces the cost of subsequent treatment.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
An organic composite aluminum sulfate water treatment agent is mainly prepared from the following components: printing and dyeing sludge, sulfuric acid, modified starch, modified chitosan and glacial acetic acid.
The preparation method of the organic composite aluminum sulfate water treatment agent comprises the following steps:
(1) Spreading the printing and dyeing sludge into a thin layer of 2-3 cm, naturally drying in the air, then smashing, burning for 2 hours at 500 ℃, and grinding and sieving with a 100-mesh sieve to obtain sludge powder;
(2) Dissolving sludge powder into water according to the liquid-solid ratio of 4mL/g, adding 1mol/L sulfuric acid into the sludge powder according to the proportion that the sludge powder is sulfuric acid =1g and the proportion is 0.8mL, oscillating at normal temperature for leaching for 3h, standing for 30min, and taking an upper layer solution to obtain a leaching solution;
(3) Adding a 12mol/L sulfuric acid solution into the leaching solution to adjust the pH value to 3, reacting until no precipitate is generated, keeping the temperature for 2 hours at 40 ℃, removing the precipitate, and taking supernatant to obtain an aluminum sulfate solution;
(4) Taking an aluminum sulfate solution, adding a biomass mixed solution with the mass being 2% of that of the aluminum sulfate solution under the stirring condition, and quickly stirring and reacting for 2 hours until the aluminum sulfate solution is completely dissolved to obtain the composite aluminum sulfate water treatment agent.
The preparation method of the biomass mixed solution comprises the following steps:
dissolving modified starch in distilled water according to a solid-liquid ratio of 1;
the modified starch is acrylamide modified starch, and the modified chitosan is etherified modified chitosan.
The preparation method of the acrylamide modified starch comprises the following steps:
dissolving corn starch in water with equal mass, gelatinizing for 30min at 90 ℃, heating to 120 ℃, introducing nitrogen for 30min to obtain reaction liquid, then adding ammonium sulfate into the reaction liquid, adding 2mol/L acrylamide solution, reacting for 5h, washing with acetone, and drying to obtain acrylamide modified starch;
the adding amount of the ammonium sulfate is 0.5 percent of the mass of the reaction liquid; the mass ratio of the acrylamide solution to the starch is 1.
The preparation method of the etherified modified chitosan comprises the following steps:
dissolving chitosan in a mixed solution of sodium hydroxide and isopropanol according to 0.25g/mL, stirring and heating to 50 ℃, keeping the temperature constant for 2 hours, then adding a 35% by mass 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, heating to 50 ℃, reacting at constant temperature for 6-12 hours, after the reaction is finished, adjusting the pH value to 7.0 by using dilute hydrochloric acid, carrying out suction filtration, soaking and washing filter residues by using acetone, carrying out suction filtration, soaking and washing the obtained secondary filter residues by using absolute ethyl alcohol, carrying out suction filtration, and drying the obtained tertiary filter residues in a 70 ℃ vacuum drying oven to obtain etherified modified chitosan;
the molar ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution to the chitosan solution is 3;
the mass fraction ratio of the sodium hydroxide solution to the isopropanol is 30 percent and is 1.
Example 2
An organic composite aluminum sulfate water treatment agent is mainly prepared from the following components: printing and dyeing sludge, sulfuric acid, modified starch, modified chitosan and glacial acetic acid.
The preparation method of the organic composite aluminum sulfate water treatment agent comprises the following steps:
(1) Spreading the printing and dyeing sludge into a thin layer of 2-3 cm, naturally drying in the air, then smashing, burning for 2 hours at 600 ℃, and grinding and sieving with a 100-mesh sieve to obtain sludge powder;
(2) Dissolving sludge powder in water according to the liquid-solid ratio of 5mL/g, adding 1mol/L sulfuric acid according to the mass ratio of the sludge powder to the 1 mL;
(3) Adding 18mol/L sulfuric acid solution into the leachate to adjust the pH value to 2, reacting until no precipitate is generated, keeping the temperature at 60 ℃ for 1h, removing the precipitate, and taking supernatant to obtain aluminum sulfate solution;
(4) Taking an aluminum sulfate solution, adding a biomass mixed solution with the mass of 8% of the aluminum sulfate solution under the stirring condition, and quickly stirring and reacting for 3 hours until the aluminum sulfate solution is completely dissolved to obtain the composite aluminum sulfate water treatment agent.
The preparation method of the biomass mixed solution comprises the following steps:
dissolving modified starch in distilled water according to the solid-to-liquid ratio of 1:1.5, stirring and dispersing, then adding the modified chitosan according to the mass ratio of 6;
the modified starch is acrylamide modified starch, and the modified chitosan is etherified modified chitosan.
The preparation method of the acrylamide modified starch comprises the following steps:
dissolving corn starch in water with equal mass, gelatinizing for 30min at 90 ℃, heating to 120 ℃, introducing nitrogen for 30min to obtain a reaction solution, then adding ammonium sulfate into the reaction solution, adding 2mol/L acrylamide solution, reacting for 5h, washing with acetone, and drying to obtain acrylamide modified starch;
the adding amount of the ammonium sulfate is 1 percent of the mass of the reaction liquid; the mass ratio of the acrylamide solution to the starch is 3.
The preparation method of the etherified modified chitosan comprises the following steps:
dissolving chitosan in 0.25g/mL of mixed solution of sodium hydroxide and isopropanol, stirring and heating to 50 ℃, keeping the temperature constant for 2 hours, then adding 35% by mass of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, heating to 80 ℃, reacting at constant temperature for 12 hours, after the reaction is finished, adjusting the pH to 7.0 with dilute hydrochloric acid, carrying out suction filtration, soaking and washing filter residues with acetone, carrying out suction filtration, soaking and washing the obtained secondary filter residues with absolute ethyl alcohol, carrying out suction filtration, and drying the obtained tertiary filter residues in a 70 ℃ vacuum drying oven to obtain etherified modified chitosan;
the molar ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution to the chitosan solution is 5;
the mass fraction ratio of the sodium hydroxide solution to the isopropanol is 30%, and the volume ratio of the sodium hydroxide solution to the isopropanol is 1.
Example 3
An organic composite aluminum sulfate water treatment agent is mainly prepared from the following components: printing and dyeing sludge, sulfuric acid, modified starch, modified chitosan and glacial acetic acid.
The preparation method of the organic composite aluminum sulfate water treatment agent comprises the following steps:
(1) Spreading the printing and dyeing sludge into a thin layer of 2-3 cm, naturally drying in the air, then smashing, burning for 2 hours at 550 ℃, and grinding and sieving with a 100-mesh sieve to obtain sludge powder;
(2) Dissolving sludge powder in water according to the liquid-solid ratio of 5mL/g, adding 1mol/L sulfuric acid according to the mass ratio of the sludge powder to the 1 mL;
(3) Adding a 16mol/L sulfuric acid solution into the leaching solution to adjust the pH value to 2, reacting until no precipitate is generated, keeping the temperature for 1h at 50 ℃, removing the precipitate, and taking supernatant to obtain an aluminum sulfate solution;
(4) Taking an aluminum sulfate solution, adding a biomass mixed solution with the mass of 5% of the aluminum sulfate solution under the stirring condition, and quickly stirring and reacting for 3 hours until the aluminum sulfate solution is completely dissolved to obtain the composite aluminum sulfate water treatment agent.
The preparation method of the biomass mixed solution comprises the following steps:
dissolving modified starch in distilled water according to a solid-liquid ratio of 1:1.5, stirring and dispersing, then adding modified chitosan according to a mass ratio of the modified starch to the modified chitosan of 4:1, heating to 70 ℃, adding 0.8mL/g of glacial acetic acid of the modified starch, reacting for 2h, and terminating the reaction with cold water to obtain a biomass mixed solution;
the modified starch is acrylamide modified starch, and the modified chitosan is etherified modified chitosan.
The preparation method of the acrylamide modified starch comprises the following steps:
dissolving corn starch in water with equal mass, gelatinizing for 30min at 90 ℃, heating to 120 ℃, introducing nitrogen for 30min to obtain a reaction solution, then adding ammonium sulfate into the reaction solution, adding 2mol/L acrylamide solution, reacting for 5h, washing with acetone, and drying to obtain acrylamide modified starch;
the adding amount of the ammonium sulfate is 0.8 percent of the mass of the reaction liquid; the mass ratio of the acrylamide solution to the starch is 2.
The preparation method of the etherified modified chitosan comprises the following steps:
dissolving chitosan in a mixed solution of sodium hydroxide and isopropanol according to 0.25g/mL, stirring and heating to 50 ℃, keeping the temperature constant for 2 hours, then adding a 35% by mass 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, heating to 65 ℃, reacting at constant temperature for 10 hours, after the reaction is finished, adjusting the pH value to 7.0 with dilute hydrochloric acid, carrying out suction filtration, soaking and washing filter residues with acetone, then carrying out suction filtration, soaking and washing the obtained secondary filter residues with absolute ethyl alcohol, carrying out suction filtration, and drying the obtained tertiary filter residues in a 70 ℃ vacuum drying oven to obtain etherified modified chitosan;
the molar ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution to the chitosan solution is 4;
the mass fraction ratio of the sodium hydroxide solution to the isopropanol is 30 percent and is 1.
Application example
Preparation of the Kaolin suspension
1g of kaolin and 500mL of water are respectively added into 9 beakers of 500mL, and the mixture is stirred for 15min at the rotating speed of 300r/min by a variable frequency speed regulating stirrer, so that the kaolin is uniformly dispersed in the water and is averagely divided into 3 groups, wherein each group comprises 3 beakers which are marked as a group 1, a group 2 and a group 3. The stirrer was adjusted to 150r/min, and the water treatment agents prepared in examples 1 to 3 were added to the beakers of group 1, group 2, and group 3, respectively, and stirred for 2min, followed by stirring at 60r/min for 2min. Standing for 20-30 min, taking the supernatant into a cuvette, and measuring the light transmittance at the wavelength of 560nm by using a spectrophotometer. The transmittance results of the treated wastewater are shown in Table 1.
The addition amount of the water treatment agent is 30g/L of wastewater.
TABLE 1
Application example 2
Taking water of a river in a certain area, firstly standing to precipitate silt, taking 200mL of supernatant liquid, putting the supernatant liquid into 9 beakers, evenly dividing the supernatant liquid into 3 groups, marking the groups as a group 1, a group 2 and a group 3, respectively adding the water treatment agents prepared in the embodiments 1-3, then stirring the mixture on a magnetic stirrer for 2min at a speed of 600r/min, then stirring the mixture for 2min at a speed of 150r/min, standing for 20min, taking the supernatant liquid, and measuring the turbidity of the solution. The turbidity removal rate was calculated as follows:
control sample: and (3) taking 200mL of supernatant of the river water after sediment precipitation, adding 5mL of deionized water, stirring for 2min at 600r/min on a magnetic stirrer, stirring for 2min at 150r/min, standing for 20min, taking supernatant, and measuring the turbidity of the solution to obtain the turbidity of a control sample.
The addition amount of the water treatment agent is 5g/L of wastewater.
The turbidity removal rates of the solutions of each group after treatment are shown in Table 2.
TABLE 2
As can be seen from the data in tables 1 and 2, the water treatment agent prepared by the invention has good flocculation effect, the treated wastewater has good light transmittance, and the turbidity removal rate is as high as 93.8%.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents of the invention may be made by those skilled in the art within the spirit and scope of the invention, and such modifications and equivalents should also be considered as falling within the scope of the invention.
Claims (1)
1. An organic composite aluminum sulfate water treatment agent is characterized by being mainly prepared from the following components: printing and dyeing sludge, sulfuric acid, modified starch, modified chitosan and glacial acetic acid;
the preparation method of the organic composite aluminum sulfate water treatment agent comprises the following steps:
(1) Spreading the printing and dyeing sludge into a thin layer of 2-3cm, naturally air-drying, then smashing, burning for 2 hours at 500-600 ℃, grinding and sieving with a 100-mesh sieve to obtain sludge powder;
(2) Dissolving sludge powder in water according to a liquid-solid ratio of (4 to 5) mL/g, adding 1mol/L sulfuric acid according to the sludge powder, namely sulfuric acid =1g (0.8 to 1) mL, oscillating at normal temperature for leaching for 3 hours, standing for 30 minutes, and taking an upper solution to obtain a leaching solution;
(3) Adding a sulfuric acid solution of 12 to 18mol/L into the leachate, adjusting the pH to 2 to 3, reacting until no precipitate is generated, keeping the temperature at 40 to 60 ℃ for 1 to 2h, removing the precipitate, and taking a supernatant to obtain an aluminum sulfate solution;
(4) Taking an aluminum sulfate solution, adding a biomass mixed solution with the mass of 2-8% of that of the aluminum sulfate solution under the stirring condition, and quickly stirring and reacting for 2-3 hours until the aluminum sulfate solution is completely dissolved to obtain a composite aluminum sulfate water treatment agent;
the preparation method of the biomass mixed solution comprises the following steps:
dissolving modified starch in distilled water according to the solid-to-liquid ratio of 1.5;
the modified starch is acrylamide modified starch, and the modified chitosan is etherified modified chitosan;
the preparation method of the acrylamide modified starch comprises the following steps:
dissolving corn starch in water with equal mass, gelatinizing for 30min at 90 ℃, heating to 120 ℃, introducing nitrogen for 30min to obtain reaction liquid, then adding ammonium sulfate into the reaction liquid, adding 2mol/L acrylamide solution, reacting for 5h, washing with acetone, and drying to obtain acrylamide modified starch;
the adding amount of the ammonium sulfate is 0.5 to 1 percent of the mass of the reaction liquid; the mass ratio of the acrylamide solution to the starch is (1-3) to 1;
the preparation method of the etherified modified chitosan comprises the following steps:
dissolving chitosan in a mixed solution of sodium hydroxide and isopropanol according to 0.25g/mL, stirring and heating to 50 ℃, keeping the temperature constant for 2 hours, then adding a 35% by mass 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution, heating to 50-80 ℃, reacting at constant temperature for 6-12 hours, after the reaction is finished, adjusting the pH to 7.0 by using dilute hydrochloric acid, then carrying out suction filtration, soaking and washing filter residues by using acetone, then carrying out suction filtration, soaking and washing the obtained secondary filter residues by using absolute ethyl alcohol, then carrying out suction filtration, and drying the obtained tertiary filter residues in a 70 ℃ vacuum drying oven to obtain etherified modified chitosan;
the molar ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution to the chitosan solution is (3-5) to 1;
the mass fraction ratio of the sodium hydroxide solution to the isopropanol is 30%, and the volume ratio of the sodium hydroxide solution to the isopropanol is 1.
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