阅读说明：本技术 一种复合型水质凝集净化剂及其制备方法 (Composite water quality agglutination purifying agent and preparation method thereof ) 是由 陈颖 于 2021-08-26 设计创作，主要内容包括：本申请涉及污水治理领域,具体公开了一种复合型水质凝集净化剂及其制备方法。复合型水质凝集净化剂包括以下重量份的组分：煅烧硅土550-600份、稀土瓷砂30-70份、白云母20-65份、聚铝90-120份、蛇纹石15-50份、聚丙烯酰胺15-45份；其制备方法为：将白云母和蛇纹石、稀土瓷砂分别破碎后,混合,加入重量为白云母、蛇纹石和稀土瓷砂总重10-15%的水,球磨、烘干、过筛,加入煅烧硅土、聚丙烯酰胺和聚铝,混合均匀。本申请的复合型水质凝集净化剂具有不受水温影响,炎热地区和严寒地区均适用,且适用水质范围广,对COD、TN、TP等去除率高,对藻类具有即时和长效去除效果的优点。(The application relates to the field of sewage treatment, and particularly discloses a compound water quality agglutination purifying agent and a preparation method thereof. The composite water quality agglutination purifying agent comprises the following components in parts by weight: 600 parts of calcined silica 550-doped sand, 30-70 parts of rare earth porcelain sand, 20-65 parts of muscovite, 90-120 parts of polyaluminium, 15-50 parts of serpentine and 15-45 parts of polyacrylamide; the preparation method comprises the following steps: respectively crushing the muscovite, the serpentine and the rare earth porcelain sand, mixing, adding water accounting for 10-15% of the total weight of the muscovite, the serpentine and the rare earth porcelain sand, ball-milling, drying, sieving, adding calcined silica, polyacrylamide and polyaluminium, and uniformly mixing. The composite water quality coagulation purifying agent has the advantages of no influence of water temperature, suitability in hot areas and severe cold areas, wide applicable water quality range, high removal rate of COD (chemical oxygen demand), TN (total nitrogen) and TP (total phosphorus) and the like, and instant and long-acting removal effect on algae.)

1. A composite water quality agglutination purifying agent is characterized by comprising the following components in parts by weight: calcining 600 parts of silica 550;

30-70 parts of rare earth porcelain sand;

20-65 parts of muscovite;

90-120 parts of polyaluminium;

15-50 parts of serpentine;

15-45 parts of polyacrylamide.

2. The composite water quality agglutination purifying agent according to claim 1, characterized in that: the composite water quality agglutination purifying agent comprises the following components in parts by weight:

560-590 parts of calcined silica;

40-60 parts of rare earth porcelain sand;

30-50 parts of muscovite;

100 portions of polyaluminium;

35-45 parts of serpentine;

20-40 parts of polyacrylamide.

3. A composite water quality agglutination purification agent according to claim 1, wherein the composite water quality agglutination purification agent comprises the following components in parts by weight:

calcining 580 parts of silica;

35 parts of rare earth porcelain sand;

30 parts of muscovite;

110 parts of polyaluminium;

45 parts of serpentine;

and 20 parts of polyacrylamide.

4. A composite water quality coagulation purifier according to any one of claims 1 to 3, wherein the calcined silica is prepared by a method comprising: calcining the silica at the temperature of 800-1000 ℃ for 5-6 h.

5. The composite water quality agglutination purification agent according to claim 4, wherein the silica is uniformly stirred with silver nitrate solution with concentration of 0.1-0.2moL/L at room temperature before calcination, and then dipped in vacuum and protected from light.

6. A composite water quality agglutination purification agent according to any of claims 1-3 wherein the particle size of the calcined silica is 200-400 mesh.

7. A composite water quality coagulation-clarification agent according to any one of claims 1 to 3, wherein the input amount of the composite water quality coagulation-clarification agent is 10 to 300g/m³。

8. A composite water quality agglutination purification agent according to any of claims 1-3, wherein said composite water quality agglutination purification agent further comprises 20-40 parts by weight of modified starch and 15-25 parts by weight of nano zinc oxide.

9. The composite water quality agglutination purifying agent according to claim 8, wherein the preparation method of the modified starch is as follows:

(1) mixing 8-10 parts of starch and 1.5-2 parts of oxidant, heating for 3-7min at 60-75 ℃ under the action of microwave after uniformly mixing, adjusting the pH value to 8-10, adding 1-1.5 parts of carboxymethyl cellulose and 0.1-0.3 part of sodium tetraborate, and defoaming after uniformly stirring;

(2) mixing 1.1-1.5 parts by weight of sodium bentonite and 2-3 parts by weight of distilled water to prepare a suspension, heating to 80-90 ℃, adding 0.5-1 part by weight of glycerol, stirring for 30-40min under heat preservation, adding 2.5-3 parts by weight of PVA, stirring for 1-2h under heat preservation, centrifuging, drying and grinding;

(3) mixing the product obtained in the step (1) and the product obtained in the step (2), adding 0.5-1 part by weight of initiator and 5-7 parts by weight of distilled water, heating to 45-60 ℃, keeping the temperature and stirring for 3-4h, and drying at 50-60 ℃.

10. A method for preparing a composite water quality agglutination purifying agent according to any of claims 1-9, characterized by comprising the steps of:

respectively crushing muscovite, serpentine and rare earth porcelain sand, mixing, adding water accounting for 10-15% of the total weight of the muscovite, the serpentine and the rare earth porcelain sand, ball-milling, drying, sieving, adding calcined silica, polyacrylamide and polyaluminium, and uniformly mixing to obtain the composite water quality agglutination purifying agent.

Technical Field

The application relates to the technical field of sewage treatment, in particular to a composite water quality agglutination purifying agent and a preparation method thereof.

Background

In recent years, with the increasing number of people in China and the rapid development of industrial and agricultural production, the water demand is rapidly increased, and meanwhile, the water pollution is more and more serious. The water pollution is one of the most serious pollution and the most harmful pollution in the world at present, in the sewage treatment process, coagulation and flocculation processes are indispensable important units, the variety and the quantity of water treatment flocculants are various, and the flocculants for treating industrial wastewater in China are mainly classified into three types: organic polymer flocculant, inorganic flocculant and microbial flocculant.

The inorganic flocculant is widely used, the inorganic flocculant is dissociated in water to form ions, the larger the charge density of the inorganic flocculant is, the smaller the ion volume is, and the better the flocculation effect is, therefore, only positive trivalent ions such as aluminum and iron in the inorganic flocculant have the flocculation effect, and monovalent or divalent ions such as sodium, magnesium and calcium have no flocculation effect basically. The aluminum salt flocculating agent comprises polyaluminium chloride (PAC), polyaluminium sulfate (PAS), polyaluminium phosphate (PAP) and the like, the ferric salt flocculating agent comprises polyaluminium phosphate (PFP), PFC (polyferric chloride), polyferric sulfate (PFS) and the like, but the aluminum salt flocculating agent and the ferric salt flocculating agent have certain required limits on water temperature, pH value, high oil, high salt, high emulsion, high chroma and the like, for example, when the water temperature is lower, the hydrolysis speed of the flocculating agent is slow and incomplete, and even if the input amount of the flocculating agent is increased, the good reaction condition can not be created to compensate the influence of the reduction of the water temperature on the coagulation effect; the influence of the pH value is that amphoteric aluminum hydroxide is generated after the aluminum salt is hydrolyzed, the aluminum hydroxide is easily dissolved in water under acidic and alkaline conditions, and at the moment, the aluminum salt exists in the form of a large amount of aluminum ions in the water, and because the aluminum ions do not have an adsorption and bridging effect, impurities in the water cannot be bonded together, so the coagulation effect is poor.

In view of the above-mentioned related technologies, the inventors consider that there is a need to develop a water purifying agent suitable for various climates and various sewage and wastewater difficult to flocculate.

Disclosure of Invention

In order to ensure that the flocculant has wide applicable water quality range and high efficiency and is not influenced by water temperature, pH value and the like, the application provides a compound water quality agglutination purifying agent and a preparation method thereof.

In a first aspect, the application provides a composite water quality agglutination purifying agent, which adopts the following technical scheme:

a composite water quality agglutination purifying agent comprises the following components in parts by weight:

calcining 600 parts of silica 550;

30-70 parts of rare earth porcelain sand;

20-65 parts of muscovite;

90-120 parts of polyaluminium;

15-50 parts of serpentine;

15-45 parts of polyacrylamide.

By adopting the technical scheme, as the main component of the silica is silicon dioxide, and aluminum oxide, ferric oxide, volatile matters and the like are adopted, the calcined silica is used as a purifying agent, after calcination, the bound water content of the silica is reduced, the active sites are increased, the structure is changed, aluminum polysilicate is generated, the aluminum polysilicate has an adsorption bridging effect, the flocculation effect is good, the residual aluminum content in the treated water is low, the density of flocculate is high, and the sedimentation is rapid; the rare earth porcelain sand has the advantages of high mechanical strength, wear resistance, multiple micropores, large adsorption area, strong pollutant interception capability, point contact with each other, uniform porosity, convenient use, difficult blockage and good effect on treating sewage containing suspended colloid.

The serpentine, the calcined silica and the rare earth porcelain sand have strong electrostatic effect on compositions in water, so that pollutants in water can be flocculated to generate floccules with larger particle size, and the settling speed of pollutant particles is accelerated.

Polyacrylamide cannot generate hydrolysate with adsorption effect on organic substances, the removal of the organic substances is improved only by improving the solid-liquid separation effect, the negative charges in the inorganic coagulant have the electric neutralization effect to destabilize colloid and remove large suspended particles, and the polyacrylamide can quickly adsorb and bridge neutralized colloid particles and fine colloidal particles, so that the flocculation and sedimentation effects are increased, and the flocculation and coagulation effects are improved by using the mutual cooperation of the polyacrylamide, serpentine, polyaluminium, calcined silica and the like.

After the purifying agent is put into sewage, because polyacrylamide is a non-ionic high-molecular polymer, the purifying agent can be adsorbed on the surfaces of serpentine particle particles through active groups on long carbon chains, when muscovite, calcined silica and rare earth porcelain sand contact the overhanging parts of polyacrylamide molecules, the same adhesion can occur, so that the calcined silica, the serpentine and the rare earth porcelain sand can be mutually condensed by virtue of the bridging action of the polyacrylamide, the sedimentation speed is increased, the apparent density of the particles is increased, the coagulation and the coagulation assistance are integrated, the purifying agent is not influenced by water temperature and pH value, and pollutants in various sewage can be efficiently removed.

Preferably, the compound water quality agglutination purifying agent comprises the following components in parts by weight:

560-590 parts of calcined silica;

40-60 parts of rare earth porcelain sand;

30-50 parts of muscovite;

100 portions of polyaluminium;

35-45 parts of serpentine;

20-40 parts of polyacrylamide.

By adopting the technical scheme, the contents of various components in the purifying agent are further accurate, so that the prepared purifying agent has better purifying effect on different sewage and waste water.

Preferably, the compound water quality agglutination purifying agent comprises the following components in parts by weight:

calcining 580 parts of silica;

35 parts of rare earth porcelain sand;

30 parts of muscovite;

110 parts of polyaluminium;

45 parts of serpentine;

and 20 parts of polyacrylamide.

By adopting the technical scheme, the contents of various components in the purifying agent are further accurate, so that the prepared purifying agent has better purifying effect on different sewage and waste water.

Preferably, the preparation method of the calcined silica comprises the following steps: calcining the silica at the temperature of 800-1000 ℃ for 5-6 h.

By adopting the technical scheme, the roasting temperature is the key for activating the silica, the roasting temperature is low, the dehydration is too little, the activity of the silica is poor, the roasting temperature is too high, the silica is recrystallized, and the activity is reduced.

Preferably, before the silica is calcined, the silica is uniformly stirred with silver nitrate solution with the concentration of 0.1-0.2moL/L at room temperature, and then the silica is dipped in vacuum in a dark place.

By adopting the technical scheme, the surface of the silica is covered with a large amount of hydroxyl groups, so that the surface of the silica has negative charges, the silica has a good adsorption effect on silver ions, the silver ions can perform ion exchange with metal cations immersed in a silver nitrate solution on the surface of the silica, the silver ions are loaded on the silica, after sintering, a large amount of uniformly distributed pores exist on the surface of the silica, and the silver nitrate is heated and decomposed to form silver simple substances, so that the silver simple substances are loaded on the silica, and the silver is slowly released on the surface of the silica, so that the silica has long-acting antibacterial ability, and the removal effect of the purifying agent on algae can be improved.

Preferably, the particle size of the calcined silica is 200-400 meshes.

By adopting the technical scheme, the calcined silica with the particle size of 200-400 meshes is suspended in the water phase, so that the number of particles is large, the collision probability among the particles is improved, and the natural flocculation effect is enhanced.

Preferably, the input amount of the compound water quality agglutination purifying agent is 10-300g/m³。

By adopting the technical scheme, the flocculation rate is increased along with the increase of the input amount in the same time, but when the input amount is overlarge, colloid particles are easy to adsorb excessive ions with reverse charges, so that the original charges are changed in sign, the repulsive force is increased, the re-stabilization phenomenon is generated, and the flocculation rate is reduced.

Preferably, the composite water quality agglutination purifying agent also comprises 20-40 parts by weight of modified starch and 15-25 parts by weight of nano zinc oxide.

By adopting the technical scheme, when the flocculating agent is used for removing algae, algal bloom flocs formed by the flocculating agent and the algae are loose and have poor settleability, and the algae has phototaxis and is easy to float upwards, so that the stability of the algal bloom flocs formed by the algal blooms and the flocculating agent is easy to reduce, the algae is easy to separate from the algal bloom flocs and float upwards to the surface of a water body again, and the flocculating effect of the flocculating agent is influenced; the nano zinc oxide can improve the compactness of the algal bloom flocs, so that the algal bloom flocs are easier to settle, the modified starch can improve the coating performance of the flocculant, increase the adhesion of the algal bloom and the flocculant, improve the stability of the algal bloom flocs, and ensure that the algal bloom is not easy to separate from the algal bloom flocs and returns to the surface of the body again, thereby thoroughly removing the algal bloom and prolonging the long-acting property of the flocculant.

Preferably, the preparation method of the modified starch comprises the following steps:

(1) mixing 8-10 parts of starch and 1.5-2 parts of oxidant, heating for 3-7min at 60-75 ℃ under the action of microwave after uniformly mixing, adjusting the pH value to 8-10, adding 1-1.5 parts of carboxymethyl cellulose and 0.1-0.3 part of sodium tetraborate, and defoaming after uniformly stirring;

(2) mixing 1.1-1.5 parts by weight of sodium bentonite and 2-3 parts by weight of distilled water to prepare a suspension, heating to 80-90 ℃, adding 0.5-1 part by weight of glycerol, stirring for 30-40min under heat preservation, adding 2.5-3 parts by weight of PVA, stirring for 1-2h under heat preservation, centrifuging, drying and grinding;

(3) mixing the product obtained in the step (1) and the product obtained in the step (2), adding 0.5-1 part by weight of initiator and 5-7 parts by weight of distilled water, heating to 45-60 ℃, keeping the temperature and stirring for 3-4h, and drying at 50-60 ℃.

By adopting the technical scheme, firstly, an oxidant is mixed with starch, the starch is oxidized, then the starch is crosslinked with carboxymethyl cellulose and sodium tetraborate, the viscosity of the starch is increased, then glycerol is inserted between layers of sodium bentonite to loosen the structure of the sodium bentonite, and finally, the starch and polyvinyl alcohol doped in the sodium bentonite are subjected to graft copolymerization by using an initiator to increase the water absorption of the starch, so that the modified starch can be rapidly settled after being contacted with a water body.

After the starch is oxidized, partial glycosidic bonds in molecules are broken, partial hydroxyl groups are oxidized into carboxyl groups, although the hydrogen bonding force of the carboxyl groups is not better than that of the hydroxyl groups, the carboxyl groups have better hydrophilicity, the dispersion of the starch in a water body is facilitated, the contact surface of the starch and algae is enlarged, the bonding strength is increased, and the flocculation effect is improved; the oxidized starch is mixed with the carboxymethyl cellulose and the sodium tetraborate, the carboxymethyl cellulose has intramolecular and intermolecular hydrogen bonding effects and has high viscosity, the sodium tetraborate is used as a complexing agent and has the effect of increasing the viscosity, in addition, the pH is adjusted to be alkaline, the sodium tetraborate can construct a framework, the framework is combined with lone pair electrons on the carboxymethyl cellulose and the starch to be mutually crosslinked, a crosslinking network is formed, and the bonding effect of the starch is improved.

Because glycerol is a micromolecule and can enter interlayer of the sodium bentonite more easily than PVA, the sodium bentonite has loose structure and higher water absorption rate, then the sodium bentonite is intercalated by polyvinyl alcohol, the sodium bentonite is not peeled into a single wafer after being intercalated, when starch, the sodium bentonite, an initiator and the like are mixed, the starch cannot be inserted into the interlayer of the sodium bentonite, the water absorption rate of the sodium bentonite is higher, the initiator can generate primary free radicals on the starch to initiate the graft copolymerization of the polyvinyl alcohol inserted into the sodium bentonite, the polyvinyl alcohol is grafted onto a starch molecular chain with a certain degree of polymerization, the water absorption rate and the viscosity of the starch are increased, the adhesion force of a purifying agent and the algal bloom is increased, the algal bloom floc can be rapidly settled, the separation of the algal bloom from the algal bloom floc is prevented, and the algal bloom floc is floated to the surface of a water body again.

In a second aspect, the application provides a preparation method of a composite water quality agglutination purifying agent, which adopts the following technical scheme: a preparation method of a compound water quality agglutination purifying agent comprises the following steps:

respectively crushing muscovite, serpentine and rare earth porcelain sand, mixing, adding water accounting for 10-15% of the total weight of the muscovite, the serpentine and the rare earth porcelain sand, ball-milling, drying, sieving, adding calcined silica, polyacrylamide and polyaluminium, and uniformly mixing to obtain the composite water quality agglutination purifying agent.

By adopting the technical scheme, the muscovite, the serpentine and the rare earth porcelain sand are mixed, ground by water, the particle size is reduced, and the mixture is uniformly mixed with components such as polyacrylamide after being dried, so that the prepared purifying agent is not influenced by water temperature, can efficiently remove organic pollutants in various sewage and wastewater, and is suitable for hot areas and severe cold areas.

In summary, the present application has the following beneficial effects:

1. because this application adopts components such as calcined silica, polyaluminium, polyacrylamide, serpentine to prepare the clarifier, polyacrylamide and serpentine, components such as calcined silica cooperate, can effectively make the pollutant flocculate and subside, 96% is inorganic compound in the component, the source is wide, the price is low, nontoxic, harmless, tasteless, no secondary pollution, reaction time is short, the settling rate is fast, do not receive the influence of water temperature and pH value, reach more than 90% to COD, TN, TP's clearance in the sewage of high turbidity, high salt, high oil, high suspended solid, the effect is showing, also can effectively flocculate and purify the sea water.

2. In the application, the silicon clay is preferably impregnated by a silver nitrate solution before being calcined, and due to the fact that metal cations and hydroxyl exist on the surface of the silicon clay, silver ions are loaded on the silicon clay in the form of silver simple substances under the adsorption and cation exchange effects of the hydroxyl, so that the silver ions are slowly released, and the instant and long-acting algae removal effect of the purifying agent is enhanced.

3. Preferentially mix modified starch and nanometer zinc oxide in the flocculating agent among this application, nanometer zinc oxide granule is little, can increase the closely knit degree of algal bloom floc, improves the settling velocity, and modified starch's viscosity is big, can increase the tight density of bonding of algal bloom and flocculating agent, prevents that algal bloom breaks away from and floats to the water surface again in the algal bloom floc to increase the stability of algal bloom floc, improve the long-term treatment effect of flocculating agent to algal bloom.

4. In the application, oxidized starch is preferably adopted to react with carboxymethyl cellulose and sodium tetraborate, so that the cohesiveness of the starch is improved; then, glycerin and polyvinyl alcohol are used for intercalation of the sodium bentonite, the looseness of the sodium bentonite is increased, the water absorption rate of the sodium bentonite is improved, finally, starch and the sodium bentonite are mixed under the action of an initiator, the initiator enables the polyvinyl alcohol inserted between sodium bentonite layers and the starch to be subjected to graft copolymerization, so that the polyvinyl alcohol is grafted to a starch molecular chain, the water absorption rate and the cohesiveness of the starch are increased, the adhesive force of a purifying agent and algal blooms is increased, the algal bloom flocs are rapidly settled and are not easily separated from the algal bloom flocs, and the long-acting algae purifying effect of the purifying agent is improved.

Detailed Description

Preparation example of modified starch

Preparation examples 1-7 wherein the starch is corn starch selected from Wuyi chemical technology Co., Ltd, Suzhou, cat # 014; the carboxymethyl cellulose is selected from Jiangsu Dayao chemical material Co, and the model is CMC; the sodium bentonite is selected from novel building materials of Shijiazhuang rhyme stone, and the product number is 325; the PVA is selected from Kaihua chemical industry and is PVA 088-50.

Preparation example 1: (1) mixing 8Kg of starch with 1.5Kg of oxidant, heating at 60 ℃ for 7min under the action of 400W of microwave after uniform mixing, adjusting the pH value to 8, adding 1Kg of carboxymethyl cellulose and 0.1Kg of sodium tetraborate, stirring uniformly and defoaming, wherein the oxidant is potassium permanganate with the weight percentage concentration of 1%;

(2) mixing 1.1Kg of sodium bentonite with 2Kg of distilled water to prepare a suspension, heating to 80 ℃, adding 0.5Kg of glycerol, stirring for 30min under heat preservation, adding 2.5Kg of PVA, stirring for 1h under heat preservation, centrifuging, drying and grinding;

(3) and (3) mixing the product obtained in the step (1) and the product obtained in the step (2), adding 0.5Kg of initiator and 5Kg of distilled water, heating to 45 ℃, keeping the temperature and stirring for 4 hours, and drying at 50 ℃, wherein the initiator is ammonium persulfate.

Preparation example 2: (1) mixing 10Kg of starch with 2Kg of oxidant, heating at 75 ℃ for 3min under the action of 400W of microwave after uniform mixing, adjusting the pH value to 10, adding 1.5Kg of carboxymethyl cellulose and 0.3Kg of sodium tetraborate, stirring uniformly and defoaming, wherein the oxidant is hydrogen peroxide with the weight percentage concentration of 30%;

(2) mixing 1.5Kg of sodium bentonite with 3Kg of distilled water to prepare a suspension, heating to 90 ℃, adding 1Kg of glycerol, keeping the temperature and stirring for 40min, adding 3KgPVA, keeping the temperature and stirring for 2h, centrifuging, drying and grinding;

(3) and (3) mixing the product obtained in the step (1) and the product obtained in the step (2), adding 1Kg of initiator and 7Kg of distilled water, heating to 60 ℃, keeping the temperature and stirring for 3 hours, and drying at 60 ℃, wherein the initiator is ammonium persulfate.

Preparation example 3: the difference from preparation example 1 is that the product obtained in step (2) was not added in step (3).

Preparation example 4: the difference from the preparation example 1 is that in the step (2), 2.5KgPVA is added, the heat preservation and the stirring are carried out for 2 hours, then 0.5Kg of glycerol is added, the heat preservation and the stirring are carried out for 30 minutes.

Comparative example 5: the difference from preparation example 1 is that carboxymethyl cellulose was not added in step (1).

Preparation example 6: the difference from preparation example 1 is that starch was not oxidized in step (1).

Preparation example 7: the difference from preparation example 1 is that in step (3) an equal amount of starch without any treatment was used instead of the product obtained in step (1).

Examples

In the embodiment, the cation modified starch is selected from Guangdong Hongxin biological technology limited company, and the model is YL 17; the average grain diameter of the nano zinc oxide is 10-30 nm.

Example 1: the preparation method of the compound water quality coagulation purifying agent comprises the following steps:

respectively crushing muscovite, serpentine and rare earth porcelain sand, mixing, adding water accounting for 10 percent of the total weight of the muscovite, the serpentine and the rare earth porcelain sand, performing ball milling, drying, sieving by a 200-mesh sieve, adding calcined silica, polyacrylamide and polyaluminium, and uniformly mixing to obtain the composite water quality agglutination purifying agent, wherein the particle size of the calcined diatomite is 200 meshes, and the calcined diatomite is prepared by calcining the silica at 1000 ℃ for 6 hours.

TABLE 1 raw material ratio of composite water quality agglutinant and purifying agent in examples 1-6

Examples 2 to 6: a composite water quality coagulation cleaning agent is different from the embodiment 1 in that the raw material formulation is shown in Table 1.

Example 7: a composite water quality agglutination cleaning agent is different from the embodiment 1 in that before calcination, silica is stirred with silver nitrate solution with the concentration of 0.2moL/L for 1 hour at room temperature, and then is immersed in vacuum and in a dark place for 30 minutes, and the mass ratio of the silica to the silver nitrate solution is 1: 2.

Example 8: a composite water quality agglutination cleaning agent is different from the embodiment 1 in that before calcination, silica is stirred with silver nitrate solution with the concentration of 0.1moL/L for 2 hours at room temperature, and then is immersed in vacuum and in a dark place for 40 minutes, and the mass ratio of the silica to the silver nitrate solution is 1: 2.

Example 9: a composite water quality agglutination purifying agent is different from the embodiment 7 in that the preparation method comprises the following steps: respectively crushing muscovite, serpentine and rare earth porcelain sand, mixing, adding water accounting for 10 percent of the total weight of the muscovite, the serpentine and the rare earth porcelain sand, performing ball milling, drying, sieving by a 200-mesh sieve, adding calcined silica, polyacrylamide, polyaluminium, 20Kg of modified starch and 15Kg of nano zinc oxide, and uniformly mixing to prepare the composite water quality aggregation purifying agent, wherein the modified starch is prepared by the preparation example 1.

Example 10: a composite water quality agglutination purifying agent is different from the embodiment 9 in that the addition amount of modified starch is 40Kg, the addition amount of nano zinc oxide is 25Kg, and the modified starch is prepared by the preparation example 2.

Example 11: a composite water quality coagulation cleaning agent is different from example 9 in that the sources of modified starch are shown in Table 2.

Table 2 sources of modified starches from examples 9-16

Comparative example

Comparative example 1: a composite water quality agglutination purifying agent is different from the embodiment 1 in that polyacrylamide is not added.

Comparative example 2: a composite water quality agglutination purifying agent is different from the agent in the embodiment 1 in that no polyaluminium is added.

Comparative example 3: a composite water quality agglutination purifying agent is different from the embodiment 1 in that polyacrylamide and polyaluminium are not added.

Comparative example 4: a composite water quality agglutination purifying agent is different from the embodiment 1 in that serpentine is not added.

Comparative example 5: a composite water quality agglutination purifying agent is different from the embodiment 1 in that serpentine and polyacrylamide are not added.

Comparative example 6: a composite water quality coagulation cleaning agent is different from the embodiment 1 in that calcined silica is not added.

Comparative example 7: a composite water quality agglutination cleaning agent is different from the embodiment 1 in that rare earth porcelain sand, calcined silica and serpentine are not added.

Comparative example 8: a composite purifying agent for purifying the water-free river channel comprises the following components in parts by weight: 70% of benzalkonium chloride, 15% of polymeric ferric sulfate, 8% of polyacrylamide, 5% of activated carbon, 2.0% of effervescent disintegrant, wherein the dosage of the peroxymonosulfuric acid accounts for 0.5 wt% of the total amount of the composite purifying agent, the effervescent disintegrant is prepared by mixing sodium bicarbonate and citric acid, and the weight ratio of the sodium bicarbonate to the citric acid is 3: 1; when in use, the polyferric sulfate and the polyacrylamide are firstly prepared into water solution by tap water, then the purifying agent compounded by the components is put into sewage, and the sewage is stirred and stood for precipitation.

Comparative example 9: a composite purifying agent is prepared from polyaluminium and polyacrylamide in a mass ratio of 1: 1.

Performance test

Firstly, detecting the input amount of the composite water quality agglutination purifying agent: taking the composite water quality agglutination purifying agent prepared in the embodiment 1 as an example, taking the sewage of a certain river in Beijing, and detecting the water quality of the sewage by the following main indexes: SS 154.5mg/L, COD 180.4mg/L, NH₃Adding the composite water quality agglutination purifying agent into the wastewater with different yields, stirring for 2-3h, naturally settling for 1h, sucking certain supernatant, analyzing various indexes in the wastewater, and recording the detection results in table 3, wherein N is 28.3mg/L and TP is 5.1 mg/L.

TABLE 3 Effect of input amount on composite water quality coagulation purificant

As can be seen from the data in Table 3, when the amount of the composite water quality flocculation purifying agent is 10-300g/m³The wastewater treatment method has good flocculation and purification effects on wastewater, the purified water meets the first-level discharge standard in GB8978-1996 Integrated wastewater discharge Standard, and the input amount is 150-³The effect is better.

The addition amount is increased, and the flocculation and purification effects of the purifying agent are reduced, because the colloid particles generated by flocculation change the original charge and generate the re-stabilization phenomenon, thereby reducing the flocculation effect.

Second, composite water quality agglutination purifying agent suitable for pH value and temperature detection

Taking the wastewater of a certain gas gathering station of a second gas production plant of the Changqing oil field, wherein the pH value is 6.6, and the main indexes for detecting the water quality are as follows: the COD is 496mg/L, the oil contamination pollutant is 251mg/L, the suspended matter is 96mg/L, the chroma is 337 times, then the pH value is adjusted by sulfuric acid or sodium hydroxide solution, the composite water quality agglutination purifying agent prepared in the example 1 is added into the oil field wastewater with different yields, the mixture is naturally settled for 1h after being stirred for 2 to 3h, certain supernatant is absorbed, various indexes in the wastewater are analyzed, and the detection result is recorded in the table 4.

Secondly, taking the wastewater of a certain gas gathering station of a second gas production plant of the Changqing oil field, wherein the pH value is 6.6, and the main indexes for detecting the water quality are as follows: the composite water quality agglutination purifying agent prepared in example 1 is added into the oil field wastewater with different yields, the water temperature is controlled to be 20 ℃, 30 ℃, 40 ℃ and 50 ℃, the composite water quality agglutination purifying agent is stirred for 2-3 hours and then naturally settled for 1 hour, a certain supernatant is absorbed, each index in the wastewater is analyzed, and the detection result is recorded in table 5.

TABLE 4 results of pH value measurements

As can be seen from the data in Table 4, when the pH values of the wastewater are 5 and 11, the purification effect of the wastewater is poor compared with that of the wastewater with pH values of 6, 8 and 10, and when the pH value of the wastewater is 6-10, the purifying agent has good flocculation effect and high purification efficiency, and after flocculation and purification, the water quality meets the first-level discharge standard in GB8978-1996 Integrated wastewater discharge Standard.

TABLE 5 applicable temperature detection

As can be seen from the data in Table 5, when the temperature of the wastewater is 20 ℃ or 50 ℃, the purification effect is high, which indicates that the water quality coagulation purifier prepared by the method is not affected by the temperature of water, is suitable for hot areas and cold areas, has high purification effect, and the water quality meets the first-level discharge standard in GB8978-1996 Integrated wastewater discharge Standard.

Third, the composite water quality agglutination purifying agent detects the purifying effect of various waste water

(1) Composite water quality agglutination purifying agent for purifying ore washing wastewater, coal washing wastewater and seawater

Firstly, taking ore washing wastewater of a river steel group of a Hebei stone house village, and measuring samples with the same volume, wherein the water quality indexes are as follows: SS 860mg/L, COD 213mg/L, TP 39.5mg/L, according to 150g/m³The composite water quality agglutination purification agents prepared in the examples and the comparative examples are respectively added into the sample, stirred for 2 hours, naturally settled for 1 hour, the supernatant is taken to detect each index, and the detection result is recorded in the table 6 (the ND indicates that the composite water quality agglutination purification agent is not detected).

Secondly, taking coal washing wastewater of the Hebei Tang III 28390group, and measuring samples with the same volume, wherein the water quality indexes are as follows: SS 3610mg/L, COD 97mg/L, according to 150g/m³The composite water quality agglutination purification agents prepared in the examples and the comparative examples are respectively added into the sample, stirred for 2 hours, naturally settled for 1 hour, the supernatant is taken to detect each index, and the detection result is recorded in the table 6 (the ND indicates that the composite water quality agglutination purification agent is not detected).

Taking the polluted seawater near the shore of Tianjin staphylea, measuring the sample with the same volume, wherein the turbidity is 20.5NTU, measuring the absorbance at the wavelength of 550nm, and the absorbance is expressed as B and is 150g/m³The composite water quality agglutination purification agents prepared in the examples and the comparative examples were added to the samples, stirred for 2 hours, allowed to settle naturally for 1 hour, and the absorbance of the supernatant at a wavelength of 550nm, represented by A, was calculated as the flocculation rate in terms of (B-A)/B × 100%, and the results of the measurements were recorded in Table 6.

TABLE 6 purifying effect of the composite water quality agglutinating and purifying agent on ore washing wastewater, coal washing wastewater and seawater

As can be seen from comparison of data in Table 6, the purifiers prepared in examples 1 to 6 have strong purification effects on the ore washing wastewater, the coal washing wastewater and the seawater, can completely remove SS in the wastewater, have a removal rate of over 90% on TP in the wastewater and a removal rate of over 82% on COD, and have water quality meeting the first-level discharge standard in GB8978-1996 Integrated wastewater discharge Standard after flocculation and purification of the ore washing wastewater and the coal washing wastewater.

The detection effects in examples 7 to 16 are not much different from those in examples 1 to 6, and all have excellent purification effects.

Compared with the example 1, the purifying agents in the comparative examples 1 and 2 have lower purifying effects on various types of wastewater and seawater because polyacrylamide and polyaluminium are not added in the comparative examples 1 and 2 respectively, while the purifying effects in the comparative examples 3 are not as good as those in the comparative examples 1 and 2 because the polyacrylamide and the polyaluminium are not added at the same time, which shows that the polyacrylamide and the polyaluminium have better synergistic effects.

Compared with the comparative example 4 and the comparative example 1, the effect of the comparative example 5 is remarkably reduced, and the serpentine and the polyacrylamide have better synergistic effect.

Compared with the comparative example 6 and the comparative example 4, the effect of the comparative example 6 on the purification of the ore washing wastewater, the coal washing wastewater and the seawater is obviously reduced, and the calcined silica, the serpentine and the rare earth porcelain sand have better matching effect and can improve the coagulation and coagulation aiding effects of the purifying agent.

Comparative example 8 is a composite purifying agent prepared by the prior art, the removal efficiency of pollutants in the ore washing wastewater and the coal washing wastewater is lower than that of example 1, the flocculation effect on seawater is low, and the purification effect on seawater is poor.

In comparative example 9, the purifying agent prepared by only using polyaluminium and polyacrylamide with the mass ratio of 1:1 has a better purifying effect on ore washing wastewater, coal washing wastewater and seawater than that of example 1, and the purifying agent prepared by the method has a better purifying effect on various types of wastewater.

(2) Compound water quality agglutination purifying agent for purifying slaughterhouse wastewater and textile water

Firstly, taking wastewater generated by a certain slaughter house in Beijing, and measuring samples with the same volume, wherein the water quality indexes are as follows: SS 1070mg/L, COD 5410mg/L, TN 361mg/L, TP 16.3mg/L, according to 150g/m³The composite water quality agglutination purification agents prepared in the examples and the comparative examples are respectively added into the sample, stirred for 2 hours, naturally settled for 1 hour, the supernatant is taken to detect each index, and the detection result is recorded in the table 7 (the ND indicates that the composite water quality agglutination purification agent is not detected).

Secondly, taking waste water of Shandong Zibo certain textile printing and dyeing enterprises, and measuring samples with the same volume, wherein the water quality indexes are as follows: COD 1200mg/L, BOD 840mg/L, chroma 840 times according to 150g/m³The composite water quality agglutination purification agents prepared in the examples and the comparative examples are respectively added into the sample, stirred for 2 hours, naturally settled for 1 hour, the supernatant is taken to detect each index, and the detection result is recorded in the table 7 (the ND indicates that the composite water quality agglutination purification agent is not detected).

TABLE 7 purifying effect of composite water quality agglutinating purificant on slaughterhouse wastewater and seawater

As can be seen from the data in Table 7, the composite water quality coagulation purificant prepared in examples 1-6 has high purification effect on slaughter house wastewater and printing and dyeing textile wastewater, and particularly, slaughter house wastewater with high SS content and printing and dyeing wastewater with high turbidity can ensure that the water quality is clear and transparent and meets the first-level discharge standard in GB8978-1996 Integrated wastewater discharge Standard.

The purifiers prepared in examples 7 to 16 were not much different from those of examples 1 to 6 in purification effect, and also had good flocculation and purification effects on slaughterhouse wastewater and printing and dyeing wastewater.

Compared with the example 1, the comparative example 1 has no polyacrylamide, the purifying effect of the comparative example 1 on slaughterhouse wastewater and textile wastewater is reduced, and SS cannot be completely removed.

Comparative example 2 compared with example 1, the purification effect of comparative example 2 on slaughterhouse wastewater and textile wastewater is reduced without adding polyaluminium, but the purification effect is better than that of comparative example 1.

Compared example 3 does not add polyacrylamide and polyaluminium at the same time, compared example 3 is inferior to compared example 2 in the purification effect on slaughterhouse wastewater and textile wastewater, and the polyacrylamide and polyaluminium have better synergistic effect.

Compared with the comparative example 4 and the comparative example 1, the effect of the comparative example 5 is remarkably reduced, and the serpentine and the polyacrylamide have better synergistic effect.

Compared with the comparative example 6 and the comparative example 4, the effect of the comparative example 6 on the purification of slaughterhouse wastewater and textile wastewater is obviously reduced, and the calcined silica, the serpentine and the rare earth porcelain sand have better matching effect and can improve the coagulation and coagulation aiding effects of the purifying agent.

Comparative example 8 is a composite purifying agent prepared by the prior art, and the purifying effect on slaughterhouse wastewater and textile wastewater is inferior to that of example 1 of the application.

In comparative example 9, the purifying agent prepared by only using polyaluminium and polyacrylamide with the mass ratio of 1:1 has poor purifying effect on SS in slaughterhouse wastewater and poor chroma removing effect on textile wastewater.

(3) Purifying effect of composite water quality agglutination purifying agent on algae

The wastewater from the plain section of the Hechang of Langchang, Beijing Wenchui elm was sampled as test water, the content of chlorophyll a in the wastewater was measured to be 152.4. mu.g/L according to HJ897-2017 spectrophotometry for measuring chlorophyll a in water, the wastewater for test was divided into 21 portions each of which was 1L, and the purifying agents prepared in example 1, examples 7-16 and comparative examples 1-9 were added to 26 portions of the wastewater for test, respectively, the amount of the purifying agent added per portion of the wastewater was 150g/m³Stirring for 10min at the rotating speed of 600r/min, naturally settling for 1h, taking the supernatant, detecting the content of chlorophyll a in the sewage according to HJ897-2017 (Spectrophotometer method for measuring chlorophyll a in water quality), then placing the supernatant in an incubator for culturing for 12h, controlling the temperature of the incubator to be 30 ℃, controlling the illumination intensity to be 6000lx, detecting the content of chlorophyll A in water extraction every 4h, and recording the detection result in a table 8.

TABLE 8 Long-term purifying effect of composite water quality agglutination purifier on algae

As can be seen from the data in Table 8, the purifying agent prepared in example 1 has a good purifying effect on algae, but the stability of algal bloom flocs is insufficient, and the algal bloom flocs are easily separated and float up to the surface of water extraction again.

The calcined silica prepared by calcining the silica impregnated with the silver nitrate solution in examples 7 and 8 has a bactericidal effect on algae in a water body with a slow release effect of silver ions, thereby preventing the floating algae from growing and propagating and thus prolonging the algae purification effect of the purification agent.

Compared with the example 7, the purifying agent in the examples 9 and 10 has better purifying effect on the algae-containing sewage and increased floc stability, and the content of the chlorophyll a in the supernatant is slowly increased along with the increase of time, so that the purifying agent has better long-acting purifying effect.

Example 11 compared to example 9, using the modified starch prepared in preparation example 3, in which the sodium bentonite prepared in step (2) was not added, example 11 showed a decrease in the initial purification effect on algae-containing wastewater, and the chlorophyll a content in the supernatant increased significantly with time, indicating that the addition of sodium bentonite increased the sedimentation of flocs and prevented the algal bloom flocs from floating up to the surface of the water body.

Example 12 in comparison with example 9, the modified starch was prepared by adding PVA and glycerol, and the purifying effect of the purifying agent on algae was not much different from that of example 9, but as the culture proceeded, the content of chlorophyll a in the supernatant gradually increased, the stability of algal bloom flocs decreased, and algae easily separated from algal bloom flocs and floated to the water surface.

Example 13 compared with example 9, in case that modified starch was selected from preparation example 5, without using carboxymethyl cellulose, the purifying effect of the purifying agent on algae was decreased, and the chlorophyll a content was increased to a large extent, indicating that carboxymethyl cellulose can enhance the long-lasting algae removal effect of the purifying agent.

Example 14 compared to example 9, when modified starch was prepared, no oxidation of starch was performed, and the data in table 8 shows that the initial content of chlorophyll a in the supernatant was increased, and the chlorophyll a content was significantly increased with time, indicating that hydroxyl groups on the surface of starch did not form carboxyl groups, and did not form a good cross-linked network with carboxymethyl cellulose, and algae were captured.

Example 15 compared with example 9, the purifying agent using starch treated with carboxymethyl cellulose, sodium tetraborate, etc. has a reduced purifying effect on algae-containing sewage and a reduced long-lasting purifying performance.

Example 16 compared with example 9, the modified starch used was a cationic modified starch, which was inferior to example 9 of the present application in terms of purification effect and long-lasting purification performance.

As can be seen from the data in Table 8, the purifiers prepared in comparative examples 1 to 7 have no better purifying effect than that of example 1 on the algae-containing sewage and have weak long-term purifying effect, while the purifying effects of comparative examples 8 and 9 are not as good as that of the present application.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.