CN103991987A - Process for pre-treating high-concentration phosphorus-containing wastewater to remove total phosphorus (TP) and process system thereof - Google Patents

Abstract

The invention discloses a process for pre-treating high-concentration phosphorus-containing wastewater to remove total phosphorus (TP) and a process system thereof, and in particular discloses to a process system for pre-treating high-concentration phosphorus-containing wastewater to remove TP through multi-point dosing based on a chemical method; the process system disclosed by the invention mainly comprises a sewage storage tank, an adjusting sedimentation tank, a first chemical reaction tank, a first high-efficiency clarification tank, a second chemical reaction tank, a second high-efficiency clarification tank, a buffer tank, a third chemical reaction tank, a third high-efficiency clarification tank, a coagulation mixing tank, solid-liquid separation equipment, a white mud concentrating and storing tank and a yellow mud concentrating and storing tank and is characterized in that chemical agents, such as calcium salt, acid, an oxidizing agent, a complexing agent and the like, are respectively added through the chemical method after high-concentration phosphorus-containing wastewater is aerated, homogenized and pre-oxidized in the sewage storage tank; oxidization reaction for many times, sedimentation reaction, and complexation coagulation reaction are realized; after solid-liquid separation is carried out for many times, the effluent TP is decreased from 2000 mg/L to about 10 mg/L; the removing rate is up to 99%; and pre-treated wastewater can be further subjected to biochemical treatment by entering a municipal pipe. The process system disclosed by the invention is capable of realizing resource recovery, effectively removing the phosphorus content in wastewater and greatly reducing the treatment burden of municipal wastewater.

Description

A process for pretreating high-phosphorus wastewater to remove total phosphorus and its process system

technical field

The present invention relates to an industrial wastewater treatment process, in particular to a process and a process system for pretreating high-phosphorus wastewater to remove total phosphorus, and in particular to a process based on chemical multi-point dosing to pretreat high-concentration phosphorus-containing wastewater to remove total phosphorus and its crafting system. the

Background technique

Phosphorus pollution can cause harm to the human body, marine organisms, soil, and water bodies in different degrees, especially phosphorus in water bodies in the form of orthophosphate ions, polymeric phosphates, and organic forest compounds. The total phosphorus concentration in still water bodies exceeds 86ug/L, it is judged that the water body is eutrophic and polluted. Excessive phosphorus in the water body will cause red tides, algae blooms, fish and shrimp deaths and other malignant phenomena. the

Chemicals such as sulfuric acid, nitric acid, phosphoric acid, and hypophosphite will be used in large quantities in the production process of electronics, electroplating industry, printed circuit board industry, chemical foil wastewater, and some precious metal catalysts, making the hypophosphite in the discharged high-concentration phosphorus-containing wastewater , Phosphite has become a difficult point in wastewater treatment technology. Phosphate-rich discharge into water bodies, under favorable light and other environmental conditions, is sufficient to promote excessive growth of algae in the water body, and in the subsequent algae death and subsequent metabolic activities of heterotrophic microorganisms, the water body Dissolved oxygen is likely to be depleted, resulting in deterioration of water quality and damage to the structure of the aquatic ecological environment. the

At present, the commonly used phosphorus-containing wastewater treatment method is chemical precipitation method, that is, adjusting the pH value of phosphorus-containing wastewater with lime, and adding metal replenishing agents for neutralization, coagulation, flocculation, and precipitation. In addition, there are ion exchange method, adsorption method, electrodialysis method, evaporation concentration method and reverse osmosis method, but the wastewater treated by these methods cannot achieve the ideal phosphorus removal effect, and contains these phosphorus-containing wastewater that has not been treated up to the standard Outflow will not only lead to environmental pollution, but also cause waste of resources. Moreover, some industrial phosphorus-containing wastewater is more difficult to treat. In addition to hypophosphorous acid and phosphorous acid that need to be oxidized, there are still a large amount of organic complexing agents in the waste liquid. The high chemical oxygen demand (COD) also requires a large amount of oxidant consumption. , so the added oxidizing agent disperses the power, and often cannot meet the oxidation requirements of hypophosphorous acid and phosphorous acid, so the removal effect is not good. The industry generally uses Fenton (Fenton's reagent), iron salt, aluminum salt coagulation and other methods to treat high phosphorus wastewater, but its stability is difficult to control, and the discharge water usually cannot meet the standard. the

Therefore, it is of great significance to find a new chemical precipitation process to overcome the deficiencies of coagulation methods such as Fenton (Fenton's reagent), iron salts, aluminum salts, etc., and to improve the removal effect of total phosphorus. the

Contents of the invention

The technical problem to be solved by the present invention is to provide a process for pretreating high-phosphorus wastewater to remove total phosphorus and its process system, especially to provide a chemical method based on multi-point dosing to pretreat high-concentration phosphorus-containing wastewater to remove total phosphorus process and its The process system overcomes the shortcomings of unsatisfactory treatment effect and high cost of the existing technology, and can effectively eliminate the phosphorus content in wastewater. It is an ideal method for treating high-concentration phosphorus-containing wastewater at present. the

The present invention is based on the following principles:

Theoretically, the chemical method can add treatment agents at one time, but the present invention chooses to add raw materials such as calcium chloride, acid, and oxidant several times in order to save costs and enhance the treatment effect. Phosphorus removal by chemical precipitation is accomplished through the process of chemical precipitation. By adding inorganic metal salt agents to sewage, it mixes with soluble salts in sewage, such as phosphate and phosphite, to form granular, insoluble Sexual substances, this process involves the so-called phase transfer process, and the reaction equation is shown in Equation 1. In fact, after the chemical agent is added, not only the precipitation reaction but also the chemical flocculation reaction are carried out in the sewage. the

According to water quality analysis, chemical precipitation considers the use of calcium salt as a precipitation agent. Under strongly alkaline conditions, the formation of calcium phosphite and calcium phosphate is carried out according to reaction formula 1:

3Ca ²⁺ +2PO3 ^3- →Ca ₃ (PO ₃ ) ₂ ↓ (pH≥8.5) Formula 1

3Ca ²⁺ +2PO4 ^3- →Ca ₃ (PO ₄ ) ₂ ↓

Studies have shown that a single oxidant has no significant removal effect on total phosphorus, and can only oxidize part of hypophosphite and phosphite into orthophosphate. FeSO4 alone has a low effect on phosphorus removal, and its removal rate of phosphate in water is only It is about 10-20%. However, the oxidant-FeSO4 combined process has multiple mechanisms such as oxidation, adsorption, and complexation precipitation, and shows good efficiency in removing pollutants in water. Experiments show that the reaction of KMnO4 and FeSO4 will generate new ecological iron-manganese oxides in situ. Among them, the introduction of manganese oxide has a very obvious effect on the removal of phosphate. The chemical reaction equation is reaction formula 2:

3Fe ²⁺ +MnO4 ^- +5H2O＝3Fe(OH)3↓+MnO2+H+ Formula 2

The phosphorus removal effect of KMnO4-FeSO4 process increases with the increase of iron salt dosage, and the phosphorus removal rate increases gradually with the increase of oxidant to FeSO4 molar ratio. the

Experiments have shown that the presence of common inorganic ions in water such as Ca2+, on the one hand, can increase the surface zeta potential of the floc particles solid-phase iron-manganese oxides formed by the KMnO4-FeSO4 process and reduce the relationship between phosphorus and solid-phase iron-manganese oxides. repulsion, which is beneficial to the adsorption and removal of phosphorus; on the other hand, at a higher pH value of the solution, the presence of Ca2+ is conducive to the transfer of solid iron oxides in the solution, increasing the amount of solid iron and manganese oxides used for adsorption of phosphorus. The effective amount of KMnO4-FeSO4 and Fe2(SO4)3 co-precipitation to remove phosphorus through a variety of mechanisms. The removal effect of KMnO4-FeSO4 process on phosphorus is much higher than the removal rate of each single substance in the process. The process shows good phosphorus removal efficiency, and has the advantages of high efficiency, economy and convenience. Deeply strengthened decontamination technology for polluted water bodies. the

The present invention uses calcium salt as a precipitating agent and generates calcium phosphite with high utilization value through excessive dosing. Since calcium phosphite is a slightly soluble substance, while calcium phosphate is an insoluble substance, in order to meet the standard of drainage TP (total phosphorus content) ≤ 10mg/L, the remaining phosphite must be oxidized into orthophosphate by chemical oxidation, and then mixed with Excess calcium chloride in water is removed by precipitation of calcium phosphate. the

The technical problem to be solved by the present invention is achieved through the following technical solutions:

A kind of technology of pretreating high phosphorus waste water to remove total phosphorus, comprises the following steps, comprises following chemical precipitation reaction;

Including at least the first chemical precipitation reaction: aeration, homogenization and pre-oxidation of high-concentration phosphorus-containing wastewater; adding an appropriate amount of acid to adjust the pH value to 8.5-10.0, adding excess calcium salt and stirring thoroughly, and performing the first chemical precipitation reaction to obtain white The sludge is precipitated to obtain the first treatment water; the aeration homogenization makes the high-phosphorus wastewater discharged from different batches of different concentrations uniformly mixed; the pre-oxidation uses the oxygen in the air to oxidize part of the hypophosphite into phosphorous acid Salt or orthophosphate, such as calcium phosphate and calcium phosphite white mud precipitates out, reducing the dosage of oxidant in the later stage. the

Or/and, it also includes at least the second chemical precipitation reaction: add an appropriate amount of acid, oxidant, and complexing agent solution to the sewage after the first treatment, adjust the pH value to 3.5-4.5, and perform the second chemical precipitation , oxidation, and complex coagulation reaction, the yellow mud precipitates out, and the supernatant for the second treatment is obtained; 

Or/and, it also includes at least the third chemical precipitation reaction: add an appropriate amount of oxidant to the supernatant of the second treatment, aerate and mix, add calcium salt, oxidant, and ferrous sulfate to the sewage after the oxidation reaction, and perform the second Three times of chemical precipitation, oxidation, and complex coagulation reaction, yellow mud precipitates out, and the third treatment supernatant is obtained; the third treatment supernatant is mixed with sodium hydroxide, polyaluminum chloride (PAC), poly Acrylamide (PAM), mixed for solid-liquid separation, to remove suspended matter, to obtain the treated low-phosphorus discharge water that meets the standard; furthermore, the discharge water enters the municipal pipe network for further biochemical treatment. the

The purpose of the sodium hydroxide is to adjust the pH value of the wastewater, and the function of the PAC is to coagulate and precipitate through the four aspects of compressing the electric double layer, electrically neutralizing, coiling and netting, and absorbing and bridging, so that the wastewater particles The substances are precipitated and filtered out, and the PAM molecules can bridge and adsorb the suspended particles dispersed in the solution, which has a strong flocculation effect. the

The step also includes mud-water separation: after the white mud and yellow mud sludge are dewatered, the sludge is recycled. the

The acid is one or more selected from hypochlorous acid (HClO), hydrochloric acid (HCl), sulfuric acid (H ₂ SO ₄ ), and the addition ratio of the components is any ratio >0;

The calcium salt is one or more selected from calcium chloride (CaCl ₂ ), calcium oxide (CaO), calcium carbonate (CaCO ₃ ), calcium hypochlorite Ca(ClO) ₂ , and the addition ratio of the components is any ratio >0;

The oxidant is selected from hypochlorous acid (HClO), sodium hypochlorite (NaClO), chlorine dioxide (ClO ₂ ), chlorine gas (Cl ₂ ), potassium permanganate (KMnO ₄ ), sodium permanganate (NaMnO ₄ ), One or more of potassium ferrate, ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), the addition ratio of the components is any ratio >0; but potassium permanganate (KMnO ₄ ) and hydrogen peroxide are excluded (H ₂ O ₂ ) added at the same time;

The complex coagulant is one or more of ferrous sulfate, ferrous chloride, and polyferric sulfate, and the addition ratio of the components is any ratio >0. the

The calcium salt consumption is that the molar ratio of Ca and P (phosphorus) in the waste water is 2:1-10:1; the molar ratio of P (phosphorus) in the oxidant and the supernatant is added in the described second treatment supernatant. The ratio is 2:1-20:1; wherein the amount of sodium hydroxide added is 0.2-0.5g/L waste water, polyaluminum chloride (PAC) added amount is 0.5-2g/L waste water, polyacrylamide (PAM) 0.01-0.05/L waste water;

The molar ratio of FeSO ₄ ·7H ₂ O and oxidant is 3:1-10:1; especially the molar ratio of FeSO ₄ ·7H ₂ O and KMnO ₄ is 3:1-10:1;

The present invention also provides the process system for pretreating high-phosphorus wastewater to remove total phosphorus, which includes mutually configured sewage storage tanks, regulating sedimentation tanks, coagulation mixing tanks, solid-liquid separation equipment, and sedimentation concentration storage tanks. After adjusting the sedimentation tank, there are also the first chemical reaction tank, the first high-efficiency clarification tank, the second chemical reaction tank, the second high-efficiency clarification tank, the third chemical reaction tank, and the third high-efficiency clarification tank;

The regulating sedimentation tank can homogenize the water quality and settle part of the suspended solids in the waste water. the

There is also a buffer tank between the second high-efficiency clarifier and the third chemical reaction tank. Since there is a direct height difference between the high-efficiency clarifier and the chemical reaction tank, overflow cannot be relied on. null;

The sediment concentration storage tank is divided into a white mud concentration storage tank and a yellow mud concentration storage tank. the

The sediment concentration storage tank is also equipped with sludge dewatering equipment, and the sludge dewatering equipment (14) is selected from one or more of known plate and frame filter presses and screw dehydrators. the

The solid-liquid separation equipment is one or more serial combinations of known dissolved air flotation equipment and inclined plate sedimentation tanks. the

Compared with the prior art, the process of the present invention and its process system adopt the technical effect of the above-mentioned technical scheme:

1. The removal rate of total phosphorus is high. Under the condition of the same chemical dosage, adding reagents at multiple points can reduce the amount of precipitation reaction reagents and save operating costs. the

2. Low operating cost, low processing cost, and obvious economic and social benefits. the

3. The chemical agents such as calcium salt, acid, oxidizing agent and complexing agent added in the process of the present invention realize multiple oxidation, precipitation, complex coagulation reactions, and after multiple solid-liquid separations, ensure that the total phosphorus in the effluent (TP ) from 2000mg/L to about 10mg/L, the removal rate is as high as 99%, and the pretreated wastewater can directly enter the municipal pipe network for further biochemical treatment. the

4. This process system can realize the recovery of resources, effectively eliminate the phosphorus content in wastewater, and greatly reduce the burden of municipal sewage treatment. the

Description of drawings

Fig. 1 is a structural representation of the process system of the present invention

Among them: 1-sewage storage tank, 2-regulating sedimentation tank, 3-first chemical reaction tank, 4-first high-efficiency clarification tank, 5-second chemical reaction tank, 6-second high-efficiency clarification tank, 7-buffer tank , 8-the third chemical reaction tank, 9-the third high-efficiency clarification tank, 10-coagulation stirring tank, 11-solid-liquid separation equipment, 12-white mud concentration storage tank, 13-yellow mud concentration storage tank, 14-pollution Mud dehydration equipment

Detailed ways

The present invention will be further described below in conjunction with specific examples, but not as a limitation to the present invention. the

As shown in Figure 1, a process for pretreating high-phosphorus wastewater to remove total phosphorus and a process system thereof, completes the removal of total phosphorus from wastewater through the following steps, so as to obtain wastewater that reaches the standard of direct exclusion:

(1) The first chemical precipitation: High-concentration phosphorus-containing wastewater enters the sewage storage tank 1, is aerated and homogenized by industrial wind, and enters the regulating sedimentation tank 2 after being pre-oxidized; the raw material sludge produced in the regulating sedimentation tank 2 is recycled, and the supernatant The liquid is lifted to the first chemical reaction tank 3 through the primary lifting pump, and an appropriate amount of hydrochloric acid is added through the metering pump to control the pH value of the sewage at 8.5-10.0, and excess calcium chloride is added; the acid is 30% hydrochloric acid, or it can be already The concentration of common knowledge, such as one or more replacements of hypochlorous acid, hydrochloric acid, sulfuric acid with a percentage concentration of 10-99%, said multiple combinations adding component ratios are any proportion of known common sense > 0, During the concrete embodiment, be the ratio of 1:1 between the components;

The calcium salt is one or more selected from calcium chloride, calcium oxide, calcium carbonate, and calcium hypochlorite, and the ratio of the components added in combination is any ratio of known common sense > 0, such as the component Between be the ratio of 1:1; Described calcium salt consumption is that the molar ratio of Ca and phosphorus in waste water is 2:1, 6:1 or 10:1;

Stir fully to make the phosphate, phosphite and calcium ions in the wastewater fully react to produce calcium phosphate and calcium phosphite precipitation, and the effluent enters the first effect clarification tank 4 for the first chemical precipitation, and the precipitated calcium phosphate and phosphorous acid Calcium white mud enters the white mud concentration storage tank 12 by gravity flow, and the produced water of the first sedimentation treatment enters the second chemical reaction tank 5;

(2) chemical precipitation for the second time: add hydrochloric acid, potassium permanganate, ferrous sulfate solution simultaneously in the waiting water of described second chemical reaction tank 5; Wherein the selected concentration is 30% hydrochloric acid, dosage is 2ml /L waste water, the molar ratio of phosphorus in the oxidant potassium permanganate and the supernatant to be treated is 2:1-20:1, specifically 2:1, 10:1 or 20:1; the ferrous sulfate The dosage is 10:1, 8:1, or 12:1 when the mol ratio of FeSO4.7H2O and phosphorus is counted as the embodiment; the mol ratio of the described FeSO4.7H2O and potassium permanganate is 3 when the embodiment is :1, 6:1 or 10:1. The flow is controlled by the metering pump, so that the pH value of the sewage is controlled at 3.5-4.5, specifically pH 3.5, 4 or 4.5, or the pH value that can be inferred from known common sense, and the second chemical precipitation, oxidation, and complexation are performed. coagulation reaction. The reaction effluent overflows into the second high-efficiency clarifier 6, and the precipitated yellow mud is pumped into the yellow mud concentration storage tank 13, and the supernatant enters the buffer tank 7 by gravity flow;

The complex coagulant is one or more of ferrous sulfate, ferrous chloride, and polyferric sulfate, and the addition ratio of the components is any ratio >0. the

(3) The third chemical precipitation: the sewage in the buffer tank 7 is lifted to the third chemical reaction tank 8 by the secondary lift pump; before entering the third chemical reaction tank 8, an appropriate amount of high Potassium manganate, the molar ratio of potassium permanganate and P is 3:1, 6:1 or 10:1; after aeration and mixing, the oxidation reaction is carried out in the sewage storage tank 1; the sewage after the reaction is mixed through the pipeline After mixed with calcium chloride, potassium permanganate, and ferrous sulfate at the same time, the molar ratio of calcium chloride dosage is Ca and phosphorus in wastewater is 5:1, and the dosage of ferrous sulfate is FeSO4 7H2O and The mol ratio of P is 10:1, 8:1, or 12:1 during the embodiment; FeSO 7H O and the mol ratio of potassium permanganate during the embodiment are 3:1, 6:1 or 10:1;

After mixing, the third chemical precipitation, oxidation, and complex coagulation reactions are carried out. The effluent flows into the third high-efficiency clarifier 9 by gravity, and the formed yellow mud also enters the yellow mud concentration storage tank 13, while the supernatant enters the mixing tank 9 by gravity flow. Coagulation and stirring tank 10; in the coagulation and stirring tank, the supernatant is mixed with sodium hydroxide, polyaluminum chloride, polyacrylamide, wherein the ratio of addition to waste water is, sodium hydroxide is 0.2-0.5g/L waste water, Polyaluminum chloride is 0.5-2g/L waste water, polyacrylamide is 0.01-0.05/L waste water; The specific addition amount in the embodiment is: sodium hydroxide is 0.2g/L waste water, 0.3g/L waste water or 0.5g/L waste water; polyaluminum chloride is 0.5g/L waste water, 1.2g/L waste water or 2g/L waste water; polyacrylamide is 0.01g/L waste water, 0.03g/L waste water or 0.05/L waste water, After mixing, enter the solid-liquid separation equipment (11) for solid-liquid separation to remove suspended matter. So far, the treatment is completed, and the final product water can enter the municipal pipe network for further biochemical treatment. the

(4) Separation of mud and water: the sludge concentrated in the white mud concentration storage tank 12 and the yellow mud concentration storage tank 13 enters the sludge dewatering equipment 14 for dehydration, which can achieve sludge recycling and save resources. the

Test run example 1

The phosphorus content in the wastewater discharged from a polyacrylamide unit of a refinery company in Heilongjiang is extremely high, and its total phosphorus (TP) concentration reaches about 1800mg/L. Phosphorus content is seriously exceeded. the

For the phosphorus-containing sewage discharged from the polyacrylamide plant, the project design treatment capacity: 240m ³ /d (10m ³ /h). After the traditional process system treatment, choose to add excessive calcium chloride precipitation combined with chlorine dioxide oxidation process method, the water quality after treatment is as follows: total phosphorus ≥ 50mg/L, not up to the standard, not up to the discharge standard. Afterwards, adopt technology of the present invention to carry out rectification to traditional technology, adopt chemical method to add calcium chloride, potassium permanganate, ferrous sulfate in stages, wherein calcium chloride dosage is Ca and P (phosphorus) in waste water The molar ratio is 5:1. The dosage of ferrous sulfate is FeSO ₄ 7H ₂ O and P molar ratio is 10:1; the molar ratio of FeSO ₄ 7H ₂ O and potassium permanganate is 10:1 to achieve secondary oxidation, precipitation Combined coagulation reaction, because the solid-phase iron-manganese oxide formed by the KMnO ₄ -FeSO ₄ joint process has a strong combination of complexation precipitation and adsorption, the process works well, and the total phosphorus (TP) in the effluent is reduced from 2000mg/L down to about 10mg/L.

Using this process to run and debug the processing results of each unit is as follows:

the Total Phosphorus pH Raw water inflow (mg/L) ≤2000 12-13 1# high efficiency clarifier effluent (mg/L) ≤300 12-13 2# high efficiency clarifier effluent (mg/L) ≤150 4-5 3# high efficiency clarifier effluent (mg/L) ≤50 4-5 Solid-liquid separation equipment effluent (mg/L) ≤10 6-9 Final effluent (mg/L) ≤10 6-9

Test run example 2

In this example, a beaker experiment was carried out in combination with the above-mentioned process. The specific steps and results are as follows:

Test run example 3

In this example, a beaker experiment was carried out in combination with the above-mentioned process. The specific steps and results are as follows:

The above-mentioned embodiments are only one of the selected specific implementation manners of the present invention, rather than limiting the implementation manners. For those skilled in the art, other changes in different forms can also be made on the basis of the above description. The obvious changes and substitutions derived therefrom shall be included in the protection scope of the present invention. the

Claims (10)

1. A process for pretreatment of high-phosphorus wastewater to remove total phosphorus, comprising the following steps: Including at least the first chemical precipitation reaction: aeration homogenization and pre-oxidation of high-concentration phosphorus-containing wastewater; adding an appropriate amount of acid to adjust the pH value to 9-10, adding excess calcium salt and stirring thoroughly, and performing the first chemical precipitation reaction, white mud Precipitate out, get the water to be treated for the first time; Or/and, also include at least the second chemical precipitation reaction: adding an appropriate amount of acid to the sewage after the first treatment to adjust the pH value to 3.5-4.5, and also adding oxidant and ferrous sulfate solution to carry out the second chemical precipitation reaction Precipitation, oxidation, complex coagulation reaction, precipitation of yellow mud, and supernatant to be treated for the second time; Or/and, it also includes at least the third chemical precipitation reaction: add an appropriate amount of oxidant to the supernatant of the second treatment, aerate and mix, add calcium salt, oxidant, and complexing agent to the sewage after the oxidation reaction, and carry out The third time chemical precipitation, oxidation, complex coagulation reaction, the precipitation of yellow mud separates out, obtains the supernatant liquid of processing for the 3rd time; Polyacrylamide (PAM) is mixed for solid-liquid separation, suspended solids are removed, and treated low-phosphorus effluent water is obtained. 2. the process for removing total phosphorus from pretreatment high-phosphorus wastewater according to claim 1, said step also includes mud-water separation, after white mud and yellow mud sedimentation sludge dehydration, sludge recycling is carried out; said low-phosphorus up to standard discharge The water also enters the municipal pipe network for further biochemical treatment. 3. the technology that the pretreatment high phosphorus waste water according to claim 1 removes total phosphorus, in the described step, The acid is one or more selected from hypochlorous acid (HClO), hydrochloric acid (HCl), sulfuric acid (H ₂ SO ₄ ), and the addition ratio of the components is any ratio >0; The calcium salt is one or more selected from calcium chloride (CaCl ₂ ), calcium oxide (CaO), calcium carbonate (CaCO ₃ ), calcium hypochlorite Ca(ClO) ₂ , and the addition ratio of the components is any ratio >0; The oxidant is selected from hypochlorous acid (HClO), sodium hypochlorite (NaClO), chlorine dioxide (ClO ₂ ), chlorine gas (Cl ₂ ), potassium permanganate (KMnO ₄ ), sodium permanganate (NaMnO ₄ ), One or more of potassium ferrate, ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), the addition ratio of the components is any ratio >0; but potassium permanganate (KMnO ₄ ) and hydrogen peroxide are excluded (H ₂ O ₂ ) added at the same time; The complex coagulant is one or more of ferrous sulfate, ferrous chloride, and polyferric sulfate, and the addition ratio of the components is any ratio >0. 4. according to claim 1 or 3 described pretreatment process of high phosphorus waste water removing total phosphorus, described calcium salt consumption is that the mol ratio of P (phosphorus) in Ca and waste water is 2:1-10:1; The molar ratio of adding oxidant to the liquid to be treated and P (phosphorus) in the treatment liquid is 2:1-20:1; the addition of sodium hydroxide is 0.2-0.5g/L waste water, polyaluminum chloride (PAC) The addition amount is 0.5-2g/L waste water, polyacrylamide (PAM) is 0.01-0.05/L waste water. 5 . The process for pretreating high phosphorus wastewater to remove total phosphorus according to claim 3 , wherein the molar ratio of FeSO ₄ .7H ₂ O to oxidant is 3:1-10:1. 6. the system of the technology of the pretreatment high-phosphorus wastewater removal total phosphorus of one of claim 1-5, comprises the sewage storage pond (1) that configures mutually, regulates sedimentation pond (2), coagulation stirring pond (10), solidification Liquid separation equipment (11), a sedimentation and concentration storage tank, is characterized in that: the first chemical reaction tank (3), the first high-efficiency clarification tank (4), the second chemical reaction pool (5), the second high-efficiency clarification pool (6), the third chemical reaction pool (8), and the third high-efficiency clarification pool (9). 7. according to the system of the pretreatment process of high-phosphorus wastewater removal of total phosphorus according to claim 6, it is characterized in that: a buffer pool is also configured between the second high-efficiency clarification tank (6) and the third chemical reaction tank (8) (7). 8. The process system for pretreating high-phosphorus wastewater to remove total phosphorus according to claim 6, characterized in that: said sediment concentration storage tanks respectively have a white mud concentration storage tank (12) and a yellow mud concentration storage tank (13). 9. according to the system of the technology of the pretreatment high-phosphorus wastewater removal total phosphorus of claim 6, it is characterized in that: described sedimentation concentration storage tank is equipped with sludge dewatering equipment (14), and described sludge dewatering equipment (14) selects One or more of plate and frame filter press and screw dehydrator. 10. according to the system of the process system of pretreatment high phosphorus wastewater removal total phosphorus of claim 6, it is characterized in that: described solid-liquid separation equipment (11) is selected from one of dissolved air flotation equipment, inclined plate sedimentation tank or Various series combinations.