CN112678987A - Treatment method and application of high-COD high-phosphorus heavy metal-containing sewage - Google Patents
Treatment method and application of high-COD high-phosphorus heavy metal-containing sewage Download PDFInfo
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Abstract
The invention relates to the field of sewage treatment, and discloses a method for treating high-COD high-phosphorus heavy metal-containing sewage, which comprises the following steps: step one, adjusting the pH value of the sewage to 5.6-7.6; step two, adding iron salt into the sewage obtained in the step one to perform a first mixing reaction, and then adding zeolite modified cationic polyacrylamide to perform a second mixing reaction; step three, carrying out solid-liquid separation on the mixed liquid obtained in the step two to obtain solid-phase flocs and separated water; concentrating the solid-phase floc, and then performing filter pressing to obtain concentrated supernatant and filter-pressed effluent, and returning to the step two; and step four, discharging the separated water after the adsorption treatment of an organic titanium adsorbent. The method can synchronously remove heavy metals, phosphorus elements and COD in the sewage, so that the contents of the heavy metals and the phosphorus in the discharged water and the COD of the discharged water reach the standard.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a treatment method and application of high-COD, high-phosphorus and heavy metal-containing sewage.
Background
With the increasing environmental requirements, the discharge of COD, total phosphorus and heavy metals is more strictly limited. GB31571-2015 and GB 31570-2015 stipulate that the emission limits of COD and total phosphorus are 60mg/L and 1.0mg/L respectively, for regions with beginning weakening environmental bearing capacity and the like, special emission limits of COD50mg/L and total phosphorus 0.5mg/L are also required, the emission requirements for heavy metals are stricter, a monitoring point is advanced to a wastewater discharge port of a workshop or a production facility, and specific emission limits of total lead, total arsenic, total cadmium, total nickel, total mercury and total chromium are limited.
The treatment difficulty of the sewage containing heavy metals with high COD is two, one is the removal of COD, and the other is the removal of heavy metals.
The method has application in the treatment of high COD sewage, such as coagulating sedimentation method, advanced oxidation method, electrochemical method, etc. The coagulating sedimentation method is mainly used for removing suspended matters and refractory macromolecular organic matters by adding a coagulant and a flocculant, and has the defect of limited removal effect; the advanced oxidation method (ozone, Fenton reagent and the like) degrades organic matters through the oxidation of generated strong oxidative hydroxyl radicals, is more and more widely applied to the treatment of organic wastewater difficult to degrade, and has the defects of low ozone utilization rate, insufficient oxidation capacity, unstable Fenton oxidation performance, large sludge production, increased chromaticity of iron ions in effluent and the like.
The methods for removing heavy metals from sewage are roughly classified into three types, i.e., chemical treatment methods (chemical precipitation, electrolysis, redox, etc.), physical treatment methods (adsorption, ion exchange, membrane separation, etc.), and biological treatment methods (biological adsorption, biological flocculation, phytoremediation, etc.).
The chemical precipitation method is easy to operate and low in cost, and is the most widely applied heavy metal treatment method. The chemical precipitation method includes a neutralization precipitation method, a sulfide precipitation method and a ferrite method. The neutralization precipitation method is to adjust the pH value to enable heavy metal ions to generate insoluble hydroxide precipitate for separation, can remove most heavy metals, but the optimal pH values of different heavy metal precipitates are different, and if various heavy metals exist in sewage, the removal effect of the heavy metals is poor. The sulfide precipitation method is an effective method for removing heavy metal ions in sewage by using sulfide, compared with the neutralization precipitation method, the sulfide precipitation method can precipitate the heavy metal ions under the condition of relatively low pH value, but a sulfide precipitator is easy to generate hydrogen sulfide gas under the acidic condition, so that secondary pollution is generated. The ferrite method is that ferric salt or ferrous salt is added into sewage, heated and stirred under alkaline condition, and proper amount of additive Na is added2CO3Form ferrite, and the heavy metal ions replace Fe in the ferrite lattice through the actions of adsorption, wrapping and entrainment2+Or Fe3+The ferrite method needs to be heated to about 70 ℃ or higher, and is slowly oxidized in the air, so that the operation time is long and the energy consumption is high.
CN102452745A discloses a treatment process of wastewater containing heavy metals, which comprises the steps of adjusting the pH value to 9-10 and adding hydroxide precipitator to remove the heavy metals. This method may be effective for removal of single or double heavy metal ions, but the removal of multiple heavy metal ions will be poor, and the patent does not deal with removal of high COD and total phosphorus.
CN108609804A discloses a BDP wastewater treatment method, which comprises the steps of ozone oxidation, biochemical treatment and membrane treatment, wherein the wastewater can reach the discharge standard after long-flow treatment.
Disclosure of Invention
The invention aims to solve the problem that heavy metals, COD (chemical oxygen demand) and phosphorus elements in sewage cannot be removed simultaneously in the prior art, and provides a method for treating high-COD high-phosphorus heavy metal-containing sewage.
In order to achieve the above object, a first aspect of the present invention provides a method for treating high-COD, high-phosphorus and heavy metal-containing sewage, comprising the steps of:
step one, adjusting the pH value of the sewage to 5.6-7.6;
step two, adding iron salt into the sewage obtained in the step one to perform a first mixing reaction, and then adding zeolite modified cationic polyacrylamide to perform a second mixing reaction;
step three, carrying out solid-liquid separation on the mixed liquid obtained in the step two to obtain solid-phase flocs and separated water; concentrating the solid-phase floc, and then performing filter pressing to obtain concentrated supernatant and filter-pressed effluent, and returning to the step two;
and step four, discharging the separated water after the adsorption treatment of an organic titanium adsorbent.
The second aspect of the invention provides an application of the method in the treatment of high-COD, high-phosphorus and heavy metal-containing sewage.
Through the technical scheme, the treatment method of the high-COD high-phosphorus heavy metal-containing sewage provided by the invention has the following beneficial technical effects:
the sewage treatment method provided by the invention can realize the synchronous removal of heavy metal elements, COD and phosphorus in the sewage, and the heavy metal content, COD value and phosphorus content in the treated sewage all meet the discharge requirement.
Furthermore, the method provided by the invention can be suitable for treating sewage containing heavy metal elements, COD is 8000mg/L and total phosphorus is 1-5mg/L (calculated as P), so as to synchronously remove COD, phosphorus and heavy metals in the sewage, and the treated sewage has low contents of COD, total phosphorus and heavy metal elements and can meet the discharge requirement specified in GB31571-2015, preferably, the discharge requirement specified in DB 11/307-2013.
Furthermore, in the method provided by the invention, the solid-phase floc obtained by solid-liquid separation partially flows back to the coagulation reaction stage, so that the contents of heavy metal, COD (chemical oxygen demand) and phosphorus in the treated effluent can be further reduced.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for treating high-COD high-phosphorus heavy metal-containing sewage, which comprises the following steps:
step one, adjusting the pH value of the sewage to 5.6-7.6;
step two, adding iron salt into the sewage obtained in the step one to perform a first mixing reaction, and then adding zeolite modified cationic polyacrylamide to perform a second mixing reaction;
step three, carrying out solid-liquid separation on the mixed liquid obtained in the step two to obtain solid-phase flocs and separated water; concentrating the solid-phase floc, and then performing filter pressing to obtain concentrated supernatant and filter-pressed effluent, and returning to the step two;
and step four, discharging the separated water after the adsorption treatment of an organic titanium adsorbent.
According to the invention, by carrying out accurate regulation of the pH value, coagulation sedimentation and organic titanium adsorption treatment on the high-COD, high-phosphorus and heavy metal-containing sewage, the synchronous removal of phosphorus elements, COD and heavy metal elements in the sewage can be realized, the sewage treatment process is greatly simplified, and the contents of heavy metals, COD and phosphorus in the treated effluent meet the discharge requirements specified in GB31571 and DB11/307 and 2013.
In the process of sewage treatment, the pH value of the sewage has a great influence on the effect of sewage treatment, particularly on the removal of heavy metal elements, COD and phosphorus elements in the sewage.
In the present invention, when the pH of the wastewater is 6.6 to 7.0, the wastewater treatment effect is more excellent.
According to the invention, acidic and/or alkaline substances are used to adjust the pH of the waste water.
According to the invention, the acidic substance is selected from at least one of hydrochloric acid, sulfuric acid and nitric acid; the alkaline substance is at least one selected from calcium hydroxide, sodium hydroxide and potassium hydroxide.
According to the invention, the heavy metal element comprises at least one of lead, mercury, nickel, cobalt and manganese.
According to the invention, the COD value of the sewage is more than 1500mg/L, preferably 2000-8000 mg/L.
According to the invention, the total phosphorus concentration in the sewage is more than 1mg/L, preferably 1.5-5mg/L, calculated as P.
According to the invention, the method also comprises the step of refluxing a part of the solid-phase flocs to the step two.
In the invention, in order to further reduce the contents of heavy metal and phosphorus elements and the COD value in the treated effluent, the solid-phase floc obtained by solid-liquid separation is partially refluxed to the second step, and the contents of the heavy metal elements and the phosphorus elements and the COD value in the treated effluent are further reduced through detection.
Further, in the present invention, the solid-phase flocs are refluxed to the second step at a reflux ratio of 20 to 70%, preferably 25 to 60%. In the present invention, the reflux ratio is a weight ratio of the solid-phase flocs returned to the step two to the whole solid-phase flocs.
According to the invention, in the second step, the amount of the iron salt is 1000-3000mg, preferably 1500-2500mg, relative to 1L of the sewage.
According to the invention, the iron salt is selected from at least one of ferric chloride, ferric sulfate, polymeric ferric chloride, polymeric ferric sulfate, polymeric ferric silicate and polymeric ferric silicate sulfate.
According to the invention, the zeolite modified cationic polyacrylamide is prepared by the following method:
(1) mixing zeolite and an acid solution for reaction, filtering, washing with water until the filtrate is neutral, and drying to obtain pretreated zeolite;
(2) and mixing the pretreated zeolite, cationic polyacrylamide and water, and carrying out a first reaction to obtain zeolite modified cationic polyacrylamide.
According to the invention, the zeolite modified cationic polyacrylamide prepared by the method is matched with ferric salt, and when the high-COD, high-phosphorus and heavy metal-containing sewage is treated by the method, COD, phosphorus elements and heavy metal elements in the sewage can be synchronously removed, so that the COD value and the contents of the phosphorus elements and the heavy metal elements in the treated effluent are remarkably reduced, and the effluent meets the discharge requirement.
According to the invention, the zeolite is selected from natural zeolites; preferably at least one of mordenite, stilbite, chabazite and heulandite.
According to the invention, the particle size of the zeolite is-60 mesh to +100 mesh.
In the present invention, the-60 mesh means that the zeolite is a molecular sieve capable of passing through 60 mesh, and the +100 mesh means that the zeolite is a molecular sieve incapable of passing through 100 mesh.
According to the present invention, the acidic solution is selected from at least one of a hydrochloric acid solution, a sulfuric acid solution, and a nitric acid solution.
According to the invention, after the zeolite is mixed and reacted with the acidic solution, impurities in pores of the zeolite can be removed, so that the zeolite has more excellent adsorption performance.
According to the invention, the concentration by mass of the acidic solution is between 0.2 and 5 wt.%, preferably between 0.5 and 2.5 wt.%.
In the present invention, the amount of the zeolite to be used is 0.4 to 4g, preferably 0.7 to 3g, relative to 100mL of the acidic solution.
In order to ensure the pretreatment effect of the zeolite, in the present invention, the zeolite is reacted with the acidic solution with stirring for at least 2 hours, preferably 3 to 5 hours.
In the present invention, the drying conditions include: the drying temperature is 50-70 ℃, preferably 55-65 ℃; the drying time is 5-8h, preferably 5.5-7 h.
According to the present invention, in the step (2), the cationic polyacrylamide is used in an amount of 0.2 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight, relative to 1000 parts by weight of water.
In the invention, the cationic degree of the cationic polyacrylamide is 30-80%, preferably 40-70%.
According to the present invention, in step (2), the pretreated zeolite is used in an amount of 0.5 to 3 parts by weight, preferably 0.7 to 2.6 parts by weight, relative to 1000 parts by weight of water.
In the present invention, the dissolution of the cationic polyacrylamide can be promoted by conventional methods in the prior art, such as ultrasonic and/or stirring, and specifically, the cationic polyacrylamide is stirred at 500-800rpm for 2-3h to dissolve in water.
According to the invention, in step (2), the reaction conditions include: the reaction temperature is 50-70 ℃, and preferably 55-65 ℃; the reaction time is 8-13h, preferably 9-11 h.
According to the invention, in the second step, the dosage of the zeolite modified cationic polyacrylamide is 2-10mg, preferably 4-8mg, relative to 1L of the sewage.
According to the invention, in the fourth step, the organic titanium adsorbent is used in an amount of 1 to 7 wt%, preferably 2 to 5 wt%, relative to the amount of the separated water.
According to the invention, in the second step, the time of the first mixing reaction is 1-15min, preferably 2-10min, and the time of the second mixing reaction is 2-7min, preferably 3-6 min.
According to the invention, in the fourth step, the time of the adsorption treatment is 5-40min, preferably 10-30 min.
In the present invention, the method further comprises: and regenerating the organic titanium adsorbent which is subjected to adsorption saturation after the separated water is subjected to adsorption treatment.
In the invention, the regeneration process comprises the following steps: contacting the adsorption saturated organic titanium adsorbent with acid and alkali.
In a second aspect, the invention provides an application of the method in treating high-COD high-phosphorus heavy metal-containing sewage.
The present invention will be described in detail below by way of examples.
In the following examples, the heavy metal content, phosphorus content and COD value in water were measured by HJ700-2014, HJ 694-.
In the examples and comparative examples, the respective starting materials were all commercially available products unless otherwise specified.
Preparation example
Examples and comparative examples the zeolite-modified cationic polyacrylamides used were prepared as described below.
(1) Pretreatment of zeolite: putting 1g of zeolite with the particle size of-60 meshes to +100 meshes into a beaker, adding 100mL of 1% HCl, stirring for reaction for 3 hours, filtering, washing with deionized water until the filtrate is neutral, and drying the solid at 60 ℃ for 6 hours;
(2) dissolution of cationic polyacrylamide: adding 1g of cationic polyacrylamide into 1L of deionized water, and stirring for 3h at 800 rpm;
(3) zeolite modified cationic polyacrylamide: and (3) adding 0.2g of the zeolite treated in the step (1) into the mixture in the step (2), stirring the mixture at the temperature of 60 ℃ to react for 4 hours, and then continuing the reaction in an oven at the temperature of 60 ℃ for 6 hours to obtain the zeolite modified polyacrylamide.
The kind of zeolite and the cationic degree of the cationic polyacrylamide are shown in table 1.
TABLE 1
| Zeolite-modified cationic polyacrylamides | Zeolite species | Cationic degree of cationic polyacrylamide |
| A1 | Mordenite zeolite | 70％ |
| A2 | Stilbite | 40％ |
| A3 | Chabazite zeolite | 60％ |
| A4 | Flake zeolite | 50％ |
| A5 | Mordenite zeolite | 60％ |
| A6 | Stilbite | 80％ |
| A7 | Chabazite zeolite | 30％ |
Example 1
(1) Adjusting the pH value of the sewage to 7.6 in a sewage adjusting tank;
(2) automatically flowing sewage into a reaction tank, adding 2500mg/L ferric chloride, stirring to react for 10min, adding mordenite modified cationic polyacrylamide A18 mg/L, and continuously stirring to react for 6 min;
(3) allowing the mixed solution to flow into a sedimentation tank for solid-liquid separation, allowing the mixed solution to stay for 10min, allowing 60% of flocs to flow back to the reaction tank, concentrating the residual flocs, press-filtering, burying, allowing the floc concentrated supernatant and press-filtered effluent to flow back to the reaction tank;
(4) and (3) allowing the effluent of the sedimentation tank to enter an organic titanium adsorption reaction tank, wherein the dosage of the organic titanium adsorbent is 5 per mill, and the reaction time is 30 min. The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Example 2
(1) Adjusting the pH value of the sewage to 5.6 in a sewage adjusting tank;
(2) automatically flowing sewage into a reaction tank, adding 1500mg/L ferric sulfate, stirring for reaction for 2min, adding stilbite modified cationic polyacrylamide A24 mg/L, and continuously stirring for reaction for 3 min;
(3) allowing the mixed solution to flow into a sedimentation tank for solid-liquid separation, allowing the mixed solution to stay for 5min, allowing 25% of flocs to flow back to the reaction tank, concentrating the residual flocs, press-filtering, burying, allowing the floc concentrated supernatant and press-filtered effluent to flow back to the reaction tank;
(4) and (3) allowing the effluent of the sedimentation tank to enter an organic titanium adsorption reaction tank, wherein the addition amount of the organic titanium adsorbent is 2 per mill, and the reaction time is 10 min. The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Example 3
(1) Adjusting the pH value of the sewage to 6.6 in a sewage adjusting tank;
(2) automatically flowing sewage into a reaction tank, adding 2000mg/L of polyferric chloride, stirring and reacting for 6min, adding chabazite modified cationic polyacrylamide A36 mg/L, and continuously stirring and reacting for 4 min;
(3) allowing the mixed solution to flow into a sedimentation tank for solid-liquid separation, allowing the mixed solution to stay for 7min, allowing 40% of flocs to flow back to the reaction tank, concentrating the residual flocs, press-filtering, burying, allowing the floc concentrated supernatant and press-filtered effluent to flow back to the reaction tank;
(4) and (3) introducing the effluent of the sedimentation tank into an organic titanium adsorption reaction tank, wherein the addition amount of the organic titanium adsorbent is 3.5 per mill, and the reaction time is 20 min. The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Example 4
(1) Adjusting the pH value of the sewage to 6.0 in a sewage adjusting tank;
(2) automatically flowing sewage into a reaction tank, adding 1800mg/L of polymeric ferric sulfate, stirring for reacting for 4min, adding 45 mg/L of zeolite modified cationic polyacrylamide, and continuously stirring for reacting for 4 min;
(3) allowing the mixed solution to flow into a sedimentation tank for solid-liquid separation, allowing the mixed solution to stay for 6min, allowing 30% of flocs to flow back to the reaction tank, concentrating the residual flocs, press-filtering, burying, allowing the floc concentrated supernatant and press-filtered effluent to flow back to the reaction tank;
(4) and (3) introducing the effluent of the sedimentation tank into an organic titanium adsorption reaction tank, wherein the addition amount of the organic titanium adsorbent is 3 per mill, and the reaction time is 15 min. The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Example 5
(1) Adjusting the pH value of the sewage to 7.0 in a sewage adjusting tank;
(2) automatically flowing sewage into a reaction tank, adding 2300mg/L of polysilicate iron, stirring for reacting for 8min, adding mordenite modified cationic polyacrylamide A57 mg/L, and continuously stirring for reacting for 5 min;
(3) allowing the mixed solution to flow into a sedimentation tank for solid-liquid separation, allowing the mixed solution to stay for 9min, allowing 50% of flocs to flow back to the reaction tank, concentrating the residual flocs, press-filtering, burying, allowing the floc concentrated supernatant and press-filtered effluent to flow back to the reaction tank;
(4) and (3) allowing the effluent of the sedimentation tank to enter an organic titanium adsorption reaction tank, wherein the addition amount of the organic titanium adsorbent is 4.5 per mill, and the reaction time is 25 min. The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Example 6
(1) Adjusting the pH value of the sewage to 7.3 in a sewage adjusting tank;
(2) automatically flowing the sewage into a reaction tank, adding 2700mg/L of polymeric ferric silicate sulfate, stirring for reacting for 13min, adding stilbite modified cationic polyacrylamide A69 mg/L, and continuously stirring for reacting for 7 min;
(3) allowing the mixed solution to flow into a sedimentation tank for solid-liquid separation, allowing the mixed solution to stay for 13min, allowing 65% of flocs to flow back to the reaction tank, concentrating the residual flocs, press-filtering, burying, allowing the floc concentrated supernatant and press-filtered effluent to flow back to the reaction tank;
(4) and (3) allowing the effluent of the sedimentation tank to enter an organic titanium adsorption reaction tank, wherein the addition amount of the organic titanium adsorbent is 6 per mill, and the reaction time is 35 min. The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Example 7
(1) Adjusting the pH value of the sewage to 5.8 in a sewage adjusting tank;
(2) automatically flowing sewage into a reaction tank, adding 1200mg/L ferric chloride, stirring for reacting for 1min, adding chabazite modified cationic polyacrylamide A73 mg/L, and continuously stirring for reacting for 2 min;
(3) allowing the mixed solution to flow into a sedimentation tank for solid-liquid separation, allowing the mixed solution to stay for 4min, allowing 20% of flocs to flow back to the reaction tank, concentrating the residual flocs, press-filtering, burying, allowing the floc concentrated supernatant and press-filtered effluent to flow back to the reaction tank;
(4) and (3) allowing the effluent of the sedimentation tank to enter an organic titanium adsorption reaction tank, wherein the addition amount of the organic titanium adsorbent is 1.5 per mill, and the reaction time is 7 min. The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Example 8
The procedure is as in example 1, with the only modification that no floc reflux is carried out in step (3). The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Comparative example 1
The procedure is as in example 1, with the only modification that the pH of the effluent is adjusted to 7.8 in step (1) and that no floc reflux is carried out in step (3). The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Comparative example 2
The procedure is as in example 1, with the only modification that the pH of the effluent is adjusted to 5.4 in step (1) and that no floc reflux is carried out in step (3). The contents of heavy metals and COD value in the effluent were as shown in Table 2.
Comparative example 3
The procedure is as in example 1, with the only modification that the ferric chloride is replaced by polyaluminium chloride in step (2).
Comparative example 4
The procedure is as in example 1, with the only modification that the mordenite-modified cationic polyacrylamide in step (2) is replaced by a cationic polyacrylamide.
Comparative example 5
The procedure is as in example 1, with the only modification that the organic titanium is replaced by activated carbon in step (4).
TABLE 2
As shown in Table 2, after the high-COD, high-phosphorus and heavy metal-containing sewage is treated by the method disclosed by the invention, COD, total phosphorus and heavy metals are synchronously removed, and the sewage can reach the discharge standard.
Furthermore, the solid floc part obtained by solid-liquid separation flows back to the coagulation treatment stage, so that the content of heavy metals and the COD value in the treated effluent can be further reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for treating high-COD high-phosphorus heavy metal-containing sewage comprises the following steps:
step one, adjusting the pH value of the sewage to 5.6-7.6;
step two, adding iron salt into the sewage obtained in the step one to perform a first mixing reaction, and then adding zeolite modified cationic polyacrylamide to perform a second mixing reaction;
step three, carrying out solid-liquid separation on the mixed liquid obtained in the step two to obtain solid-phase flocs and separated water; concentrating the solid-phase floc, and then performing filter pressing to obtain concentrated supernatant and filter-pressed effluent, and returning to the step two;
and step four, discharging the separated water after the adsorption treatment of an organic titanium adsorbent.
2. The treatment method according to claim 1, wherein the heavy metal elements in the sewage comprise at least one of lead, mercury, nickel, cobalt and manganese;
the COD value of the sewage is more than 1500mg/L, preferably 2000-8000 mg/L;
in the sewage, the total phosphorus concentration is more than 1mg/L, preferably 1.5-5mg/L calculated by P.
3. The process of claim 1 or 2 further comprising refluxing a portion of the solid floes to step two;
preferably, the reflux ratio of the solid-phase flocs is 20 to 70%, preferably 25 to 60%.
4. The treatment method according to any one of claims 1 to 3, wherein in the first step, the pH value of the wastewater is adjusted by using an acidic substance and/or a basic substance;
more preferably, the acidic substance is selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid; the alkaline substance is at least one selected from calcium hydroxide, sodium hydroxide and potassium hydroxide.
5. The treatment method according to any one of claims 1 to 4, wherein in the second step, the amount of the iron salt is 1000-3000mg, preferably 1500-2500mg, relative to 1L of the wastewater;
preferably, the iron salt is selected from at least one of ferric chloride, ferric sulfate, polymeric ferric chloride, polymeric ferric sulfate, polymeric ferric silicate, and polymeric ferric silicate sulfate.
6. The treatment method according to any one of claims 1 to 5, wherein the zeolite-modified cationic polyacrylamide is prepared by the following method:
(1) mixing zeolite and an acid solution for reaction, filtering, washing with water until the filtrate is neutral, and drying to obtain pretreated zeolite;
(2) and mixing the pretreated zeolite, cationic polyacrylamide and water, and reacting to obtain the zeolite modified cationic polyacrylamide.
7. The treatment process of claim 6, wherein the zeolite is selected from natural zeolites; preferably at least one of mordenite, stilbite, chabazite and heulandite;
preferably, the particle size of the zeolite is-60 meshes to +100 meshes;
preferably, the acidic solution is selected from at least one of a hydrochloric acid solution, a sulfuric acid solution, and a nitric acid solution;
more preferably, the mass concentration of the acidic solution is 0.2 to 5 wt%, preferably 0.5 to 2.5 wt%;
preferably, the zeolite is used in an amount of 0.4 to 4g, preferably 0.7 to 3g, relative to 100mL of the acidic solution;
preferably, in the step (2), the cationic polyacrylamide is used in an amount of 0.2 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight, relative to 1000 parts by weight of water;
preferably, in the step (2), the pretreated zeolite is used in an amount of 0.5 to 3 parts by weight, preferably 0.7 to 2.6 parts by weight, relative to 1000 parts by weight of water;
preferably, in step (2), the reaction conditions of the reaction include: the reaction temperature is 50-70 ℃, and preferably 55-65 ℃; the reaction time is 8-13h, preferably 9-11 h.
8. The treatment method according to any one of claims 1 to 7, wherein in the second step, the amount of the zeolite-modified cationic polyacrylamide is 2 to 10mg, preferably 4 to 8mg, relative to 1L of the wastewater;
preferably, in the fourth step, the amount of the organic titanium adsorbent is 1 to 7 wt%, preferably 2 to 5 wt%, relative to the amount of the separated water.
9. The process according to any one of claims 1 to 8, wherein in step two, the time of the first mixing reaction is 1 to 15min, preferably 2 to 10min, and the time of the second mixing reaction is 2 to 7min, preferably 3 to 6 min;
preferably, in the fourth step, the time of the adsorption treatment is 5-40min, preferably 10-30 min.
10. Use of the treatment method according to any one of claims 1 to 9 for the treatment of high COD, high phosphorous heavy metal containing wastewater.
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