CN116002834B - Heavy metal organic coupling agent and treatment method applied to sewage treatment - Google Patents
Heavy metal organic coupling agent and treatment method applied to sewage treatment Download PDFInfo
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Abstract
The invention discloses a heavy metal organic coupling agent, which comprises a starch organic flocculant, a modified compound additive and a medium modified liquid, wherein the mass ratio of the starch organic flocculant to the modified compound additive to the medium modified liquid is (4-5) 2: (9-11). The starch organic flocculant is better matched with the modified compound additive, the chitosan aqueous solution has the effects of capacity increase and permeability increase, the compatibility of raw materials of a product system is enhanced, the surfactant and the organic acid are matched, the medium modified liquid is used as an intermediate, the starch organic flocculant and the modified compound additive are better mutually compatible and mutually assisted in the system, and the formed coupling agent can be used for excellently adsorbing heavy metals and the product has excellent stability in treating the heavy metals in an acid corrosion environment.
Description
Technical Field
The invention relates to the technical field of heavy metal sewage treatment, in particular to a heavy metal organic coupling agent and a treatment method applied to sewage treatment.
Background
The sewage treatment is a process for purifying sewage to meet the water quality requirement of being discharged into a certain water body or reused. The sewage treatment is widely applied to various fields of buildings, agriculture, traffic, energy sources, petrifaction, environmental protection, urban landscapes, medical treatment, catering and the like, and the sewage treatment is increasingly carried into the daily life of common people. Heavy metal pollution is environmental pollution caused by heavy metal ions and compounds thereof, is difficult to degrade in the environment, can be accumulated in animals and plants, is gradually enriched through a food chain, causes great damage to kidneys, livers, brains, nerves, vision and the like after entering a human body, and is one of pollutants with the greatest harm to human health. The source of heavy metal ions mainly refers to the discharge of wastewater in industrial production, such as enterprises of electroplating, electrolysis, hardware, circuit board production, printing and dyeing, leather manufacturing and the like.
In the organic coupling, organic polymer coupling heavy metals are mostly adopted to form flocculation sedimentation treatment, and the existing organic coupling agent can remove heavy metals, but has general effect, especially in an acid corrosion environment, the stability of the coupling agent is reduced, and the removal treatment efficiency of the heavy metals is further limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a heavy metal organic coupling agent and a treatment method applied to sewage treatment so as to solve the problems in the prior art.
The invention solves the technical problems by adopting the following technical scheme:
the invention provides a heavy metal organic coupling agent, which comprises a starch organic flocculant (the raw materials in the prior art, see the specific implementation contents of the specification in detail), a modified compound additive and a medium modifying liquid, wherein the mass ratio of the starch organic flocculant to the modified compound additive to the medium modifying liquid is (4-5) 2: (9-11).
Preferably, the preparation method of the modified compound additive comprises the following steps:
s01: firstly placing bentonite at 310-330 ℃ for reaction for 10-20min, and then cooling to room temperature at a speed of 1-3 ℃/s for standby;
s02: adding 2-3 parts of lanthanum sulfate into 10-20 parts of deionized water, adding 0.2-0.5 part of phosphoric acid buffer solution, wherein the pH value of the phosphoric acid buffer solution is 3-5, then adding 1-3 parts of sodium alginate solution, and stirring fully to obtain a synergistic dispersion adjustment auxiliary liquid;
s03: placing the S01 product into 3-5 times of dispersion-assisting liquid for stirring reaction, and after stirring, washing and drying to obtain bentonite dispersion-assisting agent;
s04: the bentonite synergist is sent into the hydroxyapatite agent, uniformly stirred according to the weight ratio of the bentonite synergist to the hydroxyapatite agent of 1:5, and finally washed and dried to obtain the modified compound additive.
The inventor finds that the modified compound additive and the medium modification liquid are adopted for treatment and synergism, and the modified compound additive and the medium modification liquid are synergistic, so that the adsorptivity of the product and the adsorption stability of the acid environment are enhanced;
in the preparation of the modified compound additive, bentonite is not treated in the step S01, the modified compound additive is not treated by adopting a co-dispersion adjustment auxiliary liquid, the adsorption performance and the adsorption stability of the product are both prone to deterioration, the treatment methods of the bentonite are different, and the performance effects of the product are different;
in addition, the inventor of the invention also finds that lanthanum sulfate and phosphoric acid buffer solution are not added in the preparation of the synergistic dispersion auxiliary liquid, the performance of the product is poor, and the product has optimal performance effect only through the treatment of the synergistic dispersion auxiliary liquid prepared by the method of the invention and the treatment of the bentonite step S01;
the bentonite raw material is replaced by layered mica powder, the performance of the product is poor, and the bentonite raw material is also specific.
Preferably, the mass fraction of the sodium alginate solution is 10-20%.
Preferably, the stirring rotation speed of the stirring reaction of the S03 is 450-500r/min, the stirring time is 10-20min, and the stirring temperature is 45-50 ℃.
Preferably, the hydroxyapatite agent comprises the following raw materials in parts by weight:
3-5 parts of hydroxyapatite, 10-15 parts of hydrochloric acid solution, 1-3 parts of stearic acid and 0.2-0.5 part of sodium oxalate.
The inventor of the invention surprisingly found that compared with the method without adding the hydroxyapatite, the method without adding sodium oxalate and hydrochloric acid solution has the greatest influence factor on the preparation of the modified compound additive, the effect of the hydroxyapatite in a product system is excellent, in addition, the inventor also surprisingly found that the hydroxyapatite is replaced by graphene and carbon nano tubes, the adsorption effect can be optimized in a neutral environment, but the performance is poor in an acid corrosion environment, so that the hydroxyapatite has the speciality in selection.
Preferably, the mass fraction of the hydrochloric acid solution is 2-6%.
Preferably, the preparation method of the medium modification liquid comprises the following steps:
s11: adding 3-5 parts of titanate coupling agent into 10-15 parts of ethanol solvent, adding 1-3 parts of chitosan aqueous solution, and uniformly stirring;
s12: stirring and mixing 2-4 parts of surfactant and 1-3 parts of organic acid to obtain an additive;
s13: and (3) feeding the additive into the S11 product, and stirring and mixing the mixture fully to obtain the medium modified liquid.
Preferably, the mass fraction of the chitosan aqueous solution is 20-30%.
Preferably, the surfactant is one of fatty alcohol polyoxyethylene ether and coconut diethanol amine; the organic acid is one of citric acid and tartaric acid.
The invention also provides application of the treatment method of the heavy metal organic coupling agent in sewage treatment, wherein the treatment method of the heavy metal organic coupling agent comprises the steps of adding the starch organic flocculant and the modified compound additive into the medium modified liquid, stirring thoroughly, and then sending the mixture into sewage to stir uniformly.
Compared with the prior art, the invention has the following beneficial effects:
the heavy metal organic coupling agent is prepared by adopting a starch organic flocculant, a modified compound additive and a medium modified liquid, wherein the starch organic flocculant adopts the existing organic polymer chelating flocculation, the starch organic flocculant adopts bentonite to carry out thermal reaction, and then is cooled at constant temperature, in order to improve the interlayer spacing of the bentonite, the bentonite optimized by the co-dispersion and the auxiliary liquid can be cooperated more efficiently in the hydroxyapatite agent, the bentonite in the modified compound additive is optimized to provide stable interfacial property for a product system, the bentonite is alternated in the medium modified liquid to assist the starch organic flocculant, the coupling adsorption waste stability of the starch organic flocculant is enhanced, the bentonite is cooperated by the hydroxyapatite, and the bentonite is cooperated with high efficiency, so that the bentonite dispersing effect is stronger; the medium modified liquid adopts a titanate coupling agent, and the starch organic flocculant and the modified compound additive are better cooperated with each other through the amphiphilic effect and the organophilic and inorganic bridge effect, so that the chitosan aqueous solution has the capacity-increasing and permeability-increasing effects, the raw material compatibility of a product system is enhanced, and the medium modified liquid is used as an intermediate through the cooperation of the surfactant and the organic acid, so that the starch organic flocculant and the modified compound additive are better mutually compatible and mutually assisted in the system, and the formed coupling agent can have excellent heavy metal adsorption and excellent stability of the product for treating heavy metal in an acid corrosion environment.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The starch organic flocculant is prepared by referring to the preparation method of the organic polymer heavy metal chelating flocculant in application number CN201510077197.3 and the preparation method and application of the organic polymer heavy metal chelating flocculant in example 3, wherein the organic polymer heavy metal chelating flocculant is an existing raw material.
The heavy metal organic coupling agent comprises a starch organic flocculant, a modified compound additive and a medium modifying liquid, wherein the mass ratio of the starch organic flocculant to the modified compound additive to the medium modifying liquid is (4-5) 2: (9-11).
The preparation method of the modified compound additive of the embodiment comprises the following steps:
s01: firstly placing bentonite at 310-330 ℃ for reaction for 10-20min, and then cooling to room temperature at a speed of 1-3 ℃/s for standby;
s02: adding 2-3 parts of lanthanum sulfate into 10-20 parts of deionized water, adding 0.2-0.5 part of phosphoric acid buffer solution, wherein the pH value of the phosphoric acid buffer solution is 3-5, then adding 1-3 parts of sodium alginate solution, and stirring fully to obtain a synergistic dispersion adjustment auxiliary liquid;
s03: placing the S01 product into 3-5 times of dispersion-assisting liquid for stirring reaction, and after stirring, washing and drying to obtain bentonite dispersion-assisting agent;
s04: the bentonite synergist is sent into the hydroxyapatite agent, uniformly stirred according to the weight ratio of the bentonite synergist to the hydroxyapatite agent of 1:5, and finally washed and dried to obtain the modified compound additive.
The mass fraction of the sodium alginate solution in the embodiment is 10-20%.
The stirring speed of the stirring reaction of S03 in the embodiment is 450-500r/min, the stirring time is 10-20min, and the stirring temperature is 45-50 ℃.
The hydroxyapatite agent of the embodiment comprises the following raw materials in parts by weight:
3-5 parts of hydroxyapatite, 10-15 parts of hydrochloric acid solution, 1-3 parts of stearic acid and 0.2-0.5 part of sodium oxalate.
The mass fraction of the hydrochloric acid solution in this example is 2-6%.
The preparation method of the medium modified liquid in the embodiment comprises the following steps:
s11: adding 3-5 parts of titanate coupling agent into 10-15 parts of ethanol solvent, adding 1-3 parts of chitosan aqueous solution, and uniformly stirring;
s12: stirring and mixing 2-4 parts of surfactant and 1-3 parts of organic acid to obtain an additive;
s13: and (3) feeding the additive into the S11 product, and stirring and mixing the mixture fully to obtain the medium modified liquid.
The mass fraction of the chitosan aqueous solution of the embodiment is 20-30%.
The surfactant of the embodiment is one of fatty alcohol polyoxyethylene ether and coconut diethanol amine; the organic acid is one of citric acid and tartaric acid.
The treatment method of the heavy metal organic coupling agent is that a starch organic flocculant and a modified compound additive are added into a medium modification liquid to be fully stirred, and then the mixture is sent into sewage to be uniformly stirred.
Example 1
The heavy metal organic coupling agent comprises a starch organic flocculant, a modified compound additive and a medium modifying liquid, wherein the mass ratio of the starch organic flocculant to the modified compound additive to the medium modifying liquid is 4:2:9.
the preparation method of the modified compound additive of the embodiment comprises the following steps:
s01: firstly placing bentonite at 310 ℃ for reaction for 10min, and then cooling to room temperature at a speed of 1 ℃/s for standby;
s02: adding 2 parts of lanthanum sulfate into 10 parts of deionized water, adding 0.2 part of phosphoric acid buffer solution, wherein the pH value of the phosphoric acid buffer solution is 4.5, then adding 1 part of sodium alginate solution, and stirring fully to obtain a synergistic dispersion adjustment auxiliary liquid;
s03: placing the S01 product into 3 times of dispersion-assisting and mixing auxiliary liquid, stirring for reaction, washing with water, and drying to obtain bentonite dispersion-assisting agent;
s04: the bentonite synergist is sent into the hydroxyapatite agent, uniformly stirred according to the weight ratio of the bentonite synergist to the hydroxyapatite agent of 1:5, and finally washed and dried to obtain the modified compound additive.
The mass fraction of the sodium alginate solution of this example was 10%.
The stirring speed of the stirring reaction at S03 in this example was 450r/min, the stirring time was 10min, and the stirring temperature was 45 ℃.
The hydroxyapatite agent of the embodiment comprises the following raw materials in parts by weight:
3 parts of hydroxyapatite, 10 parts of hydrochloric acid solution, 1 part of stearic acid and 0.2 part of sodium oxalate.
The mass fraction of the hydrochloric acid solution of this example was 2%.
The preparation method of the medium modified liquid in the embodiment comprises the following steps:
s11: adding 3 parts of titanate coupling agent into 10 parts of ethanol solvent, adding 1 part of chitosan aqueous solution, and uniformly stirring;
s12: stirring and mixing 2 parts of surfactant and 1 part of organic acid to obtain an additive;
s13: and (3) feeding the additive into the S11 product, and stirring and mixing the mixture fully to obtain the medium modified liquid.
The mass fraction of the chitosan aqueous solution of this example was 20%.
The surfactant of the embodiment is fatty alcohol polyoxyethylene ether; the organic acid is citric acid.
The treatment method of the heavy metal organic coupling agent is that a starch organic flocculant and a modified compound additive are added into a medium modification liquid to be fully stirred, and then the mixture is sent into sewage to be uniformly stirred.
Example 2
The heavy metal organic coupling agent comprises a starch organic flocculant, a modified compound additive and a medium modifying liquid, wherein the mass ratio of the starch organic flocculant to the modified compound additive to the medium modifying liquid is 5:2:11.
the preparation method of the modified compound additive of the embodiment comprises the following steps:
s01: firstly placing bentonite at 330 ℃ for reaction for 20min, and then cooling to room temperature at a speed of 3 ℃/s for standby;
s02: adding 3 parts of lanthanum sulfate into 20 parts of deionized water, adding 0.5 part of phosphoric acid buffer solution, wherein the pH value of the phosphoric acid buffer solution is 4.5, then adding 3 parts of sodium alginate solution, and stirring fully to obtain a synergistic dispersion adjustment auxiliary liquid;
s03: placing the S01 product into 5 times of the dispersion-assisting and mixing auxiliary liquid, stirring for reaction, washing with water, and drying to obtain bentonite dispersion-assisting agent;
s04: the bentonite synergist is sent into the hydroxyapatite agent, uniformly stirred according to the weight ratio of the bentonite synergist to the hydroxyapatite agent of 1:5, and finally washed and dried to obtain the modified compound additive.
The mass fraction of the sodium alginate solution of this example was 20%.
The stirring speed of the stirring reaction at S03 in this example was 500r/min, the stirring time was 20min, and the stirring temperature was 50 ℃.
The hydroxyapatite agent of the embodiment comprises the following raw materials in parts by weight:
5 parts of hydroxyapatite, 15 parts of hydrochloric acid solution, 3 parts of stearic acid and 0.5 part of sodium oxalate.
The mass fraction of the hydrochloric acid solution of this example was 6%.
The preparation method of the medium modified liquid in the embodiment comprises the following steps:
s11: adding 5 parts of titanate coupling agent into 15 parts of ethanol solvent, adding 3 parts of chitosan aqueous solution, and uniformly stirring;
s12: mixing 4 parts of surfactant and 3 parts of organic acid under stirring to obtain an additive;
s13: and (3) feeding the additive into the S11 product, and stirring and mixing the mixture fully to obtain the medium modified liquid.
The mass fraction of the chitosan aqueous solution of this example was 30%.
The surfactant of this example is coconut diethanol amine oleate; the organic acid is one of citric acid and tartaric acid.
The treatment method of the heavy metal organic coupling agent is that a starch organic flocculant and a modified compound additive are added into a medium modification liquid to be fully stirred, and then the mixture is sent into sewage to be uniformly stirred.
Example 3
The heavy metal organic coupling agent comprises a starch organic flocculant, a modified compound additive and a medium modifying liquid, wherein the mass ratio of the starch organic flocculant to the modified compound additive to the medium modifying liquid is 4.5:2:10.
the preparation method of the modified compound additive of the embodiment comprises the following steps:
s01: firstly, putting bentonite at 320 ℃ for reaction for 15min, and then cooling to room temperature at a speed of 2 ℃/s for standby;
s02: adding 2.5 parts of lanthanum sulfate into 15 parts of deionized water, adding 0.35 part of phosphoric acid buffer solution, wherein the pH value of the phosphoric acid buffer solution is 4.5, then adding 2 parts of sodium alginate solution, and stirring fully to obtain a synergistic dispersion auxiliary liquid;
s03: placing the S01 product into 4 times of the dispersion-assisting and mixing auxiliary liquid, stirring for reaction, washing with water, and drying to obtain bentonite dispersion-assisting agent;
s04: the bentonite synergist is sent into the hydroxyapatite agent, uniformly stirred according to the weight ratio of the bentonite synergist to the hydroxyapatite agent of 1:5, and finally washed and dried to obtain the modified compound additive.
The mass fraction of the sodium alginate solution of this example was 15%.
The stirring speed of the stirring reaction at S03 in this example was 470r/min, the stirring time was 15min, and the stirring temperature was 47 ℃.
The hydroxyapatite agent of the embodiment comprises the following raw materials in parts by weight:
4 parts of hydroxyapatite, 12.5 parts of hydrochloric acid solution, 2 parts of stearic acid and 0.35 part of sodium oxalate.
The mass fraction of the hydrochloric acid solution of this example was 4%.
The preparation method of the medium modified liquid in the embodiment comprises the following steps:
s11: adding 4 parts of titanate coupling agent into 12.5 parts of ethanol solvent, adding 2 parts of chitosan aqueous solution, and uniformly stirring;
s12: 3 parts of surfactant and 2 parts of organic acid are stirred and mixed to obtain an additive;
s13: and (3) feeding the additive into the S11 product, and stirring and mixing the mixture fully to obtain the medium modified liquid.
The mass fraction of the chitosan aqueous solution of this example was 25%.
The surfactant of the embodiment is fatty alcohol polyoxyethylene ether; the organic acid is citric acid.
The treatment method of the heavy metal organic coupling agent is that a starch organic flocculant and a modified compound additive are added into a medium modification liquid to be fully stirred, and then the mixture is sent into sewage to be uniformly stirred.
Example 4
The heavy metal organic coupling agent comprises a starch organic flocculant, a modified compound additive and a medium modifying liquid, wherein the mass ratio of the starch organic flocculant to the modified compound additive to the medium modifying liquid is 4.2:2:10.
the preparation method of the modified compound additive of the embodiment comprises the following steps:
s01: firstly placing bentonite at 315 ℃ for reaction for 12min, and then cooling to room temperature at a speed of 2 ℃/s for standby;
s02: adding 2.2 parts of lanthanum sulfate into 12 parts of deionized water, adding 0.3 part of phosphoric acid buffer solution, wherein the pH value of the phosphoric acid buffer solution is 4.5, then adding 2 parts of sodium alginate solution, and stirring fully to obtain a synergistic dispersion auxiliary liquid;
s03: placing the S01 product into 4 times of the dispersion-assisting and mixing auxiliary liquid, stirring for reaction, washing with water, and drying to obtain bentonite dispersion-assisting agent;
s04: the bentonite synergist is sent into the hydroxyapatite agent, uniformly stirred according to the weight ratio of the bentonite synergist to the hydroxyapatite agent of 1:5, and finally washed and dried to obtain the modified compound additive.
The mass fraction of the sodium alginate solution in this example was 12%.
The stirring speed of the stirring reaction at S03 in this example was 460r/min, the stirring time was 12min, and the stirring temperature was 47 ℃.
The hydroxyapatite agent of the embodiment comprises the following raw materials in parts by weight:
4 parts of hydroxyapatite, 12 parts of hydrochloric acid solution, 2 parts of stearic acid and 0.3 part of sodium oxalate.
The mass fraction of the hydrochloric acid solution of this example was 3%.
The preparation method of the medium modified liquid in the embodiment comprises the following steps:
s11: adding 4 parts of titanate coupling agent into 12 parts of ethanol solvent, adding 2 parts of chitosan aqueous solution, and uniformly stirring;
s12: 3 parts of surfactant and 2 parts of organic acid are stirred and mixed to obtain an additive;
s13: and (3) feeding the additive into the S11 product, and stirring and mixing the mixture fully to obtain the medium modified liquid.
The mass fraction of the chitosan aqueous solution of this example was 22%.
The surfactant of the embodiment is fatty alcohol polyoxyethylene ether; the organic acid is citric acid.
The treatment method of the heavy metal organic coupling agent is that a starch organic flocculant and a modified compound additive are added into a medium modification liquid to be fully stirred, and then the mixture is sent into sewage to be uniformly stirred.
Comparative example 1
The difference from example 3 is that no modified compounding additive was added.
Comparative example 2
The difference from example 3 is that bentonite is not treated by the step S01 in the preparation of the modified compound additive.
Comparative example 3
The difference from example 3 is that no dispersion-aiding and liquid-aiding treatment is adopted in the preparation of the modified compound additive.
Comparative example 4
The difference from example 3 is that lanthanum sulfate is not added in the preparation of the dispersion-aiding and conditioning liquid.
Comparative example 5
The difference from example 3 is that no phosphate buffer solution was added in the preparation of the co-dispersion co-liquid.
Comparative example 6
The difference from example 3 is that the bentonite raw material in the preparation of the dispersion-aiding and conditioning aid is replaced by layered mica powder.
Comparative example 7
The difference from example 3 is that the modified built additive was not treated with a hydroxyapatite agent in the preparation.
Comparative example 8
The difference from example 3 is that no treatment with the medium-modifying liquid was used.
Comparative example 9
The difference from example 3 is that no titanate coupling agent is added in the treatment of the medium modifying liquid.
Comparative example 10
The difference from example 3 is that no aqueous chitosan solution was added to the medium modification liquid treatment.
Comparative example 11
Unlike example 3, no organic acid was added to the medium-modified liquid treatment.
Comparative example 12
The difference from example 3 is that the organic coupling agent is a starch organic flocculant.
0.1g of the products prepared in examples 1-4 and comparative examples 1-12 was taken and 50mL of Cd having a concentration of 100mg/L was added 2+ 、Sb 5+ In the sewage (neutral environment), stirring for 30min at room temperature, and detecting Cd in the sewage 2+ 、Sb 5+ The removal rate was further increased to 50mL of Cd at a concentration of 100mg/L 2+ 、Sb 5+ Adding 5mL of hydrochloric acid solution with mass fraction of 2% into the sewage, and continuously testing the adsorption stability in an acid environment;
examples 1-4 and comparative examples 1-12 product performance tests:
as can be seen from examples 1 to 4 and comparative examples 1 to 12, the product of example 3 of the present invention has excellent Cd 2+ 、Sb 5+ The removal rate, especially in acid environment, the product still has excellent stable adsorptivity;
as can be seen from example 3, comparative example 1, comparative examples 8 and 12, cd in the product was treated without adding a modified compounding additive or a medium modifying liquid 2+ Adsorption rate, sb 5+ The adsorption rate has a tendency of reducing the stability of the adsorption rate in a neutral environment, but the adsorption rate has obvious reduction efficiency in an acid environment, and meanwhile, the adsorption performance of the independent starch organic flocculant in the acid environment is obviously reduced when the independent starch organic flocculant is adopted to reach 99.2 in the neutral environment without adding one of a modified compound additive and a medium modified liquid treatment;
therefore, the modified compound additive and the medium modification liquid are adopted for treatment and synergism, and the adsorptivity of the product and the adsorption stability of the acid environment are enhanced;
as can be seen from comparative examples 2 to 6, bentonite is not treated in the step S01 in the preparation of the modified compound additive, the modified compound additive is not treated by the co-dispersion and co-liquid treatment in the preparation of the modified compound additive, the adsorption performance and adsorption stability of the product are both prone to deterioration, the treatment methods of the bentonite are different, and the performance effects of the product are different;
in addition, lanthanum sulfate and phosphoric acid buffer solution are not added in the preparation of the synergistic dispersion auxiliary liquid, the performance of the product is poor, and the product has optimal performance effect only through the synergistic dispersion auxiliary liquid treatment prepared by the method and the treatment of the bentonite step S01;
the bentonite raw material is replaced by layered mica powder, the performance of the product is poor, and the bentonite raw material is also specific;
as shown in comparative examples 8 to 11, one of the titanate coupling agent, the organic acid and the chitosan aqueous solution is not added in the treatment of the medium modified liquid, the performance of the product tends to be poor, the titanate coupling agent, the organic acid and the chitosan aqueous solution are coordinated in a mutual coordination manner, the raw materials are mutually matched in a mutual coordination manner, and the medium modified liquid formed together is optimal in improving the performance effect of the product;
as can be seen from comparative examples 2-6 and comparative example 7, the modified compound additive is not treated by the hydroxyapatite agent, the performance of the product has the largest influence factor in the preparation of the modified compound additive, and the adsorption performance of the product is changed most obviously, so the modified compound additive is further explored and treated by the invention.
The hydroxyapatite agent comprises the following raw materials in parts by weight:
4 parts of hydroxyapatite, 12 parts of hydrochloric acid solution, 2 parts of stearic acid and 0.3 part of sodium oxalate.
The mass fraction of the hydrochloric acid solution of this example was 3%.
Experimental example 1
The same raw materials as those of the product of example 3 except that no hydroxyapatite was added to the hydroxyapatite agent.
Experimental example 2
The same raw materials as those of the product of example 3 except that the hydroxyapatite in the hydroxyapatite agent was replaced with nano silica.
Experimental example 3
The same raw materials as those of the product of example 3 except that the hydroxyapatite in the hydroxyapatite agent was replaced with carbon nanotubes.
Experimental example 4
The same raw materials as those of the product of example 3 except that sodium oxalate was not added to the hydroxyapatite agent.
Experimental example 5
The raw materials are the same as those of the product of example 3, except that deionized water is used instead of hydrochloric acid solution.
The results of the performance tests of experimental examples 1 to 5 are as follows
From experimental examples 1-5, compared with the method without adding sodium oxalate and hydrochloric acid solution, the method has the advantages that the influence factor of the non-added hydroxyapatite on the preparation of the modified compound additive is the largest, the effect of the hydroxyapatite in a product system is excellent, in addition, the method has the advantages that the hydroxyapatite is replaced by graphene and carbon nano tubes, the adsorption effect can be optimized in a neutral environment, but the performance is poor in an acid corrosion environment, so that the hydroxyapatite is proprietary;
in addition, the sodium oxalate and the hydrochloric acid solution are added, the performance of the product has an optimized and improved effect, the product has a synergistic effect on hydroxyapatite, the adsorption effect of the product can be optimized in a neutral environment, the performance is stable in an acid corrosion environment, meanwhile, the performance advantage of the product after the hydrochloric acid solution is added is better than that of a sodium oxalate raw material, the raw materials are matched together, and the product still has excellent heavy metal treatment stability in an acid environment.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (4)
1. The heavy metal organic coupling agent is characterized in that the organic coupling agent comprises a starch organic flocculant, a modified compound additive and a medium modifying liquid, wherein the mass ratio of the starch organic flocculant to the modified compound additive to the medium modifying liquid is (4-5) 2: (9-11);
the preparation method of the modified compound additive comprises the following steps:
s01: firstly placing bentonite at 310-330 ℃ for reaction for 10-20min, and then cooling to room temperature at a speed of 1-3 ℃/s for standby;
s02: adding 2-3 parts of lanthanum sulfate into 10-20 parts of deionized water, adding 0.2-0.5 part of phosphoric acid buffer solution, wherein the pH value of the phosphoric acid buffer solution is 3-5, then adding 1-3 parts of sodium alginate solution, and stirring thoroughly to obtain a synergistic dispersion adjustment auxiliary liquid, wherein the mass fraction of the sodium alginate solution is 10-20%;
s03: placing the S01 product into 3-5 times of dispersion-assisting liquid for stirring reaction, and after stirring, washing and drying to obtain bentonite dispersion-assisting agent;
s04: the bentonite synergist is sent into a hydroxyapatite agent, uniformly stirred according to the weight ratio of the bentonite synergist to the hydroxyapatite agent of 1:5, and finally washed and dried to obtain a modified compound additive;
wherein, the hydroxyapatite agent comprises the following raw materials in parts by weight: 3-5 parts of hydroxyapatite, 10-15 parts of hydrochloric acid solution, 1-3 parts of stearic acid and 0.2-0.5 part of sodium oxalate, wherein the mass fraction of the hydrochloric acid solution is 2-6%;
the preparation method of the medium modified liquid comprises the following steps:
s11: adding 3-5 parts of titanate coupling agent into 10-15 parts of ethanol solvent, adding 1-3 parts of chitosan aqueous solution, and uniformly stirring, wherein the mass fraction of the chitosan aqueous solution is 20-30%;
s12: stirring and mixing 2-4 parts of surfactant and 1-3 parts of organic acid to obtain an additive;
s13: and (3) feeding the additive into the S11 product, and stirring and mixing the mixture fully to obtain the medium modified liquid.
2. The heavy metal organic coupling agent according to claim 1, wherein the stirring speed of the stirring reaction of S03 is 450-500r/min, the stirring time is 10-20min, and the stirring temperature is 45-50 ℃.
3. The heavy metal organic coupling agent according to claim 1, wherein the surfactant is one of fatty alcohol polyoxyethylene ether and coconut diethanol amine; the organic acid is one of citric acid and tartaric acid.
4. Use of the treatment method of the heavy metal organic coupling agent according to any one of claims 1-3 in sewage treatment, wherein the treatment method of the heavy metal organic coupling agent comprises the steps of adding a starch organic flocculant and a modified compound additive into a medium modification liquid, stirring thoroughly, and then sending into sewage to stir uniformly.
Priority Applications (1)
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| DE102007034726A1 (en) * | 2007-07-23 | 2009-01-29 | Henkel Ag & Co. Kgaa | Removal of by-products from crosslinkable preparations |
| CN101940913A (en) * | 2010-09-27 | 2011-01-12 | 浙江农林大学 | Production method for adsorbent coupling chitosan and bamboo charcoal by dialdehyde |
| FR2993876B1 (en) * | 2012-07-27 | 2015-02-27 | Roquette Freres | PROCESS FOR POTABILIZATION |
| ES2716604T3 (en) * | 2014-04-16 | 2019-06-13 | Omya Int Ag | Adsorption and / or reduction of the amount of organic materials in an aqueous medium with the use of precipitated colloidal calcium carbonate |
| CN104649398B (en) * | 2015-02-12 | 2017-03-22 | 广东电网有限责任公司电力科学研究院 | Organic polymer heavy metal chelating flocculant as well as preparation method and application thereof |
| CN105776579A (en) * | 2016-05-26 | 2016-07-20 | 许婷 | Waste plastic recovery processing sewage treating agent and preparation method thereof |
| CN106745389A (en) * | 2016-12-27 | 2017-05-31 | 郑州源冉生物技术有限公司 | A kind of dyeing and printing sewage treatment agent |
| CN108439525A (en) * | 2018-04-17 | 2018-08-24 | 湖南善循环保科技有限公司 | A kind of sewage-treating agent for heavy metal pollution |
| CN109205748A (en) * | 2018-10-30 | 2019-01-15 | 成都其其小数科技有限公司 | A kind of flocculant and preparation method for heavy metal-polluted water process |
| CN111875018A (en) * | 2020-07-21 | 2020-11-03 | 山东胜伟盐碱地科技有限公司 | Flocculating agent for treating sewage in livestock breeding land and preparation method thereof |
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