CN111072116A - Composite inorganic high polymer iron-based flocculant and preparation and application thereof - Google Patents
Composite inorganic high polymer iron-based flocculant and preparation and application thereof Download PDFInfo
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- CN111072116A CN111072116A CN201911315594.4A CN201911315594A CN111072116A CN 111072116 A CN111072116 A CN 111072116A CN 201911315594 A CN201911315594 A CN 201911315594A CN 111072116 A CN111072116 A CN 111072116A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
Abstract
The invention provides a composite inorganic high polymer iron-based flocculant, a preparation method and an application thereof, wherein the iron-based flocculant is an auxiliary cation additive and Fe3+The cation in the auxiliary cation additive is Al3+、Mg2+、Zn2+、Ti4+Either or both of the compositions, Fe3+The composite flocculant is a novel iron-based composite flocculant prepared by compounding various cations according to a reasonable raw material ratio, has excellent flocculation efficiency and strong stability, is used for treating printing and dyeing wastewater and papermaking wastewater, has COD (chemical oxygen demand) and decolorization removal rates respectively up to 84.6% and 99.5% above, is safe and environment-friendly, and is worthy of industrial popularization and application.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a composite inorganic high polymer iron-based flocculant and preparation and application thereof.
Background
Water is a source of life, clean and rich water resources are a necessary premise for human survival and development, and along with the continuous deepening of the industrialization process, particularly the development of Chinese reform is opened for 30 years, the modern industrial production is increased at a high speed, the discharge amount of industrial and domestic wastewater is greatly increased, wherein the wastewater discharged by most enterprises contains a large amount of toxic and harmful substances, the self-cleaning capacity of water bodies can not keep up with the pollution speed, the water pollution is increasingly serious, and the production and life quality of people is seriously influenced. China is a country with scarce water resources, and the rapid development of the industry causes great damage to the water environment. Research and application of novel efficient pollution-free water treatment agents are important ways for improving water quality and promoting water resource recycling. The flocculant can solve the problem of water pollution to a great extent, so that the application of a flocculation precipitation method in industrial wastewater treatment is wide and plays a very important role, the main theoretical basis of the action mechanism is colloid chemistry and interface chemistry, for example, the traditional water treatment flocculant of DLVO theory is low-molecular inorganic salt, but the flocculant needs a large amount of investment and has poor effect, and is gradually replaced by a high-molecular flocculant.
Among many flocculants, inorganic polymeric polycationic flocculants have many related researches and applications because the flocculation efficiency is much better than that of traditional flocculants. Compared with the traditional aluminum salt, the polyaluminium has a further improvement on the water treatment effect, such as polyaluminium chloride (PAC), aluminum zinc polysilicate and the like, and the chromaticity and the removal rate of COD are obviously improved. However, aluminum is a toxic substance, and residual aluminum in water has adverse effects on human health. Meanwhile, floccules coagulated by aluminum salt are loose, slow in sedimentation and narrow in application range of pH, and a novel efficient flocculant needs to be found for replacing the floccules.
The ferric salt flocculant has the advantages that ① iron can prolong the flocculation time, the formed alum flocs are compact, the sedimentation speed is high, the application range of the pH value of ② is wide, ③ has strong decoloration and deodorization effects, ④ has stronger removal effects on COD, BOD and heavy metal ions compared with PAC, and the residual quantity of the iron ions in the liquid after ⑤ treatment is small, so that toxic and side effects cannot be caused.
The traditional ferric salt flocculating agent generally only contains one metal component, namely Fe3+, and then other anions are introduced to form two or more acid radical ions to be compounded, so that the traditional ferric salt flocculating agent is formed by compounding the two or more acid radical ions, and the traditional ferric salt flocculating agent is mature in application, such as poly-ferric silicate sulfate, poly-ferric phosphate sulfate, poly-ferric chloride sulfate and the like, is non-toxic and safe, has long stabilization period and wider requirements on a pH range, and is one of the well-developed ecological water treatment agents.
However, the existing iron-based flocculant has single type of cation capable of flocculating and precipitating, and the flocculated precipitate has loose tissue structure and is easy to be disturbed and scattered, so that the flocculation effect is not ideal and the precipitation time is longer, therefore, a great number of researchers begin to research the multi-cation high-polymer iron-based flocculant prepared by different cations so as to obtain the flocculant with better flocculation performance.
Disclosure of Invention
Aiming at the problems, the invention provides a composite inorganic high polymer iron-based flocculant and preparation and application thereof, the novel iron-based composite flocculant is prepared by adopting multiple cations through reasonable raw material proportion, has excellent flocculation efficiency and strong stability, is used for treating printing and dyeing wastewater and paper industry wastewater, has COD (chemical oxygen demand) and decoloration removal rates respectively reaching more than 83.6 percent and 99.5 percent, is safe and environment-friendly, and is worthy of industrial popularization and application.
In order to achieve the above object, the present invention adopts the following technical solutions:
a composite iron-series inorganic high-polymer flocculant is prepared from auxiliary cationic additive and Fe3+The cation in the auxiliary cation additive is Al3+、Mg2+、Zn2+、Ti4+Either or both of which are Fe3+Accounting for 30-60% of the total mole of the cations in the iron-based flocculant.
Preferably, said Fe3+Introducing Al from pickling waste liquid containing iron or ferrous sulfate heptahydrate or a combination of the two as raw materials3+Introducing polymeric aluminum ferric sulfate silicate or RE-silicon aluminum molecular sieve or the combination of the two as raw materials, Mg2+Zn is introduced from magnesium sulfate or magnesium trisilicate or a combination of the magnesium sulfate and the magnesium trisilicate as raw materials2+Any one or more of zinc sulfate, activated zinc silicate and polysilicate zinc sulfate is used as raw material, Ti4+Is introduced by using titanium polysilicate or TS-1 molecular sieve or the combination of the two as raw materials.
Preferably, the rare earth in the RE-silicon aluminum molecular sieve is selected from one or more of La, Ce, Sm and Sc, and the molar ratio in the molecular sieve is RE: (Si + Al) ═ 0.01-0.05: 1.
Preferably, the preparation method of the compound inorganic high polymer iron-based flocculant comprises the following steps:
1) preparing iron-containing pickling waste liquid or ferrous sulfate heptahydrate into iron-containing solution by adding deionized water, adding appropriate amount of concentrated sulfuric acid into the iron-containing pickling waste liquid or iron-containing solution, stirring for 3-5min, adding chlorate, heating to 70-75 deg.C, stirring, and reacting for 2 hr to obtain solution A;
2) taking auxiliary cation additives, respectively stirring and dissolving the auxiliary cation additives in deionized water, and then regulating the pH value to 3-5 by using sulfuric acid and sodium hydroxide as acid-base regulators to obtain solutions containing auxiliary cations;
3) and sequentially adding the solutions containing the auxiliary cations into the solution A under the stirring condition, obtaining a total mixed solution after the addition is finished, adjusting the temperature to be 45-50 ℃, and stirring for reaction for 1-3 hours to obtain the composite inorganic high polymer iron-based flocculant.
Preferably, the total iron content in the iron-containing pickling waste liquid or iron-containing solution in the step 1) is 5.6-6%.
Preferably, the molar ratio of the addition amount of the concentrated sulfuric acid in the step 1) to the total iron in the iron-containing acid washing waste liquid or the iron-containing solution is 1:2, the chlorate is 5-6% of potassium chlorate or sodium chlorate by mass, and the molar ratio of the chlorate to the total iron in the iron-containing acid washing waste liquid or the iron-containing solution is 1: 8.
Preferably, the concentration of the sulfuric acid and the concentration of the sodium hydroxide in the step 2) are both 0.1-0.15 mol/L.
Preferably, chlorate and a stabilizer are added in the stirring reaction process in the step 3), wherein the addition amount of the chlorate is 3-10% of the mass of the total mixed solution, and the addition amount of the stabilizer is 0.5-2% of the mass of the total mixed solution.
Preferably, the chlorate is 5-6% of potassium chlorate or sodium chlorate by mass fraction, and the stabilizer comprises the following components in parts by weight: 40-50 parts of polyacrylamide, 30-40 parts of polyethylene glycol 400and 3-6 parts of tetrabutyl titanate. The preparation method of the stabilizer comprises the following steps: adding tetrabutyl titanate into polyethylene glycol 400, stirring at 30-40 deg.C for 20-60min, adding polyacrylamide under stirring, performing ultrasonic treatment for 2-3 times at intervals, and standing at 40-50 deg.C for 2-5 h. Wherein the interval ultrasonic treatment is carried out at an interval of 1h every two times, and the ultrasonic treatment is carried out at a frequency of 30-32KHz, a temperature of 35-38 ℃ and a time of 5-10 m.
Preferably, the compound inorganic high polymer iron flocculant prepared by the preparation method is applied as follows: the composite inorganic high polymer iron flocculant is used for flocculation treatment of printing and dyeing wastewater and papermaking wastewater, and the dosage of the composite inorganic high polymer iron flocculant is 1-3% of the mass of the wastewater.
Due to the adoption of the technical scheme, the invention has the beneficial effects that: the novel iron-based composite flocculant prepared by compounding various cations through reasonable raw material proportion has excellent flocculation efficiency and strong stability, is used for treating printing and dyeing wastewater and paper industry wastewater, has COD (chemical oxygen demand) and decolorization removal rate respectively reaching over 84.6 percent and 99.5 percent, is safe and environment-friendly, and is worthy of industrial popularization and application.
Compared with the traditional single-cation iron-based flocculant, the flocculant has the advantages that various cations are compounded, the flocculant has an excellent structure modification effect, a long-chain structure is more stable, the cations are combined in a multi-azimuth substitution manner and adsorbed and combined with anions in wastewater for coagulation, the bridging sweeping effect is better, simultaneously, the generated alum floc is compact and stable, the volume is larger, the precipitation rate is high, and the treatment efficiency and effect of the wastewater are obviously improved.
In the preparation process, still add the stabilizer, with current organic polymer flocculation composition and inorganic polymer flocculation composition mating reaction, be favorable to carrying out the modification combination to the structure of flocculating the active ingredient on the one hand, improve space area of contact, accelerate the adsorption coagulation effect, on the other hand has good space portability, in the in-process that contacts the mixed flocculation with sewage, the activation of accessible zinc, magnesium, titanium etc., the cross-linking realizes the crane span structure of leaving the net passageway, effective amount's cation has not only been guaranteed, the compactness of flocculation alum blossom has been improved greatly simultaneously, the flocculation adsorption efficiency is high, the settling rate is fast, the suspended solid volume reduces in the solution, purifying effect is showing and improves.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
a composite iron-series inorganic high-polymer flocculant is prepared from auxiliary cationic additive and Fe3+The cation in the auxiliary cation additive is Al3+、Zn2+Composition of Fe3+Accounting for 40 percent of the total molar weight of the cations in the iron-based flocculant.
Wherein: fe3+Introducing pickling waste liquid containing iron as raw material, Al3+Is introduced by taking RE-silicon-aluminum molecular sieve as raw material, Zn2+Zinc sulfate and an activated zinc silicate composition (the molar ratio of the zinc sulfate to the activated zinc silicate in the composition is 1:2) are taken as raw materials.
In the RE-silicon aluminum molecular sieve, the rare earth is selected from any one or more of La, Ce, Sm and Sc, preferably the composition of Ce and Sm, the mass ratio of the two is 1:1, and the molar ratio of the RE to the Sm in the molecular sieve is (Ce + Sm): (Si + Al) ═ 0.03: 1.
The compound inorganic high polymer iron flocculant is prepared by the following steps:
1) adding a proper amount of concentrated sulfuric acid into the iron-containing pickling waste liquid, stirring for 3-5min, adding chlorate, heating to 70-75 ℃, and stirring for reacting for 2h to obtain a solution A for later use;
2) taking auxiliary cation additives, respectively stirring and dissolving the auxiliary cation additives in deionized water, and then regulating the pH value to 3-5 by using sulfuric acid and sodium hydroxide as acid-base regulators to obtain solutions containing auxiliary cations;
3) and sequentially adding the solutions containing the auxiliary cations into the solution A under the stirring condition, obtaining a total mixed solution after the addition is finished, adjusting the temperature to be 45-50 ℃, and stirring for reaction for 1-3 hours to obtain the composite inorganic high polymer iron-based flocculant.
Wherein: the total iron content in the iron-containing pickling waste liquid in the step 1) is 5.6 percent; in the step 1), the molar ratio of the addition amount of the concentrated sulfuric acid to the total iron in the iron-containing acid pickling waste liquid is 1:2, the chlorate is potassium chlorate with the mass fraction of 5.5%, and the molar ratio of the chlorate to the total iron in the iron-containing acid pickling waste liquid is 1: 8; in the step 2), the concentrations of sulfuric acid and sodium hydroxide are both 0.15 mol/L; and 3) adding chlorate and a stabilizer in the stirring reaction process, wherein the addition amount of the chlorate is 5% of the mass of the total mixed solution, and the addition amount of the stabilizer is 1% of the mass of the total mixed solution.
The chlorate adopts 5.5 percent of potassium chlorate or sodium chlorate by mass fraction, and the stabilizer comprises the following components in parts by weight: 50 parts of polyacrylamide, 35 parts of polyethylene glycol 400and 4 parts of tetrabutyl titanate.
Example 2:
a composite iron-series inorganic high-polymer flocculant is prepared from auxiliary cationic additive and Fe3+The cation in the auxiliary cation additive is Al3+、Ti4+Composition of Fe3+Accounting for 40 percent of the total molar weight of the cations in the iron-based flocculant.
Wherein: fe3+Introducing pickling waste liquid containing iron as raw material, Al3+Is introduced by taking RE-silicon-aluminum molecular sieve as raw material, Ti4+The titanium polysilicate and the TS-1 molecular sieve composition (the molar ratio of the titanium polysilicate to the TS-1 molecular sieve in the composition is 1:1) are taken as raw materials to be introduced.
In the RE-silicon aluminum molecular sieve, the rare earth is selected from any one or more of La, Ce, Sm and Sc, preferably the Ce and Sm composition, the mass ratio of the two is 1:1, and the molar ratio of the RE to the Sm in the molecular sieve is (Ce + Sm): (Si + Al) ═ 0.05: 1.
The compound inorganic high polymer iron flocculant is prepared by the following steps:
1) adding a proper amount of concentrated sulfuric acid into the iron-containing pickling waste liquid, stirring for 3-5min, adding chlorate, heating to 70-75 ℃, and stirring for reacting for 2h to obtain a solution A for later use;
2) taking auxiliary cation additives, respectively stirring and dissolving the auxiliary cation additives in deionized water, and then regulating the pH value to 3-5 by using sulfuric acid and sodium hydroxide as acid-base regulators to obtain solutions containing auxiliary cations;
3) and sequentially adding the solutions containing the auxiliary cations into the solution A under the stirring condition, obtaining a total mixed solution after the addition is finished, adjusting the temperature to be 45-50 ℃, and stirring for reaction for 1-3 hours to obtain the composite inorganic high polymer iron-based flocculant.
Wherein: the total iron content in the iron-containing pickling waste liquid in the step 1) is 6 percent; in the step 1), the molar ratio of the addition amount of the concentrated sulfuric acid to the total iron in the iron-containing acid pickling waste liquid is 1:2, the chlorate is 5% of potassium chlorate by mass, and the molar ratio of the chlorate to the total iron in the iron-containing acid pickling waste liquid is 1: 8; in the step 2), the concentrations of sulfuric acid and sodium hydroxide are both 0.15 mol/L; and 3) adding chlorate and a stabilizer in the stirring reaction process, wherein the addition amount of the chlorate is 5% of the mass of the total mixed solution, and the addition amount of the stabilizer is 2% of the mass of the total mixed solution.
The chlorate adopts 5 percent of potassium chlorate by mass fraction, and the stabilizer comprises the following components in parts by weight: 50 parts of polyacrylamide, 35 parts of polyethylene glycol 400and 4 parts of tetrabutyl titanate.
Example 3:
a composite iron-series inorganic high-polymer flocculant is prepared from auxiliary cationic additive and Fe3+The cation in the auxiliary cation additive is Zn2+、Ti4+Composition of Fe3+Accounting for 60 percent of the total molar weight of the cations in the iron-based flocculant.
Wherein: fe3+Introducing Zn from pickling waste liquid containing iron as raw material2+Introduced from activated zinc silicate as raw material, Ti4+The titanium polysilicate and the TS-1 molecular sieve composition (the molar ratio of the titanium polysilicate to the TS-1 molecular sieve in the composition is 1:1) are taken as raw materials to be introduced.
The compound inorganic high polymer iron flocculant is prepared by the following steps:
1) adding a proper amount of concentrated sulfuric acid into the iron-containing pickling waste liquid, stirring for 3-5min, adding chlorate, heating to 70-75 ℃, and stirring for reacting for 2h to obtain a solution A for later use;
2) taking auxiliary cation additives, respectively stirring and dissolving the auxiliary cation additives in deionized water, and then regulating the pH value to 3-5 by using sulfuric acid and sodium hydroxide as acid-base regulators to obtain solutions containing auxiliary cations;
3) and sequentially adding the solutions containing the auxiliary cations into the solution A under the stirring condition, obtaining a total mixed solution after the addition is finished, adjusting the temperature to be 45-50 ℃, and stirring for reaction for 1-3 hours to obtain the composite inorganic high polymer iron-based flocculant.
Wherein: the total iron content in the iron-containing pickling waste liquid in the step 1) is 5.8 percent; in the step 1), the molar ratio of the addition amount of the concentrated sulfuric acid to the total iron in the iron-containing acid pickling waste liquid is 1:2, the chlorate adopts 6 mass percent of potassium chlorate, and the molar ratio of the chlorate to the total iron in the iron-containing acid pickling waste liquid is 1: 8; in the step 2), the concentrations of sulfuric acid and sodium hydroxide are both 0.15 mol/L; and 3) adding chlorate and a stabilizer in the stirring reaction process, wherein the addition amount of the chlorate is 10% of the mass of the total mixed solution, and the addition amount of the stabilizer is 2% of the mass of the total mixed solution.
The chlorate adopts 6 percent of potassium chlorate by mass fraction, and the stabilizer comprises the following components in parts by weight: 40 parts of polyacrylamide, 40 parts of polyethylene glycol 40040 parts and 6 parts of tetrabutyl titanate.
Example 4:
a composite iron-series inorganic high-polymer flocculant is prepared from auxiliary cationic additive and Fe3+The cation in the auxiliary cation additive is Zn2+、Ti4+Composition of Fe3+Accounting for 50 percent of the total molar weight of the cations in the iron-based flocculant.
Wherein: fe3+Introducing Zn from pickling waste liquid containing iron as raw material2+Introducing zinc sulfate and activated zinc silicate composition (the molar ratio of zinc sulfate to activated zinc silicate in the composition is 0.5:1) as raw materials, and Ti4+Comprises a titanium polysilicate and a TS-1 molecular sieve composition (the molar ratio of the titanium polysilicate to the TS-1 molecular sieve in the composition is 1:1)Introduced as a feedstock.
The compound inorganic high polymer iron flocculant is prepared by the following steps:
1) adding a proper amount of concentrated sulfuric acid into the iron-containing pickling waste liquid, stirring for 3-5min, adding chlorate, heating to 70-75 ℃, and stirring for reacting for 2h to obtain a solution A for later use;
2) taking auxiliary cation additives, respectively stirring and dissolving the auxiliary cation additives in deionized water, and then regulating the pH value to 3-5 by using sulfuric acid and sodium hydroxide as acid-base regulators to obtain solutions containing auxiliary cations;
3) and sequentially adding the solutions containing the auxiliary cations into the solution A under the stirring condition, obtaining a total mixed solution after the addition is finished, adjusting the temperature to be 45-50 ℃, and stirring for reaction for 1-3 hours to obtain the composite inorganic high polymer iron-based flocculant.
Wherein: the total iron content in the iron-containing pickling waste liquid in the step 1) is 6 percent; in the step 1), the molar ratio of the addition amount of the concentrated sulfuric acid to the total iron in the iron-containing acid pickling waste liquid is 1:2, the chlorate is 5% of potassium chlorate by mass, and the molar ratio of the chlorate to the total iron in the iron-containing acid pickling waste liquid is 1: 8; in the step 2), the concentrations of sulfuric acid and sodium hydroxide are both 0.1 mol/L; and 3) adding chlorate and a stabilizer in the stirring reaction process, wherein the addition amount of the chlorate is 10% of the mass of the total mixed solution, and the addition amount of the stabilizer is 2% of the mass of the total mixed solution.
The chlorate adopts 5 percent of potassium chlorate by mass fraction, and the stabilizer comprises the following components in parts by weight: 40 parts of polyacrylamide, 40 parts of polyethylene glycol 40040 parts and 6 parts of tetrabutyl titanate.
Example 5:
a composite iron-series inorganic high-polymer flocculant is prepared from auxiliary cationic additive and Fe3+The cation in the auxiliary cation additive is Al3+、Mg2+Composition of Fe3+Accounting for 30 percent of the total molar weight of the cations in the iron-based flocculant.
Wherein: fe3+Introducing pickling waste liquid containing iron as raw material, Al3+From RE-aluminosilicate molecular sievesIntroduced as raw material, Mg2+Is introduced by taking magnesium trisilicate as a raw material.
In the RE-silicon aluminum molecular sieve, the rare earth is selected from any one or more of La, Ce, Sm and Sc, preferably the Ce and Sm composition, the mass ratio of the two is 1:0.5, and the molar ratio of the RE to the Sm in the molecular sieve is (Ce + Sm): (Si + Al) ═ 0.05: 1.
The compound inorganic high polymer iron flocculant is prepared by the following steps:
1) adding a proper amount of concentrated sulfuric acid into the iron-containing pickling waste liquid, stirring for 3-5min, adding chlorate, heating to 70-75 ℃, and stirring for reacting for 2h to obtain a solution A for later use;
2) taking auxiliary cation additives, respectively stirring and dissolving the auxiliary cation additives in deionized water, and then regulating the pH value to 3-5 by using sulfuric acid and sodium hydroxide as acid-base regulators to obtain solutions containing auxiliary cations;
3) and sequentially adding the solutions containing the auxiliary cations into the solution A under the stirring condition, obtaining a total mixed solution after the addition is finished, adjusting the temperature to be 45-50 ℃, and stirring for reaction for 1-3 hours to obtain the composite inorganic high polymer iron-based flocculant.
Wherein: the total iron content in the iron-containing pickling waste liquid in the step 1) is 5.6 percent; in the step 1), the molar ratio of the addition amount of the concentrated sulfuric acid to the total iron in the iron-containing acid pickling waste liquid is 1:2, the chlorate is potassium chlorate with the mass fraction of 5.5%, and the molar ratio of the chlorate to the total iron in the iron-containing acid pickling waste liquid is 1: 8; in the step 2), the concentrations of sulfuric acid and sodium hydroxide are both 0.1 mol/L; and 3) adding chlorate and a stabilizer in the stirring reaction process, wherein the addition amount of the chlorate is 3% of the mass of the total mixed solution, and the addition amount of the stabilizer is 1.5% of the mass of the total mixed solution.
The chlorate adopts 5.5 percent of potassium chlorate by mass fraction, and the stabilizer comprises the following components in parts by weight: 40 parts of polyacrylamide, 35 parts of polyethylene glycol 400and 3 parts of tetrabutyl titanate.
Example 6:
a composite iron-series inorganic high-polymer flocculant is prepared from auxiliary cationic additive and Fe3+A multi-element cationic polymeric flocculant, a process for preparing the same, and a use thereofThe cation in the auxiliary cation additive is Mg2+、Zn2+Composition of Fe3+Accounting for 40 percent of the total molar weight of the cations in the iron-based flocculant.
Wherein: fe3+Introducing pickling waste liquid containing iron as raw material, Mg2+Magnesium sulfate and magnesium trisilicate composition (magnesium sulfate and magnesium trisilicate in the molar ratio of 1:0.8) are used as raw material, Zn is added2+Zinc sulfate and an activated zinc silicate composition (the molar ratio of the zinc sulfate to the activated zinc silicate in the composition is 1:1) are taken as raw materials.
The compound inorganic high polymer iron flocculant is prepared by the following steps:
1) adding a proper amount of concentrated sulfuric acid into the iron-containing pickling waste liquid, stirring for 3-5min, adding chlorate, heating to 70-75 ℃, and stirring for reacting for 2h to obtain a solution A for later use;
2) taking auxiliary cation additives, respectively stirring and dissolving the auxiliary cation additives in deionized water, and then regulating the pH value to 3-5 by using sulfuric acid and sodium hydroxide as acid-base regulators to obtain solutions containing auxiliary cations;
3) and sequentially adding the solutions containing the auxiliary cations into the solution A under the stirring condition, obtaining a total mixed solution after the addition is finished, adjusting the temperature to be 45-50 ℃, and stirring for reaction for 1-3 hours to obtain the composite inorganic high polymer iron-based flocculant.
Wherein: the total iron content in the iron-containing pickling waste liquid in the step 1) is 5.8 percent; the mol ratio of the addition amount of the concentrated sulfuric acid in the step 1) to the total iron in the iron-containing acid pickling waste liquid is 1:2, the mass fraction of the chlorate is 6 percent of sodium chlorate, and the mol ratio of the chlorate to the total iron in the iron-containing acid pickling waste liquid is 1: 8; in the step 2), the concentrations of sulfuric acid and sodium hydroxide are both 0.15 mol/L; and 3) adding chlorate and a stabilizer in the stirring reaction process, wherein the addition amount of the chlorate is 5% of the mass of the total mixed solution, and the addition amount of the stabilizer is 0.5% of the mass of the total mixed solution.
The chlorate adopts sodium chlorate with the mass fraction of 6 percent, and the stabilizer comprises the following components in parts by weight: 40 parts of polyacrylamide, 30 parts of polyethylene glycol 400and 3 parts of tetrabutyl titanate.
The composite inorganic high polymer iron-based flocculant prepared in the embodiment is respectively used for flocculation treatment of printing and dyeing wastewater and papermaking wastewater, and the dosage of the composite inorganic high polymer iron-based flocculant is 2% of the mass of the wastewater (the dosage of the flocculant can be 20ml/L according to the mass-volume ratio).
When the method is used, the pH value of the wastewater is adjusted to 10.8-11.5, then a flocculating agent is added, the wastewater is stirred and treated for 20min at room temperature (25 +/-2 ℃), the wastewater is kept stand and settled for 0.5-1h, and the wastewater on the upper layer is taken for detection and analysis, wherein the data is as follows:
comparative examples 1 to 3 were made with reference to inventive example 4, in which:
comparative example 1: only the prepared iron-containing cation solution A is used as a flocculating agent, the preparation condition is unchanged, and the using method is the same as that of the embodiment 4;
comparative example 2: the prepared flocculating agent comprises Fe3+And Zn2+The preparation conditions were the same as in example 4;
comparative example 3: the prepared flocculating agent comprises Fe3+And Ti4+The preparation conditions were the same as in example 4;
comparative examples 1 to 3 were also subjected to wastewater treatment (printing wastewater/paper-making wastewater) with the following data:
the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The composite inorganic high polymer iron flocculant features that the iron flocculant is assistant cationic additive and Fe3+The cation in the auxiliary cation additive is Al3+、Mg2+、Zn2+、Ti4+Either or both of which are Fe3+Accounting for 30-60% of the total mole of the cations in the iron-based flocculant.
2. The compound inorganic high polymer iron-based flocculant according to claim 1, characterized in that: said Fe3+Introducing Al from pickling waste liquid containing iron or ferrous sulfate heptahydrate or a combination of the two as raw materials3+Introducing polymeric aluminum ferric sulfate silicate or RE-silicon aluminum molecular sieve or the combination of the two as raw materials, Mg2+Zn is introduced from magnesium sulfate or magnesium trisilicate or a combination of the magnesium sulfate and the magnesium trisilicate as raw materials2+Any one or more of zinc sulfate, activated zinc silicate and polysilicate zinc sulfate is used as raw material, Ti4+Is introduced by using titanium polysilicate or TS-1 molecular sieve or the combination of the two as raw materials.
3. The compound inorganic high polymer iron-based flocculant according to claim 2, characterized in that: the RE-silicon aluminum molecular sieve is characterized in that the rare earth in the RE-silicon aluminum molecular sieve is selected from any one or a plurality of compositions of La, Ce, Sm and Sc, and the molar ratio in the molecular sieve is RE: (Si + Al) ═ 0.01-0.05: 1.
4. The compound inorganic high polymer iron-based flocculant according to any one of claims 1 to 3, characterized by being prepared by the following steps:
1) preparing iron-containing pickling waste liquid or ferrous sulfate heptahydrate into iron-containing solution by adding deionized water, adding appropriate amount of concentrated sulfuric acid into the iron-containing pickling waste liquid or iron-containing solution, stirring for 3-5min, adding chlorate, heating to 70-75 deg.C, stirring, and reacting for 2 hr to obtain solution A;
2) taking auxiliary cation additives, respectively stirring and dissolving the auxiliary cation additives in deionized water, and then regulating the pH value to 3-5 by using sulfuric acid and sodium hydroxide as acid-base regulators to obtain solutions containing auxiliary cations;
3) and sequentially adding the solutions containing the auxiliary cations into the solution A under the stirring condition, obtaining a total mixed solution after the addition is finished, adjusting the temperature to be 45-50 ℃, and stirring for reaction for 1-3 hours to obtain the composite inorganic high polymer iron-based flocculant.
5. The compound inorganic high polymer iron-based flocculant according to claim 4, characterized in that: the total iron content in the iron-containing pickling waste liquid or the iron-containing solution in the step 1) is 5.6-6%.
6. The compound inorganic high polymer iron-based flocculant according to claim 4, characterized in that: the mol ratio of the addition amount of the concentrated sulfuric acid in the step 1) to the total iron in the iron-containing acid pickling waste liquid or the iron-containing solution is 1:2, the chlorate adopts 5-6% by mass of potassium chlorate or sodium chlorate, and the mol ratio of the chlorate to the total iron in the iron-containing acid pickling waste liquid or the iron-containing solution is 1: 8.
7. The compound inorganic high polymer iron-based flocculant according to claim 4, characterized in that: in the step 2), the concentrations of the sulfuric acid and the sodium hydroxide are both 0.1-0.15 mol/L.
8. The compound inorganic high polymer iron-based flocculant according to claim 4, characterized in that: and 3) adding chlorate and a stabilizer in the stirring reaction process, wherein the addition amount of the chlorate is 3-10% of the mass of the total mixed solution, and the addition amount of the stabilizer is 0.5-2% of the mass of the total mixed solution.
9. The compound inorganic high polymer iron-based flocculant according to claim 8, characterized in that: the chlorate adopts 5-6% of potassium chlorate or sodium chlorate by mass fraction, and the stabilizer comprises the following components in parts by weight: 40-50 parts of polyacrylamide, 30-40 parts of polyethylene glycol 400and 3-6 parts of tetrabutyl titanate.
10. The use of the composite inorganic high polymer iron-based flocculant prepared by the preparation method of claim 4, wherein: the composite inorganic high polymer iron flocculant is used for flocculation treatment of printing and dyeing wastewater and papermaking wastewater, and the dosage of the composite inorganic high polymer iron flocculant is 1-3% of the mass of the wastewater.
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