CN106745624B - Inorganic-organic hybrid flocculation material and preparation method thereof - Google Patents
Inorganic-organic hybrid flocculation material and preparation method thereof Download PDFInfo
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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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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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Abstract
The invention provides an inorganic-organic hybrid flocculant and a preparation method thereof, wherein the raw material components of the inorganic-organic hybrid flocculant comprise an initiator, an inorganic flocculant and an organic monomer in a mass ratio of 1:9-1:6, the organic monomer comprises dimethyldiallylammonium chloride and acrylamide in a mass ratio of 1:9-1:5, and the mass of the initiator is 0.02-5% of the mass of the organic monomer. The inorganic-organic hybrid flocculant is obtained by introducing acrylamide and dimethyl diallyl ammonium chloride into an inorganic flocculant to initiate in-situ copolymerization of two monomers in an inorganic system. The inorganic-organic hybrid flocculant can better adapt to the sedimentation of charged fine-grained tailings by reasonably selecting raw materials and proportioning, can obviously improve the sedimentation rate of a tailing suspension liquid under the condition of low addition amount, reduces the turbidity of supernatant, improves the quality of return water while reducing the wastewater treatment cost, and achieves the purposes of energy conservation and emission reduction.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and relates to an inorganic-organic hybrid flocculation material and a preparation method thereof.
Background
In the beneficiation industry, ore is sorted to produce typically 10% to 20% tailings suspension. At present, the tailings have a series of problems: (1) in order to effectively extract valuable elements in the ore, the ore particles are ground to be extremely fine, namely d50 is below 30 mu m, and the surfaces of the particles are adsorbed and hydrolyzed to carry negative charges, so that suspended particles are difficult to rapidly settle in suspension under the influence of factors such as small gravity, large electrostatic repulsion and the like; (2) the residual quantity of fine particles in the tailing supernatant obtained by natural sedimentation is high, the direct reuse can influence the beneficiation effect due to serious argillization phenomenon and the like, and the outward discharge can cause environmental pollution due to the residue of beneficiation reagents; (3) the tailings have low water return rate, and low-density transportation consumes a large amount of electric power. Therefore, effective dehydration of tailings for achieving the purposes of rapid sedimentation of tailing particles, low solid content of backwater, recycling of beneficiation wastewater and the like is a problem to be solved urgently at present.
The flocculation technology is an economical, simple and effective tailing dewatering treatment method for realizing solid-liquid separation at present, so that the efficient flocculating agent occupies an irreplaceable position in the tailing dewatering link. Flocculants that are currently in widespread use include inorganic flocculants, organic flocculants, microbial flocculants, and composite flocculants.
The inorganic flocculant comprises aluminum and iron low-molecular flocculant or polymeric flocculant, and generally, the flocculant has a certain amount of positive charges and can play a role of electric neutralization to neutralize the surface charges of particles so as to destabilize the particles, or form large and compact flocs through the adsorption and bridging action of inorganic macromolecules so as to rapidly settle. The inorganic flocculant is widely applied to the field of water treatment, but when the inorganic flocculant is used for the flocculation treatment of tailings with higher solid content, the addition amount is larger, and the cost is higher.
The organic flocculant comprises a synthetic organic polymer flocculant such as polyacrylamide and poly dimethyl diallyl ammonium chloride and a natural organic polymer flocculant such as starch and vegetable gum, and the flocculant has higher adsorption bridging capacity due to a long macromolecular chain, so that a better flocculation effect can be achieved under the condition of small addition amount. At present, the organic flocculant is widely applied to the tailing dewatering link of mineral separation enterprises, but has some defects in the aspects of high cost of cationic monomers, poor colloidal destabilization effect of nonionic flocculants, steric hindrance effect and the like.
Microbial flocculants originated from flocculant producing bacteria screened from activated sludge by Butterfield in 1935, and the flocculants are produced by microbial metabolism and include protein, cellulose and the like. The microbial flocculant has the advantages of small dosage, environmental protection, easy degradation and the like, but the defects of high raw material cost, low flocculant yield and the like limit the wide application of the microbial flocculant.
The composite flocculant is a novel flocculant produced after inorganic flocculant, organic flocculant and microbial flocculant are widely applied in recent years, comprises hybridization and compounding of two or more than two flocculants, and aims to have the flocculation characteristics of various flocculants so as to realize high-efficiency separation of solid and liquid in suspension. Practice proves that the flocculation effect of the composite flocculant is better than that of a single flocculant, particularly the effect of an inorganic/organic flocculant is better, and the composite flocculant is expected to become a new generation flocculant.
CN103011359A discloses an inorganic-organic composite flocculant of poly aluminum ferric chloride dimethyl diallyl ammonium chloride homopolymer, which is a simple composite of inorganic and organic components at normal temperature, has no chemical bond, has high content of inorganic components, and has large dosage and high cost when applied to tailing dehydration; CN103351047A discloses an inorganic-organic hybrid flocculant, wherein the inorganic part is polyaluminium chloride, the organic part is poly dimethyl diallyl ammonium chloride, and the two are connected by ionic bonds. The polyferric chloride accounts for a relatively high proportion in the hybrid flocculant, is slightly insufficient in the aspect of exerting the adsorption and bridging of organic polymer chains, and has the problems of high flocculant adding amount, large using amount, high cost and the like when being used for treating tailing suspension with relatively high solid content. CN1554592A discloses an organic-inorganic ionic hybrid high-efficiency flocculant, which comprises 0.5-15% of hydroxide colloid, 50-95% of acrylamide and 0-45% of cationic monomer by weight percent. The hydroxide colloid is aluminum hydroxide, ferric hydroxide, magnesium hydroxide or zinc hydroxide, the particle size of the colloid is 10-200nm, and the cationic monomer comprises N, N-dimethyl diallyl ammonium chloride or (methyl) acryloyloxy and trimethyl ammonium chloride. The preparation method of the flocculant comprises the following steps: mixing acrylamide, cationic monomer and hydroxide colloidal solution, adding deionized water, stirring, introducing nitrogen, heating to 50-60 ℃, adding initiator aqueous solvent, stirring uniformly, and reacting at constant temperature to obtain the flocculant.
Therefore, a novel inorganic-organic hybrid flocculant with high inorganic component content needs to be researched, the load capacity of the inorganic-organic hybrid flocculant is reasonably regulated and controlled, when the novel inorganic-organic hybrid flocculant is applied to dehydration treatment of tailings suspensions with different particle sizes, the effects of electric neutralization and adsorption bridging flocculation are efficiently and synergistically exerted, and the aim of achieving a better flocculation effect can be achieved under the condition of small addition amount.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an inorganic-organic hybrid flocculant and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide an inorganic-organic hybrid flocculant, the raw material components of the inorganic-organic hybrid flocculant comprise an initiator, an inorganic flocculant and an organic monomer in a mass ratio of 1:9-1:6, the organic monomer comprises dimethyldiallylammonium chloride and acrylamide in a mass ratio of 1:9-1:5, and the mass of the initiator is 0.02-5% of the mass of the organic monomer.
The mass ratio of the inorganic flocculant to the organic monomer can be 1:6.5, 1:7, 1:7.5, 1:8 or 1:8.5 and the like; the mass ratio of the dimethyl diallyl ammonium chloride to the acrylamide can be 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8 or 1:8.5 and the like; the mass of the initiator may be 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 4.5%, or the like of the mass of the organic monomer.
If the mass ratio of the inorganic flocculant to the organic monomer is not within the range, the charge capacity of the hybrid material is too low, which affects the exertion of the electric neutralization effect, or the organic molecular chain of the hybrid material is too short, which affects the exertion of the adsorption-bridging effect.
If the mass of the dimethyl diallyl ammonium chloride and the mass of the acrylamide are not in the range, the load capacity of the hybrid material or the length of a macromolecular chain are also influenced, so that the flocculation effect is influenced.
If the mass fraction of the initiator in the organic monomer is not within this range, the initiation efficiency will be low, resulting in a low molecular weight of the hybrid material, and finally in a decrease in flocculation of the material.
The structure of the inorganic-organic hybrid flocculant is the same as that of the organic-inorganic ionic hybrid high-efficiency flocculant disclosed in CN 1554592A. The difference lies in that the mass ratio of the inorganic flocculant to the organic monomer and the mass ratio of the dimethyl diallyl ammonium chloride to the acrylamide in the inorganic-organic hybrid flocculant are different.
The inorganic-organic hybrid flocculant provided by the invention has the advantages that the mass ratio of the inorganic flocculant to the organic monomer and the mass ratio of the dimethyl diallyl ammonium chloride to the acrylamide are adjusted, so that the obtained product has proper surface charge, and the inorganic-organic hybrid flocculant is suitable for settling charged fine-grained tailings and can play a role in efficient flocculation under the condition of small addition amount.
The inorganic-organic hybrid flocculant provided by the invention combines an acrylamide monomer and a dimethyl diallyl amide monomer, effectively controls the charge amount of the inorganic-organic hybrid flocculant by means of the adsorption bridging effect of an organic high-molecular long chain obtained by copolymerization and by adjusting the component proportion of the inorganic flocculant and the dimethyl diallyl monomer, synergistically plays the electric neutralization effect and the polyhydroxy adsorption effect of the inorganic flocculant, and realizes the high-efficiency separation of fine particles and water at low addition amount.
The inorganic-organic hybrid flocculant provided by the invention is formed by connecting an inorganic flocculant and an organic acrylamide-dimethyl diallyl copolymerization long chain to form an ionic bond hybrid structure. The inorganic component and the cationic monomer neutralize the charge on the surface of the particles to be treated, the repulsion force of a suspension system is reduced, the polyhydroxy and the organic polyacrylamide-dimethyl diallyl ammonium chloride long chain of the inorganic component adsorb the particles to form large flocs through strong adsorption and bridging effects, and the inorganic component and the organic polyacrylamide-dimethyl diallyl ammonium chloride long chain cooperate with each other to realize efficient flocculation.
The organic monomer comprises dimethyldiallylammonium chloride and acrylamide in a mass ratio of 1:8-1:7, such as 1:7.1, 1:7.2, 1:7.3, 1:7.5, 1:7.6 or 1: 7.8. When the organic monomers are dimethyl diallyl ammonium chloride and acrylamide in the mass ratio, the effect of the inorganic-organic hybrid flocculant is optimal.
The initiator is an oxidation-reduction initiator, and the mass ratio of the oxidant to the reducing agent in the oxidation-reduction initiator is 1.05:1-2: 1.
The oxidant is selected from ammonium persulfate and/or potassium persulfate, and the reducing agent is selected from sodium bisulfite.
The inorganic flocculant is selected from any one or a combination of at least two of aluminum hydroxide, ferric hydroxide, polyaluminum chloride, polyferric sulfate, polyaluminum silicate or polyferric silicate, and typical but non-limiting combinations are aluminum hydroxide and ferric hydroxide, ferric hydroxide and polyaluminum chloride, ferric hydroxide and polyferric sulfate, polyaluminum silicate and polyferric silicate, polyaluminum chloride, polyferric sulfate, polyaluminum silicate and polyferric silicate, preferably any one or a combination of at least two of polyaluminum chloride, polyferric sulfate, polyaluminum silicate or polyferric silicate.
The inorganic flocculant is selected from a mixture of aluminum hydroxide and polyaluminum silicate in a mass ratio of (2-5):1, such as a mass ratio of 2.5:1, 3:1, 3.5:1, 4:1 or 4.5: 1. When the mixture is selected as the inorganic flocculant, the obtained inorganic-organic hybrid flocculant has the best effect.
The second purpose of the invention is to provide a preparation method of the inorganic-organic hybrid flocculant, which comprises the following steps:
(1) mixing an inorganic flocculant solution or inorganic flocculant colloid, dimethyl diallyl ammonium chloride and acrylamide in an inert atmosphere to obtain a mixed solution; then, adding an initiator into the mixed solution to carry out polymerization reaction to obtain reaction product gel;
(2) dissolving the reaction product gel and extracting to obtain a precipitate;
(3) and drying the precipitate to obtain the inorganic-organic hybrid flocculant.
The inert atmosphere in the step (1) is selected from any one of a nitrogen atmosphere, a helium atmosphere or an argon atmosphere or a combination of at least two of the nitrogen atmosphere, the helium atmosphere and the argon atmosphere. Typical but non-limiting combinations such as nitrogen atmosphere and helium atmosphere, nitrogen atmosphere and argon atmosphere, nitrogen atmosphere, argon atmosphere and helium atmosphere.
Preferably, the initiator of step (1) is added dropwise to the mixture to make the polymerization reaction milder.
Preferably, the polymerization reaction in step (1) is carried out in a constant temperature water bath at 40-90 deg.C, such as 42 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 55 deg.C, 58 deg.C, 60 deg.C, 62 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C or 85 deg.C.
Preferably, the polymerization reaction time in step (1) is 4-12h, such as 5h, 6h, 7h, 8h, 9h, 10h or 11 h.
Dissolving the reaction product gel in the step (2) in deionized water.
Preferably, the solvent used for the extraction in step (2) is acetone.
As a preferred technical scheme, the preparation method of the inorganic-organic hybrid flocculant comprises the following steps:
(1) mixing an inorganic flocculant solution or inorganic flocculant colloid, dimethyl diallyl ammonium chloride and acrylamide in an inert atmosphere to obtain a mixed solution; then, dropping an initiator into the mixed solution, and carrying out polymerization reaction under the condition of constant-temperature water bath at the temperature of 40-90 ℃ for 4-12h to obtain reaction product gel;
(2) dissolving the reaction product gel in deionized water, and then dropwise adding the dissolved gel into acetone for extraction to obtain a precipitate;
(3) and drying the precipitate to constant weight to obtain the inorganic-organic hybrid flocculant.
Compared with the prior art, the invention has the beneficial effects that:
(1) the inorganic-organic hybrid flocculant provided by the invention can realize high-efficiency flocculation of fine particles with average particle size distribution of 0-100 mu m by reasonably regulating and controlling the charge quantity of the inorganic-organic hybrid flocculant, the sedimentation rate of a tailing suspension can be improved by more than 5 times under the condition of low addition amount within the range of 10g/t-40g/t, the turbidity removal rate of supernatant can reach more than 80%, the quality of backwater is improved while the wastewater treatment cost is reduced, and the purposes of energy conservation and emission reduction are achieved;
(2) the inorganic-organic hybrid flocculant provided by the invention introduces a low-cost inorganic flocculant, can obviously improve the charge neutralization effect, realizes colloid destabilization, and simultaneously plays a synergistic role in polyhydroxy adsorption;
(3) the inorganic-organic hybrid flocculant provided by the invention utilizes a macromolecular organic long chain obtained by copolymerizing an acrylamide monomer and dimethyl allyl ammonium chloride, realizes a strong adsorption bridging effect, can reduce a cationic monomer component in an organic component, and reduces the cost by more than 30%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) to aluminum hydroxide (Al (OH)3) Adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into the colloid until the monomers are completely dissolved, placing the colloid in a constant-temperature water bath device at the temperature of 40 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding ammonium persulfate ((NH)4)2S2O8) And sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 12 hours; wherein Al (OH)3Mass ratio of DMDAAC to AM of 1:9 to organic monomer of 1:9, mass of initiator of 0.1% to organic monomer of (NH4)2S2O8With NaHSO3The mass ratio is 1.5: 1;
(2) dissolving the gel obtained after the reaction in water, and extracting the glue solution obtained by dissolving in acetone to obtain a precipitate;
(3) and (4) placing the precipitate obtained by extraction in a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid flocculant powder.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 10.9m/h, and the turbidity of the supernatant liquid is reduced to 15.7NTU (the natural sedimentation rate of the tailings is 0.6m/h, and the turbidity of the supernatant liquid is 291.59 NTU).
Example 2
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) ferric hydroxide (Fe (OH)3) Adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into the colloid until the monomers are completely dissolved, placing the colloid in a constant-temperature water bath device at the temperature of 50 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding potassium persulfate (K)2S2O8) Sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 6 hours; wherein Fe (OH)3The mass of the initiator and the organic monomer is 1:6, the mass ratio of DMDAAC to AM is 1:8, the mass of the initiator is 0.02 percent of the mass of the organic monomer, and K is2S2O8With NaHSO3The mass ratio is 2: 1;
(2) and (3) dissolving the gel obtained after the reaction is finished in water, and extracting the dissolved glue solution in acetone to obtain a precipitate.
(3) Putting the precipitate obtained by extraction into a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid flocculant powder;
when the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 9.5m/h, and the turbidity of the supernatant liquid is reduced to 38.6NTU (the natural sedimentation rate of the tailings is 0.52m/h, and the turbidity of the supernatant liquid is 294.69NTU)
Example 3
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into a polyaluminium chloride (PAC) solution until the monomers are completely dissolved,placing in a constant temperature water bath device with a temperature of 50 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding ammonium persulfate ((NH)4)2S2O8) And sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 6 hours; wherein the mass ratio of PAC to organic monomer is 1:6, the mass ratio of DMDAAC to AM is 1:9, the mass of initiator is 5% of the mass of organic monomer, (NH4)2S2O8With NaHSO3The mass ratio is 1.05:1
(2) Dissolving the gel obtained after the reaction in water, and extracting the glue solution obtained by dissolving in acetone to obtain a precipitate;
(3) and (4) placing the precipitate obtained by extraction in a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid flocculant powder.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 11.2m/h, and the turbidity of the supernatant is reduced to 9.3NTU (the natural sedimentation rate of the tailings is 0.46m/h, and the turbidity of the supernatant is 295.69 NTU).
Example 4
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into a Polymeric Ferric Sulfate (PFS) solution until the monomers are completely dissolved, placing the solution in a constant-temperature water bath device at the temperature of 90 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding ammonium persulfate (K)2S2O8) And sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 4 hours; wherein the mass of PFS and organic monomer is 1:6, the mass ratio of DMDAAC and AM is 1:5, the mass of initiator is 0.5 percent of the mass of organic monomer, and K is2S2O8With NaHSO3The mass ratio is 2: 1;
(2) dissolving the gel obtained after the reaction in water, and extracting the glue solution obtained by dissolving in acetone to obtain a precipitate;
(3) and (3) placing the precipitate obtained by extraction in a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid white flocculant powder.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 10.4m/h, and the turbidity of the supernatant is reduced to 15.8NTU (the natural sedimentation rate of the tailings is 0.28m/h, and the turbidity of the supernatant is 298.59 NTU).
Example 5
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into a Polymeric Aluminum Silicate (PASiFC) solution until the monomers are completely dissolved, placing the solution in a constant-temperature water bath device at the temperature of 90 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding ammonium persulfate ((NH)4)2S2O8) And sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 4 hours; wherein the mass ratio of PASiFC to organic monomer is 1:8, the mass ratio of DMDAAC to AM is 1:6, the mass of initiator is 1% of the mass of organic monomer, (NH)4)2S2O8With NaHSO3The mass ratio is 2: 1;
(2) dissolving the gel obtained after the reaction in water, and extracting the glue solution obtained by dissolving in acetone to obtain a precipitate;
(3) and (4) placing the precipitate obtained by extraction in a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid flocculant powder.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 11.7m/h, and the turbidity of the supernatant is reduced to 26.7NTU (the natural sedimentation rate of the tailings is 0.20m/h, and the turbidity of the supernatant is 298.0 NTU).
Example 6
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into a polymeric ferric silicate (PSiFC) solution until the monomers are completely dissolved, placing the solution in a constant-temperature water bath device at the temperature of 80 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding ammonium persulfate ((NH)4)2S2O8) And sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 6 hours; wherein the mass ratio of PASiFC to organic monomer is 1:6, the mass ratio of DMDAAC to AM is 1:6, the mass of initiator is 1% of the mass of organic monomer, (NH)4)2S2O8With NaHSO3The mass ratio is 2: 1;
(2) dissolving the gel obtained after the reaction in water, and extracting the glue solution obtained by dissolving in acetone to obtain a precipitate;
(3) and (4) placing the precipitate obtained by extraction in a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid flocculant powder.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 8.6m/h, and the turbidity of the supernatant is reduced to 36.7NTU (the natural sedimentation rate of the tailings is 0.11m/h, and the turbidity of the supernatant is 299.78 NTU).
Example 7
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into a mixture solution of aluminum hydroxide and polyaluminum silicate in a mass ratio of 2:1 until the monomers are completely dissolved, placing the mixture solution in a constant-temperature water bath device at the temperature of 80 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding ammonium persulfate ((NH)4)2S2O8) And sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 6 hours; wherein hydrogen isThe mass ratio of the mixture of alumina and polyaluminium silicate to the organic monomer is 1:6, the mass ratio of DMDAAC to AM is 1:7.5, the mass of the initiator is 5% of the mass of the organic monomer, (NH)4)2S2O8With NaHSO3The mass ratio is 2: 1;
(2) dissolving the gel obtained after the reaction in water, and extracting the glue solution obtained by dissolving in acetone to obtain a precipitate;
(3) and (4) placing the precipitate obtained by extraction in a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid flocculant powder.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 9.6m/h, and the turbidity of the supernatant is reduced to 19.7NTU (the natural sedimentation rate of the tailings is 0.11m/h, and the turbidity of the supernatant is 299.78 NTU).
Example 8
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into a mixture solution of aluminum hydroxide and polymeric aluminum silicate with the mass ratio of 5:1 until the monomers are completely dissolved, placing the mixture solution into a constant-temperature water bath device with the temperature of 80 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding ammonium persulfate ((NH)4)2S2O8) And sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 6 hours; wherein the mass ratio of the mixture of aluminum hydroxide and polyaluminium silicate to the organic monomer is 1:7, the mass ratio of DMDAAC to AM is 1:8, the mass of the initiator is 1 percent of the mass of the organic monomer, (NH)4)2S2O8With NaHSO3The mass ratio is 2: 1;
(2) dissolving the gel obtained after the reaction in water, and extracting the glue solution obtained by dissolving in acetone to obtain a precipitate;
(3) and (4) placing the precipitate obtained by extraction in a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid flocculant powder.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 10.5m/h, and the turbidity of the supernatant is reduced to 12.6NTU (the natural sedimentation rate of the tailings is 0.11m/h, and the turbidity of the supernatant is 299.78 NTU).
Example 9
A preparation method of an inorganic-organic hybrid flocculant comprises the following steps:
(1) adding Acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) monomers into a mixture solution of aluminum hydroxide and polymeric aluminum silicate in a mass ratio of 4:1 until the monomers are completely dissolved, placing the mixture solution in a constant-temperature water bath device at the temperature of 80 ℃, introducing high-purity nitrogen for 30min, and slowly dropwise adding ammonium persulfate ((NH)4)2S2O8) And sodium bisulfite (NaHSO)3) The reaction system is sealed, and the reaction is finished after 6 hours; wherein the mass ratio of the mixture of aluminum hydroxide and polyaluminium silicate to the organic monomer is 1:8, the mass ratio of DMDAAC to AM is 1:7, the mass of the initiator is 1 percent of the mass of the organic monomer, (NH)4)2S2O8With NaHSO3The mass ratio is 2: 1;
(2) dissolving the gel obtained after the reaction in water, and extracting the glue solution obtained by dissolving in acetone to obtain a precipitate;
(3) and (4) placing the precipitate obtained by extraction in a drying oven, drying to constant weight, and grinding to obtain inorganic-organic hybrid flocculant powder.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 10.6m/h, and the turbidity of the supernatant is reduced to 15.9NTU (the natural sedimentation rate of the tailings is 0.11m/h, and the turbidity of the supernatant is 299.78 NTU).
Comparative examples 1 to 3
The comparative examples 1 to 3 are examples 1 to 3 in the specification of CN 1554592A.
When the dosage is 40g/t (dosage of the flocculating agent/dry ore content of tailings), the initial sedimentation rate reaches 4.2m/h, and the turbidity of the supernatant is reduced to 160.4NTU (the natural sedimentation rate of the tailings is 0.11m/h, and the turbidity of the supernatant is 299.78 NTU).
Comparative example 4
The procedure of example 3 was repeated, except that the mass ratio of the polyaluminum chloride to the organic monomer was 1: 5.5.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 7.4m/h, and the turbidity of the supernatant is reduced to 40.2NTU (the natural sedimentation rate of the tailings is 0.46m/h, and the turbidity of the supernatant is 295.69 NTU).
Comparative example 5
The same procedure as in example 3 was repeated, except that the mass ratio of the polyaluminum chloride to the organic monomer was 1: 9.5.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 8.8m/h, and the turbidity of the supernatant is reduced to 60.6NTU (the natural sedimentation rate of the tailings is 0.46m/h, and the turbidity of the supernatant is 295.69 NTU).
Comparative example 6
The procedure of example 3 was repeated, except that the mass ratio of dimethyldiallylammonium chloride to acrylamide was 1: 4.5.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 6.7m/h, and the turbidity of the supernatant is reduced to 28.6NTU (the natural sedimentation rate of the tailings is 0.46m/h, and the turbidity of the supernatant is 295.69 NTU).
Comparative example 7
The procedure of example 3 was repeated, except that the mass ratio of dimethyldiallylammonium chloride to acrylamide was 1: 9.5.
When the adding amount is 40g/t (the using amount of the flocculating agent/the dry ore amount of the tailings), the initial sedimentation rate reaches 7.9m/h, and the turbidity of the supernatant liquid is reduced to 55.4NTU (the natural sedimentation rate of the tailings is 0.46m/h, and the turbidity of the supernatant liquid is 295.69 NTU).
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (12)
1. The inorganic-organic hybrid flocculant for settling charged fine tailings is characterized in that raw material components of the inorganic-organic hybrid flocculant comprise an initiator, an inorganic flocculant and an organic monomer in a mass ratio of 1:9-1:6, wherein the organic monomer comprises dimethyl diallyl ammonium chloride and acrylamide in a mass ratio of 1:9-1:7, and the mass of the initiator is 0.02-5% of that of the organic monomer;
the inorganic flocculant is selected from a mixture of aluminum hydroxide and polyaluminum silicate with the mass ratio of (2-5) 1;
the inorganic-organic hybrid flocculant for settling the charged fine tailings is prepared by the following method, and the method comprises the following steps:
(1) mixing an inorganic flocculant solution or inorganic flocculant colloid, dimethyl diallyl ammonium chloride and acrylamide in an inert atmosphere to obtain a mixed solution; then, adding an initiator into the mixed solution to carry out polymerization reaction to obtain reaction product gel;
(2) dissolving the reaction product gel and extracting to obtain a precipitate;
(3) and drying the precipitate to obtain the inorganic-organic hybrid flocculant.
2. The inorganic-organic hybrid flocculant according to claim 1, wherein the organic monomers comprise dimethyldiallylammonium chloride and acrylamide in a mass ratio of 1:8 to 1:7.
3. The inorganic-organic hybrid flocculant for charged fine tailings settling according to claim 1, wherein the initiator is a redox initiator, and the mass ratio of the oxidant to the reductant in the redox initiator is 1.05:1-2: 1.
4. The inorganic-organic hybrid flocculant for charged fine tailings settling according to claim 3, wherein the oxidant is selected from ammonium persulfate and/or potassium persulfate, and the reducing agent is selected from sodium bisulfite.
5. Method for the preparation of an inorganic-organic hybrid flocculant for the sedimentation of charged fine tailings according to any one of claims 1 to 4, characterized in that the preparation method comprises the following steps:
(1) mixing an inorganic flocculant solution or inorganic flocculant colloid, dimethyl diallyl ammonium chloride and acrylamide in an inert atmosphere to obtain a mixed solution; then, adding an initiator into the mixed solution to carry out polymerization reaction to obtain reaction product gel;
(2) dissolving the reaction product gel and extracting to obtain a precipitate;
(3) and drying the precipitate to obtain the inorganic-organic hybrid flocculant.
6. The method according to claim 5, wherein the inert atmosphere in step (1) is selected from any one of a nitrogen atmosphere, a helium atmosphere, or an argon atmosphere, or a combination of at least two thereof.
7. The method of claim 5, wherein the initiator of step (1) is added dropwise to the mixture.
8. The method according to claim 5, wherein the polymerization reaction of step (1) is carried out under a thermostatic water bath having a temperature of 40-90 ℃.
9. The process of claim 5, wherein the polymerization reaction time in step (1) is 4 to 12 hours.
10. The method of claim 5, wherein the reaction product gel of step (2) is dissolved in deionized water.
11. The method according to claim 5, wherein the solvent used in the extraction in step (2) is acetone.
12. The method according to any one of claims 5 to 11, comprising the steps of:
(1) mixing an inorganic flocculant solution or inorganic flocculant colloid, dimethyl diallyl ammonium chloride and acrylamide in an inert atmosphere to obtain a mixed solution; then, dropping an initiator into the mixed solution, and carrying out polymerization reaction under the condition of constant-temperature water bath at the temperature of 40-90 ℃ for 4-12h to obtain reaction product gel;
(2) dissolving the reaction product gel in deionized water, and then dropwise adding the dissolved gel into acetone for extraction to obtain a precipitate;
(3) and drying the precipitate to constant weight to obtain the inorganic-organic hybrid flocculant.
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