CN110282715B - Preparation and application of polyquaternium in-situ composite modified polymeric ferric sulfate - Google Patents
Preparation and application of polyquaternium in-situ composite modified polymeric ferric sulfate Download PDFInfo
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Abstract
The invention discloses preparation and application of polyquaternium in-situ composite modified polyferric sulfate, wherein the preparation of the polyquaternium in-situ composite modified polyferric sulfate is carried out by starting from synthesis of modified polyferric sulfate, introducing organic/inorganic mixed acid as a reaction system, taking sodium chlorate as an oxidant, and carrying out oxidation, hydrolysis and polymerization 3 steps of reaction on ferrous sulfate to prepare the high-basicity (18-20%) modified polyferric sulfate; a PDMDAAC (molecular weight of 4500-20000) structural unit is directly introduced into a modified polymeric ferric sulfate aqueous solution by an in-situ polymerization method. The polyquaternary ammonium salt in-situ composite modified polymeric ferric sulfate prepared by the invention is environment-friendly, nontoxic and harmless, and has the advantages of both organic/inorganic polymeric water treatment agents. Has the characteristics of high flocculation speed, high density of alum floc, easy agglomeration, high sedimentation, good decolorization effect, good applicability, small dosage, low cost, convenient use and the like.
Description
Technical Field
The invention belongs to the technical field of chemical products and preparation thereof, and particularly relates to preparation of polyquaternium in-situ composite modified polymeric ferric sulfate; the prepared polyquaternium in-situ composite modified polymeric ferric sulfate is applied to the flocculation and decoloration treatment of printing and dyeing wastewater.
Background
Polyferric sulfate (also known as iron hydroxysulfate), formula: [ Fe ]2(OH)n(SO4)3-n/2]m (n is less than or equal to 2, m is more than or equal to 10) is a novel high-efficiency inorganic polymer flocculation water purifying agent, and has the advantages of strong coagulation capacity, high settling speed, wide applicable pH range, low corrosiveness and good water purifying effect; meanwhile, the flocculant is small in dosage, low in cost, excellent in water quality after treatment, non-toxic, free of aluminum pollution, good in oil breaking, deodorization, decoloration and the like, is called as a green flocculant, is widely applied to raw water purification, oil-water separation, industrial and domestic sewage treatment [ Limingyu, Tang dynasty, Zhang smoothly, research and development progress of inorganic polymer coagulant polymeric ferric sulfate [ J]Industrial water treatment, 2000,20(6),1-5.]. In 1974, Mikami et al [ Mikami Y, Kake I. ion polysulfonate solution [ P ]].JP 49-53195.1974]The synthesis and application of the flocculant are reported for the first time, the research and the application of the polymeric ferric sulfate begin in 80 years in China, and compared with the traditional flocculant, the flocculant has the following characteristics: the product has no toxicity (does not contain harmful heavy metal ions) and can be used for drinking water treatment; secondly, the flocculating agent has high forming speed, compact particles, large specific gravity, high alum floc settling speed and easy separation, and the formed sludge has good dehydration property; and the method has good removal effect on chemical oxygen demand, biochemical oxygen demand, heavy metals and chromaticity in various waste water, and has good decolorization and deodorization performance. Meanwhile, the contents of iron and nitrosamine in water can be effectively reduced; the flocculating constituent has strong binding force with the microorganism and has obvious good removal effect on plankton and the like; the pH has wide application range and can be used at low temperature; sixthly, the raw materials are widely and easily obtained, the product price is low, the adding amount is small, and the use cost is low. The polymeric ferric sulfate product has two dosage forms: firstly, a red brown viscous liquid aqua; ② light yellow amorphous solid powder. The preparation method of the polymeric ferric sulfate mainly comprises a direct oxidation method, a catalytic oxidation method, a one-step synthesis method and a two-step synthesis method.
The direct oxidation method takes ferrous sulfate and various strong oxidizers as raw materials and obtains a target product through 3 steps of oxidation, hydrolysis and polymerization. According to the different selected oxidants, the method can be divided into the following steps: the nitric acid method: uses strong oxidant nitric acid as oxidant, and simultaneously generates NO in the reaction process2The method also can play a role in reoxidation, has the advantages of higher oxidation efficiency, high reaction speed, high product specific gravity and easy preparation of powder, and has the defects of inconvenient operation due to long process route (tail gas suction setting) and environmental pollution. ② potassium chlorate method: compared with a nitric acid method, the method has the advantages of no pollution, simple and convenient operation, simple equipment, good product stability and the like, and has the defects of high raw material cost, KCl and chloride ions contained in the product and secondary treatment problem in application. ③ hypochlorous acid method: the alkaline oxidant sodium hypochlorite is used as the oxidant, and has the advantages of high oxidation potential of sodium hypochlorite, low cost of raw materials, generation of side reaction chlorine, poor product stability and incapability of long-term storage. Hydrogen peroxide method: the hydrogen peroxide as oxidant has the advantages of high active oxygen content, low cost and relatively weak oxidation activity, and certain potential safety hazard in storage and transportation
A catalytic oxidation method: this process was first proposed in japan in the 70 s. With NaNO2As a catalyst, the reaction is carried out under an acidic reaction condition, and ferrous sulfate is oxidized, hydrolyzed and polymerized to obtain a product. The method has the defects that Nitrogen Oxide (NO) is generated in the process, NaNO2Large dosage, residual nitrite ion in the product, and no application in drinking water treatment, and NaNO2The method is a carcinogenic chemical, and further limits the popularization and application of the method [ Xuying Hui. PTS preparation of NaNO2Catalytic action of [ J]Chemical metallurgy, 1998,19(4),76-78.]。
The one-step synthesis method comprises the following steps: respectively dissolving an oxidant in an alkaline or neutral potassium-containing compound to prepare a solution, preparing ferrous sulfate into a solution with a certain concentration, adding the oxidant solution into the ferrous sulfate solution at a controlled temperature to react to obtain polymeric ferric sulfate, and then washing, neutralizing and drying to obtain a powder product (the particle size is 0.2-0.7 mm). the method solves the problem of equipment corrosion caused by using sulfuric acid, and the reaction is carried out under normal pressure, the equipment utilization rate is high and the like [ a novel process for preparing solid polymeric ferric sulfate by a one-step method [ J ]. chemical industry environmental protection, 1997,20 (4): 47-49 ].
The two-step synthesis method comprises the following steps: the method combines catalytic oxidation method and direct oxidation method, and uses pickling solution and iron filings as raw materials, manganese dioxide as oxidant and NaNO2As a cocatalyst, the raw material cost is greatly reduced, but the defects of long reaction time, large consumption of oxidant and acid, high impurity content of the product, low basicity and the like exist [ Lin level, development and application of polyferric sulfate [ J ]]Industrial water treatment, 1994,14(2),35-38.]。
The polyquaternary ammonium Polymer (PQAS) is a linear structure water-soluble polymer obtained by homopolymerization of dialkyl diallyl ammonium chloride or copolymerization of dialkyl diallyl ammonium chloride, acrylamide and acrylic acid, and has the outstanding advantages of safety, no toxicity, high efficiency and low cost compared with the traditional polyacrylamide water treatment agent. The poly dimethyl diallyl ammonium chloride (hereinafter abbreviated as PDMDAAC) becomes the first polymer approved for drinking water treatment, besides, the PQAS series flocculant has many successful applications in the treatment of industrial wastewater, urban domestic wastewater and activated sludge, particularly has an adsorption and bridging effect, has good removal effect on colloidal substances and soluble organic substances, can adapt to high complex water body, has good dehydration treatment effect on printing and dyeing wastewater, domestic sewage and sludge compared with an inorganic flocculant and PAM, and also has obvious bacteriostatic and bactericidal effects.
In summary, the PQAS organic cationic flocculant has: firstly, the molecular weight is high, the flocculation effect is good, and the adsorption bridging capability to colloid substances is strong; wide application range, good product stability, less addition amount, less sludge produced and the like. The polyferric sulfate has the advantages of low cost (compared with organic polymers), easy synthesis, environmental friendliness and the like. Therefore, based on the modified polyferric sulfate, a PDMDAAC unit is introduced in situ to construct the polyquaternium composite modified polyferric sulfate, the advantages of organic/inorganic polymeric flocculant can be organically combined, and a novel organic-inorganic composite multifunctional water treatment agent which is safe, efficient and low in cost and suitable for the flocculation and decoloration treatment of printing and dyeing wastewater is provided, so that the novel organic-inorganic composite modified polyferric sulfate has important theoretical value and good industrial application prospect.
Disclosure of Invention
One of the purposes of the invention is to prepare the modified polymeric ferric sulfate with high basicity (18-20%) by introducing mixed acid consisting of organic acid (lactic acid/citric acid)/inorganic acid (sulfuric acid/phosphoric acid) as a reaction system and sodium chlorate as an oxidant and carrying out oxidation, hydrolysis and polymerization 3 steps of reaction on ferrous sulfate from the synthesis of the modified polymeric ferric sulfate; the PDMDAAC (molecular weight of 4500-20000) structural unit is directly introduced into a modified polymeric ferric sulfate aqueous solution through an in-situ polymerization method, and the poly-quaternary ammonium salt in-situ composite modified polymeric ferric sulfate and the preparation method thereof are provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of polyquaternium in-situ composite modified polyferric sulfate comprises the following steps:
step S101: adding ferrous sulfate and distilled water into a reaction bottle with magnetic stirring, dropwise adding mixed acid after completely dissolving, fully stirring, adding sodium chlorate for 3 times, controlling the reaction temperature at 60-65 ℃, and carrying out heat preservation reaction for 1h to obtain the modified polymeric ferric sulfate (the basicity is 18-20%) with the appearance of a reddish brown liquid and the viscosity is 60-80 mPa.s. Raw material ratio: ferrous sulfate: sodium chlorate: mixed acid (sulfuric acid/phosphoric acid/lactic acid/citric acid) = 17.5: 1.5: 1.3-1.5 (mass ratio), and the mixed acid is sulfuric acid: phosphoric acid: lactic acid: mixing citric acid according to the mass ratio of (0.8-1.0): (0.12-0.13): (0.1-0.2): (0.12-0.22).
Step S102: under the protection of nitrogen, 10mL of modified polymeric ferric sulfate solution, 5mL of deionized water and 10mL of dimethyl diallyl ammonium chloride aqueous solution (mass ratio of 15%) are sequentially added into a reaction bottle with magnetic stirring, the pH of the system is adjusted to be =5 by mixed acid, the temperature is raised to 40 ℃, 5mL of initiator V-44 aqueous solution (concentration of 5% (mass ratio)) is dropwise added, and the reaction is carried out for 1h after the addition is finished. The temperature is raised to 50 ℃, 5mL of initiator V-44 aqueous solution (with the concentration of 5 percent (mass ratio)) is dripped for the second time, and the reaction is kept for 2 hours after the addition. And (3) heating to 70 ℃, and curing for 5h to obtain the product polyquaternium in-situ composite modified polymeric ferric sulfate, wherein the molecular weight of the poly dimethyl diallyl ammonium chloride is 4500-25000.
The invention also aims to provide a method for carrying out flocculation and decoloration treatment on printing and dyeing wastewater by applying the polyquaternium in-situ composite modified polymeric ferric sulfate.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the polyquaternium in-situ composite modified polyferric sulfate stock solution and water are mixed in equal volume and then used in the form of a water agent, the dosage is 1.5mL/200mL, the turbidity removal rate is 92%, and the decoloration rate is 91%. The treatment method has the characteristics of environmental friendliness, no toxicity, no harm, high flocculation speed, high density of alum floc, easiness in agglomeration, high settling speed, good decoloring effect, good applicability, small dosage, low cost, convenience in use (in the form of an aqueous solution) and the like.
The invention has the beneficial effects that:
1. an organic/inorganic mixed acid system is introduced, sodium chlorate is used as an oxidant to synthesize the modified polymeric ferric sulfate with high basicity (18-20%), a novel process for conveniently and effectively preparing the polymeric ferric sulfate with high basicity is established, the basicity of the product of the organic acid system used alone is 16-17%, and the basicity of the product of the inorganic acid system used alone is below 14%;
2. directly taking a modified polymeric ferric sulfate aqueous solution as a reaction system, taking V-44 as an initiator, regulating and controlling the pH value of the system by an organic/inorganic mixed acid system, introducing a linear-structure poly dimethyl diallyl ammonium chloride unit through in-situ polymerization, and constructing the poly quaternary ammonium salt composite modified polymeric ferric sulfate, thereby realizing the integration of the advantages of PDMDAAC and the polymeric ferric sulfate;
3. the method combines the advantages of high flocculation speed of the polyferric sulfate and good flocculation effect of the polydimethydiallylammonium chloride on colloidal substances and soluble organic substances into one, and simultaneously has the advantages of easy preparation, low cost and direct use in the form of a water agent.
Drawings
FIG. 1 is an infrared spectrum of polyquaternium in-situ composite modified polymeric ferric sulfate;
FIG. 2 is an infrared spectrum of a modified polymeric ferric sulfate;
FIG. 3 is an XRD spectrum of polyquaternium in-situ composite modified polymeric ferric sulfate;
FIG. 4 is an XRD spectrum of modified polymeric ferric sulfate;
FIG. 5 shows the results of flocculation and decolorization treatment of a polyquaternium in-situ composite modified polyferric sulfate and a modified polyferric sulfate water sample, wherein (1) acid bright red wastewater, (2) kaolin suspension, and (3) direct yellow wastewater; (a) adding a processing result of in-situ composite modification of polymeric ferric sulfate by addition of quaternary ammonium salt, (b) adding a processing result of modified polymeric ferric sulfate;
FIG. 6 is an electron microscope image of polyquaternium in situ composite modified polyferric sulfate (polyquaternium molecular weight 12000).
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1: synthesis of modified polymeric ferric sulfate
Step S101: after 17.5g of ferrous sulfate and 5ml of distilled water were added to a reaction flask equipped with magnetic stirring and sufficiently dissolved, the prepared mixed acid (0.12 g of phosphoric acid, 1.0g of sulfuric acid, 0.1g of lactic acid, 0.12g of citric acid) was added and stirred at room temperature for 15 min. Adding 1.5g of sodium chlorate in 3 times, controlling the reaction temperature at 60 ℃, and reacting for 1h under heat preservation to obtain a reddish brown modified polymeric ferric sulfate solution.
Product viscosity: 60 mPa.s, 18% of basicity;
FT-IR( KBr) ，ν/cm－1: 3440，2026，1630，1138，996，619。
no obvious single characteristic peak appears in the XRD pattern, which indicates that the polymeric ferric sulfate is in an amorphous structure or exists in a polycrystalline form.
Further, the same as above except that sulfuric acid was 0.9g, phosphoric acid was 0.13g, lactic acid was 0.1g, and citric acid was 0.22g in step S101. Product viscosity: 75 mPa.s, and the basicity is 19 percent.
Further, the same as above except that sulfuric acid in the step S101 was 0.8g, phosphoric acid was 0.13g, lactic acid was 0.2g, and citric acid was 0.22 g. Product viscosity: 80 mPa.s, and the basicity is 20 percent.
Example 2 Synthesis of Polyquaternium in situ composite modified polymeric ferric sulfate
Step S201: in a reactor equipped with magnetic stirring, 10mL of a modified polymeric ferric sulfate solution, 5mL of deionized water, and 10mL of a DMDAAC aqueous solution (15% by mass) were sequentially added, and the mixture was stirred at room temperature for 20min with the system pH =5 adjusted with mixed acid. Under the protection of nitrogen, the temperature is raised to 40 ℃, 5mL of initiator V-44 aqueous solution (with the concentration of 5 percent (mass ratio)) is added dropwise, and the reaction is carried out for 1h after the addition. The temperature is raised to 50 ℃, 5mL of initiator V-44 aqueous solution (with the concentration of 5 percent (mass ratio)) is dripped for the second time, and the reaction is kept for 2 hours after the addition. And (3) heating to 70 ℃, and curing for 5h to obtain the product polyquaternium in-situ composite modified polymeric ferric sulfate, wherein the molecular weight of the poly dimethyl diallyl ammonium chloride is 12000.
FT-IR( KBr) ，ν/cm－13447, 3012, 2942, 2145, 1598 (strong absorption peak, deformation vibration of quaternary ammonium ion N +), 1474, 1366 (-CH)2Absorption peak), 1137 (C — N stretching vibration).
Compared with the infrared absorption of polyferric sulfate and PDMDAAC, the polymer chain has-CH2Blue-shift of the attraction peak, attraction of the C-N bond by SO4 3-The results of absorption peak covering and the like show that the chemical environment of the organic/inorganic polymeric structural unit in the composite system is changed, and the results prove that the organic/inorganic polymeric structural unit and the composite system are not simply mechanically mixed and form a new composite.
The XRD low-angle region presents a single absorption peak with obvious characteristic peak, which shows that the phase state of the polymeric ferric sulfate in the composite modified polymeric ferric sulfate structure is fundamentally changed from amorphous state or polycrystalline phase to single crystalline state. The result shows that the introduction of the polyquaternium through in-situ polymerization has a remarkable regulation effect on the appearance of the polymeric ferric sulfate, and on the other hand, the organic/inorganic structural unit in the complex structure is further proved to exist in a mutual fusion combination mode.
SEM shows that the target product is relatively uniform cubic particles with the dimension of 30-50 nm. The results show that the polymerization of the dimethyl diallyl ammonium chloride in the modified polymeric ferric sulfate system is sufficient and effective, the reaction is uniform, and the molecular weight distribution is relatively consistent.
Further, the procedure of step S201 was as described above except that the amount of the DMDAAC aqueous solution (15% by mass) added was 7mL for aging for 3 hours. The product has a molecular weight of 5000.
Further, the procedure of step S201 was as described above except that the amount of the DMDAAC aqueous solution (15% by mass) added was 12mL of the aging solution for 7 hours. The product had a molecular weight of 25000.
Application example 1: flocculation of kaolin suspensions
0.15g of kaolin powder is weighed and placed in a 250ml single-neck bottle, then 100ml of distilled water is added, the mixture is stirred uniformly under the stirring of a magnetic stirrer, and then the turbidity of the supernatant liquid is measured by a turbidity meter. Adding 1.5mL of polyquaternium in-situ composite modified polyferric sulfate aqueous solution (equal volume mixture of stock solution and water), stirring at room temperature for 5min, standing for 10min, measuring turbidity of supernatant, and calculating turbidity removal rate.
TABLE 1 turbidity removal results of polyquaternium in-situ composite modified polyferric sulfate
Application example 2: flocculation decolorization of printing and dyeing wastewater
Adding 100ml of factory wastewater into a beaker, uniformly stirring the wastewater by a magnetic stirrer, and taking the supernatant to measure the absorbance of the supernatant. Adding 1.5mL of polyquaternium in-situ composite modified polyferric sulfate aqueous solution (equal-volume mixture of stock solution and water), stirring at room temperature for 5min, standing for 10min, taking supernatant, measuring absorbance, and calculating decolorization rate.
TABLE 2 decolorization results of polyquaternium in-situ composite modified polymeric ferric sulfate
Application example 3: the effects of the modified polymeric sulfuric acid and the polyquaternary ammonium salt in-situ composite modified polymeric ferric sulfate are compared
100mL of kaolin suspension (with the concentration of 1.5 g/L) or 100mL of printing and dyeing wastewater is added into a reaction bottle with magnetic stirring, after stirring for 10min, a polyquaternium in-situ composite modified polymeric ferric sulfate aqueous solution (an isometric mixture of stock solution and water) is added, stirring is carried out for 5min, standing is carried out, and the turbidity removal rate and the decoloration rate are respectively measured, and the results are shown in Table 3.
TABLE 3 flocculation and decolorization results of modified polysulfuric acid and polyquaternium in-situ composite modified polyferric sulfate
Note: the salinity of the modified polymeric ferric sulfate is 20 percent; the molecular weight of the composite modified polymeric ferric sulfate is 12000, and the basicity is 20%.
The above description is only for the preparation method of the present invention, and all equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (5)
1. A preparation method of polyquaternium in-situ composite modified polymeric ferric sulfate is characterized by comprising the following steps: the method comprises the following steps:
step S101: adding distilled water and ferrous sulfate into a reaction bottle with magnetic stirring, after complete dissolution, dropwise adding mixed acid, after uniform stirring, adding sodium chlorate for 3 times, controlling the reaction temperature at 60-65 ℃, and carrying out heat preservation reaction for 1h to obtain a modified polymeric ferric sulfate solution with a reddish brown liquid appearance, wherein the viscosity is 60-80 mPa.s, and the basicity is 18-20%;
step S102: under the protection of nitrogen, sequentially adding 10mL of modified polymeric ferric sulfate solution, 5mL of deionized water, 10mL of 15wt% dimethyl diallyl ammonium chloride aqueous solution, adjusting the pH of the system to be =5, heating to 40 ℃, dropwise adding 5mL of 5wt% initiator V-44 aqueous solution, carrying out heat preservation reaction for 1h after the addition is finished, heating to 50 ℃, dropwise adding 5mL of 5wt% initiator V-44 aqueous solution for the second time, carrying out heat preservation reaction for 2h after the addition is finished, heating to 70 ℃, and curing for 5h to obtain the product, namely the polyquaternium in-situ composite modified polymeric ferric sulfate, wherein the mixed acid is a mixed system of organic acid and inorganic acid.
2. The preparation method according to claim 1, wherein the mixed acid is sulfuric acid: phosphoric acid: lactic acid: mixing citric acid according to the mass ratio of (0.8-1.0): (0.12-0.13): (0.1-0.2): (0.12-0.22).
3. The preparation method according to claim 1, wherein in step S101, the mass ratio of the materials fed is: ferrous sulfate: sodium chlorate: mixed acid = 17.5: 1.5: 1.3 to 1.5.
4. The preparation method of claim 1, wherein the molecular weight of the poly dimethyl diallyl ammonium chloride in the poly ferric sulfate in-situ composite modified by the poly quaternary ammonium salt is 4500-25000.
5. The application of the polyquaternium in-situ composite modified polymeric ferric sulfate prepared by the preparation method of claim 1, which is characterized in that: the polyquaternium in-situ composite modified polymeric ferric sulfate is directly applied to flocculation and decoloration of printing and dyeing wastewater in a water agent form.
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