CN115196734A - Composite flocculant and preparation method and application thereof - Google Patents
Composite flocculant and preparation method and application thereof Download PDFInfo
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- CN115196734A CN115196734A CN202210914468.6A CN202210914468A CN115196734A CN 115196734 A CN115196734 A CN 115196734A CN 202210914468 A CN202210914468 A CN 202210914468A CN 115196734 A CN115196734 A CN 115196734A
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- aluminum
- solution
- composite flocculant
- acid leaching
- sulfate
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 67
- 238000002386 leaching Methods 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 229920005552 sodium lignosulfonate Polymers 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001661 Chitosan Polymers 0.000 claims abstract description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 6
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 6
- 239000000661 sodium alginate Substances 0.000 claims abstract description 6
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 11
- 239000001632 sodium acetate Substances 0.000 claims description 11
- 235000017281 sodium acetate Nutrition 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000003113 alkalizing effect Effects 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002351 wastewater Substances 0.000 abstract description 11
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005189 flocculation Methods 0.000 abstract description 8
- 230000016615 flocculation Effects 0.000 abstract description 8
- 230000001954 sterilising effect Effects 0.000 abstract description 8
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 8
- 238000009360 aquaculture Methods 0.000 abstract description 2
- 244000144974 aquaculture Species 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 21
- 239000008394 flocculating agent Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000012086 standard solution Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 235000021110 pickles Nutrition 0.000 description 9
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000004042 decolorization Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical class [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical group [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
-
- 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
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention belongs to the field of water treatment, and particularly relates to a composite flocculant as well as a preparation method and application thereof. The preparation method comprises the following steps: acid leaching the aluminum ash by using a sulfuric acid solution to obtain an aluminum-containing acid leaching solution; regulating the pH value of the aluminum-containing acid leaching solution to 3-5 by using an alkalizer, and obtaining polymeric aluminum sulfate after polymerization reaction; mixing the polyaluminium sulfate with an organic high molecular compound, adding a stabilizer, and curing to obtain a composite flocculant; the organic high molecular compound comprises at least one of sodium alginate, chitosan and sodium lignosulfonate. The invention adopts sulfuric acid with low concentration to soak to obtain polyaluminium sulfate with high basicity, and the composite flocculant prepared from the polyaluminium sulfate has the effects of efficient flocculation, sterilization and ammonia nitrogen removal, can be better applied to the treatment of aquaculture wastewater and printing and dyeing wastewater, and effectively reduces the cost for treating the wastewater.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a composite flocculant as well as a preparation method and application thereof.
Background
Polyaluminium sulfate is one of the commonly used water treatment agents at present, and aluminum ash is used as hazardous waste, and can be used as a raw material for preparing the polyaluminium sulfate under the condition of selecting a proper synthesis process, so that the cost for preparing the polyaluminium sulfate is reduced. The method for preparing polyaluminum sulfate from aluminum ash at present mainly comprises the steps of removing nitrogen and fluorine, adding acid to leach aluminum, adding an alkalizer to adjust pH, heating for polymerization, and aging for a period of time to obtain the polyaluminum sulfate.
The prior art has the problems that the preparation cost of the polyaluminium sulfate process is relatively high, and the prepared polyaluminium sulfate water treatment agent has poor purification effect. For example, in the acid leaching step, the influence on the acid is less explored, and concentrated sulfuric acid is generally directly used, so that the problems of high cost and danger exist. In addition, the alkalizer is generally an alkalizer such as calcium metaaluminate, and the alkalizer is expensive.
The existing method for removing ammonia nitrogen mostly uses electricity, oxidant, magnesium salt and phosphate, the remover is expensive, the treatment mode consumes large energy, and the removal rate effect of free ammonia nitrogen in sewage by directly using flocculant is poor. Meanwhile, when water is treated, the flocculating agent has the sterilization requirement, the flocculating agent has the sterilization effect and can meet the actual requirement, but the conventional flocculating agent has a general sterilization effect, and even if the common flocculating agent polyaluminium chloride and polyacrylamide are used, the sterilization effect is only about 46% and 50%. Therefore, there is a need to find a flocculant with high sewage treatment efficiency and bactericidal effect.
Disclosure of Invention
Aiming at the defects of high cost and poor effect of the water treatment agent in the prior art, the invention provides a composite flocculant and a preparation method and application thereof.
In order to realize the purpose, the method specifically comprises the following technical scheme:
a preparation method of a composite flocculant comprises the following steps:
(1) Acid leaching the aluminum ash by using a sulfuric acid solution to obtain an aluminum-containing acid leaching solution;
(2) Adjusting the pH value of the aluminum-containing acid leaching solution in the step (1) to 3-5 by using an alkalizer, and obtaining polymeric aluminum sulfate after polymerization reaction;
(3) Mixing the polyaluminium sulfate prepared in the step (2) with an organic high molecular compound, adding a stabilizer, and curing to obtain a composite flocculant; the organic high molecular compound comprises at least one of sodium alginate, chitosan and sodium lignosulfonate.
The invention can firstly adopt low-concentration sulfuric acid to carry out acid leaching to obtain polymeric aluminum sulfate with high basicity, and then the polymeric aluminum sulfate is compounded with an organic high molecular compound to obtain the composite flocculant. The composite flocculant has high-efficiency wastewater treatment capacity and a sterilization effect.
When the pH value is adjusted to 4-4.5 in the step (2), the basicity of the prepared polyaluminium sulfate can be controlled within 51.0-78.3%, the flocculation effect of the basicity is optimal, when the pH is lower than 3, the aluminium sulfate can not be polymerized, when the pH is higher than 4.5, a large amount of precipitation of aluminium hydroxide is started, the aluminium content is reduced, and when the pH is =5, the loss rate reaches 1.35%.
In a preferred embodiment of the present invention, the mass ratio of the organic polymer compound in the step (3) to polyaluminium sulfate is 1: (50-500).
In a further preferred embodiment of the present invention, the mass ratio of the organic polymer compound to the polyaluminium sulfate in the step (3) is 1: (100-200).
In the step (3), if the content of the organic high molecular compound is too low, the ammonia nitrogen removal effect is not greatly improved, the decolorization rate is not greatly changed, and the sterilization effect is not obvious; too high a content results in too high a loss of aluminum content during the compounding process.
The natural polymer organic matter has the best effect by selecting sodium lignosulfonate, and the mass ratio of the sodium lignosulfonate to the polyaluminium sulfate is 1: the effect is optimal when the 200-time period is reached, and when the mass ratio of the sodium lignosulfonate to the polyaluminium sulfate is 1: at 100, the loss rate of the aluminum content reaches 6.82 percent.
In a preferred embodiment of the present invention, the sulfuric acid solution in the step (1) has a mass concentration of 5 to 30%.
In the step (1), the higher the acid concentration is, the higher the acid leaching rate is. The inventor of the invention finds that when the concentration of the sulfuric acid is 30%, the aluminum is completely leached, and finally the aluminum content in the pickle liquor is 8.47%; above 30%, the aluminium content does not vary much and results in the need for more alkalizing agent for subsequent pH adjustment.
As a preferable embodiment of the present invention, the acid leaching in step (1) is carried out at a temperature of 40 to 90 ℃ for 1 to 5 hours.
In a further preferred embodiment of the present invention, the temperature of the acid leaching in the step (1) is 75 to 80 ℃.
In the step (1), the leaching rate of the aluminum after acid leaching is 59-102.4%. The higher the acid leaching temperature is, the higher the leaching rate is, the aluminum is completely leached at the temperature of 80 ℃, the leaching rate of the aluminum is not changed greatly at the temperature of more than 80 ℃, the temperature is too high, the water is evaporated too much, and water needs to be added in the subsequent process.
In a preferred embodiment of the present invention, the acid leaching time in step (1) is 1 to 5 hours.
As a further preferred embodiment of the present invention, the time for the acid leaching in step (1) is 2 hours.
In the step (1), the longer the acid leaching time is, the higher the acid leaching rate is, the acid leaching time is 2 hours, the aluminum can be completely leached, the leaching rate of the aluminum is not changed greatly, the heating time is too long, the water evaporation is too much, and water needs to be supplemented in the subsequent process.
In a preferred embodiment of the present invention, the mass ratio of the sulfuric acid solution to the aluminum ash in the step (1) is 1: (2-10).
In a preferred embodiment of the present invention, the mass ratio of the sulfuric acid solution to the aluminum ash in the step (1) is 1:8.
the mass ratio of the sulfuric acid solution to the aluminum ash in the step (1) is 1: and 8, the aluminum is completely leached, the liquid volume is increased, the alkalizer is wasted subsequently, the aluminum content of the prepared flocculant is reduced, and the flocculation effect of the prepared flocculant is reduced.
In a preferred embodiment of the present invention, the aluminum ash contains 50% to 55% of aluminum on average.
As a preferred embodiment of the present invention, in step (3), the stabilizer comprises sodium acetate.
In a preferred embodiment of the present invention, the mass concentration of the stabilizer is 1 to 5%.
In a further preferred embodiment of the present invention, the mass concentration of the stabilizer is 2.8%.
As a preferred embodiment of the present invention, the polymerization reaction in the step (2) is carried out at a temperature of 30 to 90 ℃ for 0.25 to 2.5 hours.
As a further preferred embodiment of the present invention, the polymerization reaction in step (2) is carried out at a temperature of 40 ℃ for a period of 0.5 hours.
In the step (2), when the polymerization temperature is 40 ℃, the basicity can reach about 58.40%, and when the polymerization temperature is more than 40 ℃, the loss of aluminum begins, and when the polymerization temperature is 70 ℃, the loss of the aluminum content reaches 4.80%.
In the step (2), the polymerization time is preferably 0.5 hour, and the basicity does not change much after 0.5 hour.
In a preferred embodiment of the invention, the curing time in the step (3) is 12-48 h, and the temperature is 25-60 ℃; the alkalizer in the step (2) comprises at least one of sodium hydroxide, sodium carbonate, calcium hydroxide, calcium oxide and sodium bicarbonate.
As a further preferred embodiment of the present invention, the curing time in the step (3) is 24 hours, and the temperature is 50 ℃; and (3) the alkalizer in the step (2) is sodium carbonate.
In step (2), the most preferred alkalizing agent is sodium carbonate. If the alkalizer is sodium bicarbonate, the adding amount of the alkalizer is 1.5 times of that of sodium carbonate; calcium hydroxide as an alkalizer reduces the aluminum content by 3.37%; sodium hydroxide was used as an alkalizing agent, and the aluminum content was reduced by 14.20%.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts sulfuric acid with low concentration to soak to obtain the polyaluminium sulfate with high basicity, thereby achieving the purpose of reducing the preparation cost of the polyaluminium sulfate.
(2) The composite flocculant prepared by the method has the effects of efficient flocculation, sterilization and ammonia nitrogen removal, can be better applied to treatment of breeding wastewater and printing and dyeing wastewater, and effectively reduces the cost for treating the wastewater.
Drawings
FIG. 1 is a graph showing the bactericidal effect of the blank (left) and example 3 (right) flocculants in effect example 4.
FIG. 2 is a graph of the flocculation effect of example and comparative flocculants, and the effect of comparative example 1, example 5, example 3, and example 4 under flocculant and blank (without flocculant) from left to right.
FIG. 3 is a graph showing the decoloring effect of flocculants of examples and comparative examples, and a graph showing the decoloring effect of a blank group (without flocculant), flocculants prepared in comparative example 1 and example 5 in this order from left to right.
Detailed Description
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further illustrated by specific comparative examples and examples.
Example 1
(1) Weighing 5g of aluminum ash, crushing and sieving the aluminum ash, adding the crushed aluminum ash into a beaker, simultaneously adding 40mL of 30% sulfuric acid solution, carrying out acid leaching at the temperature of 80 ℃ for 2 hours, and filtering to obtain acid leaching solution, wherein the leaching rate of aluminum is 102.4%.
(2) And (2) adding sodium carbonate into the pickle liquor obtained in the step (1), adjusting the pH to 4, and polymerizing for 0.5h at the temperature of 40 ℃ to obtain polyaluminium sulfate. The prepared polyaluminium sulfate has the aluminum content of 8.47 percent and the basicity of 55.65 percent, and the product keeps clear and transparent within 120 days.
(3) Mixing the polyaluminium sulfate prepared in the step (2) with sodium lignosulfonate in a proportion of 100:1, heating for 30min at 50 ℃, adding sodium acetate accounting for 2.8wt% of the mixed solution, curing for 24h to obtain the composite flocculant, keeping the product clear and transparent within 30d, and precipitating after 30 days, wherein the loss rate of the aluminum content reaches 6.82%.
Example 2
(1) Weighing 5g of aluminum ash, crushing and sieving the aluminum ash, adding the crushed aluminum ash into a beaker, simultaneously adding 40mL of 30% sulfuric acid solution, carrying out acid leaching at the temperature of 80 ℃ for 2 hours, and filtering to obtain acid leaching solution, wherein the leaching rate of aluminum is 102.4%.
(2) And (2) adding sodium carbonate into the pickle liquor obtained in the step (1), adjusting the pH to 4, and polymerizing for 0.5h at the temperature of 40 ℃ to obtain polyaluminium sulfate. The prepared polyaluminium sulfate has the aluminum content of 8.47 percent and the basicity of 55.65 percent, and the product keeps clear and transparent within 120 days.
(3) Mixing the polyaluminium sulfate prepared in the step (2) with sodium lignosulfonate in a proportion of 200:1, heating for 30min at 50 ℃, adding sodium acetate (accounting for 2.8wt% of the mixed solution), curing for 24h to obtain the composite flocculant, and keeping the product clear and transparent within 120d without precipitation.
Example 3
(1) Weighing 5g of aluminum ash, crushing and sieving the aluminum ash, adding the crushed aluminum ash into a beaker, simultaneously adding 40mL of 30% sulfuric acid solution, carrying out acid leaching for 2h at the temperature of 75 ℃, and filtering to obtain an acid leaching solution, wherein the aluminum leaching rate is 98.6%.
(2) And (2) adding sodium carbonate into the pickle liquor in the step (1), adjusting the pH to 4.5, and polymerizing for 0.5h at 40 ℃ to obtain polyaluminium sulfate. The polyaluminium sulfate prepared in the embodiment has the aluminum content of 8.0% and the basicity of 75.12%, and the product keeps clear and transparent within 120 days.
(3) Mixing the polyaluminium sulfate prepared in the step (2) with sodium lignosulfonate in a proportion of 200:1, heating for 30min at 50 ℃, adding sodium acetate (accounting for 2.8wt% of the mixed solution), curing for 24h to obtain the composite flocculant, and keeping the product clear and transparent within 120d without precipitation.
Example 4
(1) Weighing 5g of aluminum ash, crushing and sieving the aluminum ash, adding the crushed aluminum ash into a beaker, simultaneously adding 40mL of 30% sulfuric acid solution, carrying out acid leaching for 2h at the temperature of 75 ℃, and filtering to obtain an acid leaching solution, wherein the aluminum leaching rate is 98.6%.
(2) And (2) adding sodium carbonate into the pickle liquor in the step (1), adjusting the pH to 4.5, and polymerizing for 0.5h at 40 ℃ to obtain polyaluminium sulfate. The polyaluminium sulfate prepared in the embodiment has the aluminum content of 8.0% and the basicity of 75.12%, and the product keeps clear and transparent within 120 days.
(3) Mixing the polyaluminium sulfate prepared in the step (2) with sodium alginate in a ratio of 200:1, heating for 30min at 50 ℃, adding sodium acetate (accounting for 2.8wt% of the mixed solution), curing for 24h to obtain the composite flocculant, and keeping the product clear and transparent within 120d without precipitation.
Example 5
(1) Weighing 5g of aluminum ash, crushing and sieving the aluminum ash, adding the crushed aluminum ash into a beaker, simultaneously adding 40mL of 30% sulfuric acid solution, carrying out acid leaching for 2h at the temperature of 75 ℃, and filtering to obtain an acid leaching solution, wherein the aluminum leaching rate is 98.6%.
(2) And (2) adding sodium carbonate into the pickle liquor obtained in the step (1), adjusting the pH to 4.5, and polymerizing for 0.5h at the temperature of 40 ℃ to obtain polyaluminium sulfate. The polyaluminium sulfate prepared by the embodiment has the aluminum content of 8.0 percent and the basicity of 75.12 percent, and the product keeps clear and transparent within 180 days.
(3) Mixing polyaluminium sulfate prepared in the step (2) with chitosan in a ratio of 200:1, heating for 30min at 50 ℃, adding sodium acetate (accounting for 2.8wt% of the mixed solution), curing for 24h to obtain the composite flocculant, and keeping the product clear and transparent within 120d without precipitation.
Comparative example 1
(1) Weighing 5g of aluminum ash, crushing and sieving the aluminum ash, adding the crushed aluminum ash into a beaker, simultaneously adding 40mL of 30% sulfuric acid solution, carrying out acid leaching for 2h at the temperature of 75 ℃, and filtering to obtain an acid leaching solution, wherein the aluminum leaching rate is 98.6%.
(2) And (2) adding sodium carbonate into the pickle liquor obtained in the step (1), adjusting the pH to 4.5, and polymerizing for 0.5h at the temperature of 40 ℃ to obtain polyaluminium sulfate.
(3) Mixing the polyaluminium sulfate prepared in the step (2) with water in a ratio of 200:1, heating for 30min at 50 ℃, adding sodium acetate (accounting for 2.8wt% of the mixed solution), and curing for 24h to obtain the polyaluminium sulfate flocculant.
Comparative example 2
Mixing water and sodium lignin sulfonate in a ratio of 200:1, heating for 30min at 50 ℃, adding sodium acetate (accounting for 2.8wt% of the mixed solution), and curing for 24h to obtain the sodium lignosulfonate flocculant.
Comparative example 3
Mixing water and chitosan in a ratio of 200:1, heating for 30min at 50 ℃, adding sodium acetate (accounting for 2.8wt% of the mixed solution), and curing for 24h to obtain the chitosan flocculant.
Comparative example 4
Mixing water and sodium alginate in a ratio of 200:1, heating for 30min at 50 ℃, adding sodium acetate (accounting for 2.8wt% of the mixed solution), and curing for 24h to obtain the sodium alginate flocculant.
The aluminum content detection methods of the examples and the comparative examples are as follows:
transferring 10mL of the pickle liquor into a 100mL volumetric flask, shaking to a constant volume, transferring 10.00mL of the test liquor into a 250mL conical flask, and adding the test liquor with the concentration of about 0.05 mol.L -1 And (2) adjusting the pH of the pickle liquor to be about 3.5 by using dilute ammonia water (1:1) and dilute sulfuric acid (30%) (dropping a drop of ammonia water to generate a white precipitate, shaking for one second without dissolving immediately), boiling the solution for about 3min, standing, cooling to room temperature, dropping 4-6 drops of pan indicator, adding 5mL of absolute ethyl alcohol, adding 10mL of acetic acid-sodium acetate buffer solution with the pH of 5, wherein the solution is light yellow, immediately titrating by using a copper sulfate standard solution until the solution becomes bluish purple, and does not change color within half a minute without counting. Then the solution was transferred to a plastic Erlenmeyer flask and NH was added at a concentration of 200g/L 4 And (3) 10mL of the solution F, heating the solution to slightly boil, standing, cooling to room temperature, adding 4-6 drops of pan indicator, adding 5mL of absolute ethyl alcohol, titrating to blue-purple with a copper sulfate standard solution, keeping the solution unchanged within half a minute, namely the titration end point, and recording data. The amount of aluminum recovered can be calculated according to the volume of the copper sulfate solution consumed.
c(Cu 2+ ): concentration of copper sulfate standard solutionDegree;
V(Cu 2+ ): consuming the volume of the copper sulfate standard solution;
26.98: relative atomic mass of aluminum.
Procedure for determination of salt basicity of examples and comparative examples:
transferring 20mL of polyaluminum sulfate solution into a 100mL volumetric flask, shaking to a constant volume, transferring 15.00mL of the solution from the volumetric flask into a 250mL conical flask, and adding the solution with the concentration of about 0.5000 mol.L -1 Sealing a preservative film, shaking uniformly, standing for 20min, transferring the solution into a polyethylene conical flask, adding 10mL of saturated sodium fluoride solution, shaking uniformly, standing for 5min, adding 3 drops of phenolphthalein indicator, and titrating with a sodium hydroxide standard solution until the solution becomes reddish and does not fade within half a minute. Namely, the titration end point, and data are recorded. The basicity can be calculated according to the volume of the consumed sodium hydroxide standard solution and the content of alumina.
The basicity calculation formula is as follows:
c(Cu 2+ ): the concentration of a copper sulfate standard solution used when the content of alumina is measured by samples of the same batch;
V(Cu 2+ ): when the content of alumina is measured by samples of the same batch, the volume of a copper sulfate standard solution is consumed;
c(H + ): the concentration of the hydrochloric acid standard solution;
V(H + ): volume of hydrochloric acid standard solution consumed.
Note: saturated NaF solution: weighing 200g of NaF powder in a plastic cup, adding 500mL of deionized water which is boiled for 3min and then cooled, shaking up fully, filtering, filling the filtrate in a 1000mL plastic bottle, dripping 3 drops of phenolphthalein indicator, and titrating with a sodium hydroxide standard solution until the solution becomes reddish and does not fade within half a minute.
Effect example 1
Under the condition of normal temperature, 0.2-1mL of the composite flocculant solution prepared in example 2 is added into 30mL of Congo red solution (0.1 g/L), stirred for 2min, kept stand for 40min, and the absorbance at 498nm is measured to calculate the decolorization rate, and the results are shown in Table 1.
TABLE 1 decolorization effect of composite flocculant in example
As can be seen from the above table 1, the composite flocculant prepared by the method of the invention has good decolorizing effect, and the decolorizing rate can reach 96.06%.
Effect example 2
Under the condition of normal temperature, 0.5mL of flocculant solutions of examples and comparative examples 1-4 are added into 30mL of Congo red solution (0.1 g/L), stirred for 2min, kept stand for 40min, and the absorbance of the solution is measured at the wavelength of 498nm, and the decolorization rate is calculated, and the results are shown in Table 2.
TABLE 2 decolorization effect of flocculants of examples and comparative examples
As can be seen from the above table 2, the composite flocculant prepared by the method of the present invention and polyaluminium sulfate both have good decolorizing effect, and the decolorizing speed of the compounded flocculant is obviously higher than that of a flocculant with a single component.
Effect example 3
Adding the composite flocculant (chitosan-polyaluminium sulfate) solution obtained in example 5 into 100mL of culture wastewater, stirring for 2min, standing for 40min, respectively taking the supernatant and the precipitate, adding LB culture medium and Mackanka culture medium, coating, culturing at 37 ℃ for two days, and observing the number of escherichia coli.
Table 3 example 5 composite flocculant germicidal effect
Effect example 4
Adding different flocculant solutions into 100mL of culture wastewater, stirring for 2min, standing for 40min, respectively taking supernatant and precipitate, adding LB culture medium and MacConkey culture medium for coating, and culturing at 37 ℃ for 24h to observe the number of escherichia coli.
TABLE 4 bactericidal Effect of flocculants of examples and comparative examples
As can be seen from tables 3 and 4 and in combination with FIG. 1, the composite flocculant of the present invention has an obvious bactericidal effect up to 96.19%.
Effect example 5
Adding different flocculant solutions into 100mL of culture wastewater, stirring for 2min, standing for 60min, and respectively taking supernate to detect the ammonia nitrogen content by using a Nashin reagent method.
TABLE 5 Ammonia nitrogen removal Effect of flocculants of examples and comparative examples
| Kind of flocculating agent | Comparative example 1 | Example 3 | Example 4 | Example 5 |
| Ammonia nitrogen removal rate | 43.34％ | 56.87％ | 51.52％ | 54.36％ |
| Kind of flocculating agent | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Ammonia nitrogen removal rate | 2.89％ | 3.02％ | 1.85％ |
As can be seen from Table 5, the composite flocculant of the invention has an obvious effect of removing ammonia nitrogen in sewage, and the removal rate can reach 54.36%.
Effect example 6
And adding 500 mu L of the flocculant prepared in the examples and the comparative examples into 100mL of aquaculture wastewater, stirring for 2min, standing for 30min, and observing the flocculation effect. The results are shown in fig. 2, wherein the flocculation effect of the comparative example 1, example 5, example 3, example 4 flocculant and the blank (without flocculant) are shown from left to right. Therefore, the composite flocculant prepared by the invention has obvious flocculation effect on wastewater and can be used as an efficient water treatment agent.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the composite flocculant is characterized by comprising the following steps of:
(1) Acid leaching the aluminum ash by using a sulfuric acid solution to obtain an aluminum-containing acid leaching solution;
(2) Adjusting the pH value of the aluminum-containing acid leaching solution in the step (1) to 3-5 by using an alkalizer, and obtaining polymeric aluminum sulfate after polymerization reaction;
(3) Mixing the polyaluminium sulfate obtained in the step (2) with an organic high molecular compound, adding a stabilizer, and curing to obtain a composite flocculant; the organic high molecular compound comprises at least one of sodium alginate, chitosan and sodium lignosulfonate.
2. The method according to claim 1, wherein the mass ratio of the organic polymer compound to the polyaluminium sulfate in the step (3) is 1: (50-500).
3. The production method according to claim 1, wherein the mass ratio of the organic high molecular compound to polyaluminum sulfate in the step (3) is 1: (100-200).
4. The method according to claim 3, wherein the sulfuric acid solution in the step (1) has a mass concentration of 5 to 30%.
5. The method according to any one of claims 1 to 4, wherein the stabilizer in the step (3) comprises sodium acetate; the temperature of acid leaching in the step (1) is 40-90 ℃, and the time is 1-5 h.
6. The process according to any one of claims 1 to 4, wherein the polymerization in the step (2) is carried out at a temperature of from 30 ℃ to 90 ℃ for a time of from 0.25 hours to 2.5 hours.
7. The process according to any one of claims 1 to 4, wherein the mixing in step (3) is carried out at a temperature of 20 to 60 ℃ for a time of 0.25 to 2 hours.
8. The method according to any one of claims 1 to 4, wherein the alkalizing agent in the step (2) comprises at least one of sodium hydroxide, sodium carbonate, calcium hydroxide, calcium oxide, sodium bicarbonate; the curing time in the step (3) is 12-48 h, and the temperature is 25-60 ℃.
9. The composite flocculant prepared by the preparation method of any one of claims 1 to 8.
10. Use of the composite flocculant of claim 9 in wastewater treatment.
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