CN115818810A - Composite polyaluminium chloride water treatment agent and preparation method thereof - Google Patents
Composite polyaluminium chloride water treatment agent and preparation method thereof Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 73
- 229920001661 Chitosan Polymers 0.000 claims abstract description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 10
- -1 allyl quaternary ammonium salt compound Chemical class 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 230000001588 bifunctional effect Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- RBEFRYQKJYMLCC-UHFFFAOYSA-N 4-isothiocyanatobenzoic acid Chemical compound OC(=O)C1=CC=C(N=C=S)C=C1 RBEFRYQKJYMLCC-UHFFFAOYSA-N 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 150000004676 glycans Chemical class 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 229960003151 mercaptamine Drugs 0.000 claims description 6
- 229920001282 polysaccharide Polymers 0.000 claims description 6
- 239000005017 polysaccharide Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- 239000000413 hydrolysate Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 108010009736 Protein Hydrolysates Proteins 0.000 abstract description 8
- 238000007789 sealing Methods 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002390 rotary evaporation Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000000502 dialysis Methods 0.000 description 6
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- 239000004912 1,5-cyclooctadiene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 239000002994 raw material Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a composite polyaluminium chloride water treatment agent and a preparation method thereof, belonging to the technical field of water treatment agent preparation, and the preparation steps are as follows: placing a polyaluminium chloride solution into a reaction kettle, adding KH-570 coupling agent hydrolysate, uniformly stirring, adjusting the pH to 10 by using 0.1mol/L sodium hydroxide solution, stirring for reaction for 4-6h, then adding modified octavinyl-POSS, modified chitosan and a compound emulsifier, stirring, slowly dropwise adding ammonium persulfate under the protection of nitrogen, sealing the reaction kettle, and stirring for reaction for 3-4h at the temperature of 60-65 ℃ to obtain the compound polyaluminium chloride water treatment agent.
Description
Technical Field
The invention belongs to the technical field of preparation of water treatment agents, and particularly relates to a compound polyaluminium chloride water treatment agent and a preparation method thereof.
Background
Polyaluminum chloride water treatment agent, i.e. polyaluminum chloride water purifying agent, abbreviated as PAC, having molecular formula of [ Al 2 (OH ) n Cl 6-n ] m The flocculant is a cationic inorganic polymeric flocculant of polyhydroxy and multi-core complex, is also commonly called basic aluminum chloride or coagulant, and the appearance of a solid product is light yellow.
At present, polyaluminium chloride is widely used in water treatment and sludge dewatering treatment, compared with the traditional aluminium salt flocculant, the polyaluminium chloride has the advantages of wide water quality application range, low price, good treatment effect on low-temperature and low-turbidity water, easy sedimentation, sludge dewatering and the like, but the form, the degree of polymerization and the corresponding coagulation flocculation effect of the polyaluminium chloride are still not as good as those of an organic polymer flocculant, the adsorption and bridging capacity of the polyaluminium chloride on the molecular weight and colloidal substances is much lower than that of the organic polymer flocculant, the removal efficiency of heavy metal ions is poor due to the lack of chelate groups coordinated with the heavy metal ions, and the single polyaluminium chloride often increases the solubility of aluminium ions in water in the water treatment process, and the high concentration of the aluminium ions in the water can cause human health problems such as senile dementia and the like.
In order to solve the problems, a composite polyaluminium chloride water treatment agent is commonly adopted to improve the purification performance of the polyaluminium chloride at present, for example, chinese patent CN109231387B discloses a straw/polyaluminium chloride composite water treatment material and a preparation method thereof. The material has higher specific surface area and good adsorption flocculation capacity, but the straw and the polyaluminium chloride are only combined through the action of hydrogen bonds, the interaction between the straw and the polyaluminium chloride is weak, so that the composite material has poor anti-shearing capacity in the water treatment process, flocculation is easy to break, small floc can enter filtered water through a filter layer, and the treatment effect is poor, therefore, the composite polyaluminium chloride water treatment agent with higher performance needs to be improved.
Disclosure of Invention
The invention aims to provide a composite polyaluminium chloride water treatment agent and a preparation method thereof, which aim to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the compound polyaluminium chloride water treatment agent comprises the following steps:
putting a polyaluminum chloride solution into a reaction kettle, adding KH-570 coupling agent hydrolysate, uniformly stirring, adjusting the pH value to 10 by using 0.1mol/L sodium hydroxide solution, stirring for reaction for 4-6h, then adding modified octavinyl-POSS, modified chitosan and a compound emulsifier, stirring for 20-30min, slowly dropwise adding ammonium persulfate under the protection of nitrogen, sealing the reaction kettle, stirring for reaction for 3-4h at 60-65 ℃, after the reaction is finished, precipitating a product by using ethanol, washing by using acetone, and drying at 50 ℃ to constant weight to obtain the composite polyaluminum chloride water treatment agent.
Further, the KH-570 coupling agent hydrolysate is obtained by the following steps:
adjusting pH of KH-570 with 5wt% hydrochloric acid solution to 3-4, and hydrolyzing for 12h to obtain KH-570 coupling agent hydrolysate.
Further, the mass fraction of the polyaluminium chloride solution is 10-20%, the dosage of KH-570 is 8-10% of the mass of the polyaluminium chloride, and the mass ratio of the polyaluminium chloride, the octavinyl-POSS and the modified chitosan is 100:20-23:3-10 percent of the weight sum of the octavinyl-POSS and the modified chitosan, and 0.6-0.7 percent of the weight sum of the octavinyl-POSS and the modified chitosan.
Further, the modified octavinyl-POSS is prepared by the following steps:
s11, mixing octavinyl-POSS, mercaptoethylamine, benzoin dimethyl ether and DMF, irradiating the mixture for 1 to 2 hours by using ultraviolet light with the wavelength of 365nm, and removing the DMF by rotary evaporation to obtain bifunctional POSS, wherein the dosage ratio of the octavinyl-POSS, the mercaptoethylamine, the benzoin dimethyl ether to the DMF is 3mmol:12mmol:20mg:40-50mL;
s12, mixing bifunctional POSS and dimethyl sulfoxide, dropwise adding dibutyltin dilaurate after stirring and dissolving, then adding 4-carboxyphenyl isothiocyanate, stirring for 5-10min, stirring at 50 ℃ for reacting for 4h, cooling to room temperature for reacting for 48h, after the reaction is finished, carrying out reduced pressure distillation to remove the dimethyl sulfoxide, and obtaining modified octavinyl-POSS, wherein the dosage ratio of the bifunctional POSS, the dimethyl sulfoxide, the dibutyltin dilaurate to the 4-carboxyphenyl isothiocyanate is 10.5-11.3g:80-100mL:0.3g:7.3-8.5g.
The method comprises the steps of taking octavinyl-POSS and mercaptoethylamine as raw materials, controlling the dosage ratio of the raw materials, obtaining bifunctional POSS containing active amino and unsaturated double bonds through mercapto-alkene click reaction, and then reacting the active amino with isothiocyanate of 4-carboxyphenyl isothiocyanate to obtain POSS containing a thiourea structure, carboxyl, a benzene ring and unsaturated double bonds, namely modified octavinyl-POSS.
Further, the preparation steps of the modified chitosan are as follows:
step S21, adding allyl chloride, triethanolamine and deionized water into a flask, sealing the opening of the flask by using a rubber plug and an adhesive tape, heating to 40 ℃, magnetically stirring for reaction for 24 hours, and performing rotary evaporation to remove ionized water and unreacted allyl chloride completely to obtain a trihydroxy allyl quaternary ammonium salt compound;
s22, dispersing chitosan and phthalic anhydride in DMF, heating to 120 ℃ under the protection of nitrogen, stirring for reaction for 8 hours, cooling to room temperature, pouring a reaction product into ice water, stirring for 20-30min, filtering, washing a filter cake for 3-5 times by using methanol, and freeze-drying to obtain amino-protected chitosan;
s23, placing pyridine into a flask, adding amino protective polysaccharide at 0 ℃, stirring for dissolving, slowly adding thionyl chloride, stirring for reacting for 0.5h at 80 ℃ under the protection of nitrogen, cooling to room temperature, pouring into ice water, stirring, filtering, and drying a filter cake in vacuum to obtain an intermediate product; placing tetrahydrofuran in a flask, adding a trihydroxy allyl quaternary ammonium salt compound at 0 ℃, uniformly stirring, adding NaH, stirring at 60 ℃ for 1h under the protection of nitrogen, cooling to 0 ℃, adding an intermediate product, stirring for 0.5h, stirring at 60 ℃ for 12h, pouring a reaction product into methanol after the reaction is finished, filtering, and freeze-drying a filter cake to obtain quaternary ammonium salt etherified chitosan;
and S24, dissolving quaternary ammonium salt etherified chitosan in N-methyl-2-pyrrolidone, adding a hydrazine hydrate solution with the concentration of 4mol/L, reacting for 4-6h at 100 ℃ under the protection of argon, performing rotary evaporation to remove water in the reaction solution after the reaction is finished, putting a rotary evaporation product in absolute ethyl alcohol for precipitation and centrifugation, washing the obtained solid with the absolute ethyl alcohol, putting the washed solid in a dialysis bag for dialysis for 2d, and performing freeze drying to obtain the modified chitosan.
Firstly, taking allyl chloride and triethanolamine as raw materials, obtaining a trihydroxy allyl quaternary ammonium salt compound through quaternization, then protecting active amino on a chitosan molecular chain by using phthalic anhydride, then generating hydroxyl of the chitosan molecular chain by using thionyl chloride to obtain chlorinated chitosan (an intermediate product), further generating HCl elimination reaction by using the chlorinated chitosan and the trihydroxy allyl quaternary ammonium salt compound, grafting the trihydroxy allyl quaternary ammonium salt compound on the chitosan molecular chain through ether bonds, and finally removing amino protection groups from quaternary ammonium salt etherified chitosan in a hydrazine hydrate solution to obtain modified chitosan containing the active amino, quaternary ammonium salt structures and unsaturated double bonds.
Further, in the step S21, the ratio of the allyl chloride, the triethanolamine and the deionized water is 0.1mol:0.11mol:150-200mL.
Further, the amount ratio of chitosan, phthalic anhydride and DMF in step S22 is 4.5-4.8g:13.32g:200mL.
Further, in step S23, the dosage ratio of pyridine, amino-protective polysaccharide, thionyl chloride, tetrahydrofuran, trihydroxyallyl quaternary ammonium salt compound and NaH is 100mL:2g:0.5mL:50-60mL:2.3-2.5g:1g of the total weight of the composition.
Further, in the step S24, the dosage ratio of the quaternary ammonium salt etherified chitosan, the N-methyl-2-pyrrolidone and the hydrazine hydrate solution is 2.5-3.0g:100mL of: 100mL.
Further, the compound emulsifier is an anionic emulsifier and a nonionic emulsifier according to a mass ratio of 0.5-3:1, wherein the anionic emulsifier is selected from one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium fatty alcohol ether sulfate and secondary alkyl sodium sulfonate; the nonionic emulsifier is selected from one of tween 80, span 80, alkylphenol polyoxyethylene and fatty alcohol polyoxyethylene.
The composite polyaluminium chloride water treatment agent is prepared by the preparation method.
The invention has the beneficial effects that:
the invention provides a composite polyaluminium chloride water treatment agent, which is prepared by using polyaluminium chloride as a base material and using a KH-570 coupling agent to carry out pretreatment on the polyaluminium chloride, further using unsaturated double bonds of the KH-570 coupling agent and unsaturated double bonds of modified octavinyl-POSS and modified chitosan to carry out polymerization reaction, wherein KH-570 forms a molecular bridge between inorganic hydroxyl polyaluminium chloride and organic macromolecules, so that the polyaluminium chloride, the modified octavinyl-POSS and the modified chitosan are connected through chemical bonds, the obtained composite polyaluminium chloride has more stable performance and larger surface area, and a space network structure exists in the composite polyaluminium chloride water treatment agent, and has better flocculation small particles and bridging adsorption performance than a branched structure, so that the composite polyaluminium chloride water treatment agent has strong adsorption capacity and stable formed floccules.
According to the invention, the modified octavinyl-POSS is introduced into the composite polyaluminium chloride, not only is the modified octavinyl-POSS acted together with the modified chitosan to form a space network structure on the surface of the polyaluminium chloride, but also the porous cage-type siloxane structure is introduced, so that the interaction with inorganic heavy metal ions and organic pollutants in water is facilitated, and the thiourea structure, the benzene ring and the active carboxyl group in the modified octavinyl-POSS molecule are combined, so that the interaction with the inorganic heavy metal ions and the organic pollutants can be realized through coordination and pi-pi adsorption, and the adsorption removal effect is improved.
According to the invention, the modified chitosan is introduced into the composite polyaluminium chloride, so that organic pollutants, metal ions and protein molecules are adsorbed by utilizing rich amino and hydroxyl in chitosan molecules through adsorption and coordination, and the harm of overhigh solubility of aluminum ions in water body caused by aluminum ions released by the polyaluminium chloride can be overcome through coordination between active amino and the aluminum ions.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a modified octavinyl-POSS prepared as follows:
s11, mixing 3mmol of octavinyl-POSS, 12mmol of mercaptoethylamine, 20mg of benzoin dimethyl ether and 40mL of DMF, irradiating for 1h by using ultraviolet light with the wavelength of 365nm, and performing rotary evaporation to remove the DMF to obtain bifunctional POSS;
and S12, mixing 10.5g of bifunctional POSS with 80mL of dimethyl sulfoxide, stirring to dissolve, dropwise adding 0.3g of dibutyltin dilaurate, then adding 7.3g of 4-carboxyphenyl isothiocyanate, stirring for 5min, stirring at 50 ℃ for reacting for 4h, cooling to room temperature for reacting for 48h, and after the reaction is finished, carrying out reduced pressure distillation to remove the dimethyl sulfoxide to obtain the modified octavinyl-POSS.
Example 2
This example provides a modified octavinyl-POSS prepared as follows:
s11, mixing 3mmol of octavinyl-POSS, 12mmol of mercaptoethylamine, 20mg of benzoin dimethyl ether and 50mL of DMF, irradiating for 2 hours by using ultraviolet light with the wavelength of 365nm, and removing the DMF by rotary evaporation to obtain bifunctional POSS;
and S12, mixing 11.3g of bifunctional POSS with 100mL of dimethyl sulfoxide, stirring and dissolving, then dropwise adding 0.3g of dibutyltin dilaurate, then adding 8.5g of 4-carboxyphenyl isothiocyanate, stirring for 10min, stirring at 50 ℃ for reacting for 4h, cooling to room temperature for reacting for 48h, and after the reaction is finished, carrying out reduced pressure distillation to remove the dimethyl sulfoxide to obtain the modified octavinyl-POSS.
Comparative example 1
This comparative example is an octavinyl-POSS.
Example 3
The modified chitosan is prepared by the following steps:
step S21, adding 0.1mol of allyl chloride, 0.11mol of triethanolamine and 150mL of deionized water into a flask, sealing the opening of the flask by using a rubber plug and an adhesive tape, heating to 40 ℃, magnetically stirring for reaction for 24 hours, and performing rotary evaporation to remove the ionized water and unreacted allyl chloride completely to obtain a trihydroxy allyl quaternary ammonium salt compound;
s22, dispersing 4.5g of chitosan and 13.32g of phthalic anhydride in 200mL of DMF, heating to 120 ℃ under the protection of nitrogen, stirring for reaction for 8 hours, cooling to room temperature, pouring the reaction product into ice water, stirring for 20 hours, filtering, washing a filter cake for 3 times by using methanol, and freeze-drying to obtain amino-protected polysaccharide;
step S23, placing 100mL of pyridine into a flask, adding 2g of amino protective polysaccharide at 0 ℃, stirring for dissolving, slowly adding 0.5mL of thionyl chloride, stirring for reacting for 0.5h at 80 ℃ under the protection of nitrogen, cooling to room temperature, pouring into ice water, stirring, filtering, and drying a filter cake in vacuum to obtain an intermediate product; putting 50mL of tetrahydrofuran into a flask, adding 2.3g of trihydroxy allyl quaternary ammonium salt compound at 0 ℃, uniformly stirring, adding 1g of NaH, stirring at 60 ℃ for 1h under the protection of nitrogen, cooling to 0 ℃, adding an intermediate product, stirring for 0.5h, stirring at 60 ℃ for 12h, pouring a reaction product into methanol after the reaction is finished, filtering, and freeze-drying a filter cake to obtain quaternary ammonium salt etherified chitosan;
and S24, dissolving 2.5g of quaternary ammonium salt etherified chitosan in 100mL of N-methyl-2-pyrrolidone, then adding 100mL of hydrazine hydrate solution with the concentration of 4mol/L, reacting for 4 hours at 100 ℃ under the protection of argon, removing water in the reaction solution by rotary evaporation after the reaction is finished, putting a rotary evaporation product in absolute ethyl alcohol for precipitation and centrifugation, washing the obtained solid with absolute ethyl alcohol, putting the solid in a dialysis bag for dialysis for 2d, and freeze-drying to obtain the modified chitosan.
Example 4
The modified chitosan is prepared by the following steps:
step S21, adding 0.1mol of allyl chloride, 0.11mol of triethanolamine and 200mL of deionized water into a flask, sealing the opening of the flask by using a rubber plug and an adhesive tape, heating to 40 ℃, magnetically stirring for reaction for 24 hours, and performing rotary evaporation to remove the ionized water and unreacted allyl chloride completely to obtain a trihydroxy allyl quaternary ammonium salt compound;
step S22, dispersing 4.8g of chitosan and 13.32g of phthalic anhydride in 200mL of DMF, heating to 120 ℃ under the protection of nitrogen, stirring for reaction for 8 hours, cooling to room temperature, pouring the reaction product into ice water, stirring for 30 minutes, filtering, washing a filter cake for 5 times by using methanol, and freeze-drying to obtain amino-protected chitosan;
step S23, placing 100mL of pyridine into a flask, adding 2g of amino protective polysaccharide at 0 ℃, stirring for dissolving, slowly adding 0.5mL of thionyl chloride, stirring for reacting for 0.5h at 80 ℃ under the protection of nitrogen, cooling to room temperature, pouring into ice water, stirring, filtering, and drying a filter cake in vacuum to obtain an intermediate product; placing 60mL of tetrahydrofuran in a flask, adding 2.5g of trihydroxy allyl quaternary ammonium salt compound at 0 ℃, uniformly stirring, adding 1g of NaH, stirring at 60 ℃ for 1h under the protection of nitrogen, cooling to 0 ℃, adding an intermediate product, stirring for 0.5h, stirring at 60 ℃ for 12h, pouring a reaction product into methanol after the reaction is finished, filtering, and freeze-drying a filter cake to obtain quaternary ammonium salt etherified chitosan;
and S24, dissolving 3.0g of quaternary ammonium salt etherified chitosan in 100mL of N-methyl-2-pyrrolidone, then adding 100mL of hydrazine hydrate solution with the concentration of 4mol/L, reacting for 6h at 100 ℃ under the protection of argon, removing water in the reaction solution by rotary evaporation after the reaction is finished, putting a rotary evaporation product in absolute ethyl alcohol for precipitation and centrifugation, washing the obtained solid with absolute ethyl alcohol, putting the washed solid in a dialysis bag for dialysis for 2d, and freeze-drying to obtain the modified chitosan.
Comparative example 2
This comparative example is a trihydroxyallyl quaternary ammonium salt compound prepared in step S21 of example 3.
Example 5
A preparation method of a compound polyaluminium chloride water treatment agent comprises the following steps:
adjusting the pH value of a silane coupling agent KH-570 to 3 by using a 5wt% hydrochloric acid solution, hydrolyzing for 12h to obtain a KH-570 coupling agent hydrolysate, placing a 10 wt% polyaluminum chloride solution into a reaction kettle, adding the KH-570 coupling agent hydrolysate, uniformly stirring, adjusting the pH value to 10 by using a 0.1mol/L sodium hydroxide solution, stirring for reacting for 4h, then adding the modified octavinyl-POSS of example 1, the modified chitosan of example 3 and a compound emulsifier, stirring for 20min, slowly dropwise adding ammonium persulfate under the protection of nitrogen, sealing the reaction kettle, stirring for reacting for 3h at 60 ℃, after the reaction is finished, precipitating a product by using ethanol, washing by using acetone, and drying at 50 ℃ to constant weight to obtain the composite polyaluminum chloride water treatment agent.
Wherein the dosage of KH-570 is 8% of the mass of the polyaluminium chloride, and the mass ratio of the polyaluminium chloride, the octavinyl-POSS and the modified chitosan is 100:20:3, the dosage of the compound emulsifier is 1 percent of the mass sum of the octavinyl-POSS and the modified chitosan, and the dosage of the ammonium persulfate is 0.6 percent of the mass sum of the octavinyl-POSS and the modified chitosan
Wherein the compound emulsifier is sodium dodecyl sulfate and tween 80 according to a mass ratio of 0.5: 1.
Example 6
A preparation method of a compound polyaluminium chloride water treatment agent comprises the following steps:
adjusting the pH value of a silane coupling agent KH-570 to 4 by using a 5wt% hydrochloric acid solution, hydrolyzing for 12h to obtain a KH-570 coupling agent hydrolysate, placing a 15 wt% polyaluminum chloride solution into a reaction kettle, adding the KH-570 coupling agent hydrolysate, uniformly stirring, adjusting the pH value to 10 by using a 0.1mol/L sodium hydroxide solution, stirring for reacting for 5h, then adding the modified octavinyl-POSS of example 1, the modified chitosan of example 4 and a compound emulsifier, stirring for 20min, slowly dropwise adding ammonium persulfate under the protection of nitrogen, sealing the reaction kettle, stirring for reacting for 3.5h at 64 ℃, after the reaction is finished, precipitating a product by using ethanol, washing by using acetone, and drying at 50 ℃ to constant weight to obtain the composite polyaluminum chloride water treatment agent.
Wherein the dosage of KH-570 is 9% of the mass of the polyaluminium chloride, and the mass ratio of the polyaluminium chloride, the octavinyl-POSS and the modified chitosan is 100:22:6, the dosage of the compound emulsifier is 1 percent of the mass sum of the octavinyl-POSS and the modified chitosan, and the dosage of the ammonium persulfate is 0.6 percent of the mass sum of the octavinyl-POSS and the modified chitosan.
Wherein the compound emulsifier is sodium dodecyl benzene sulfonate and span 80 according to a mass ratio of 1: 1.
Example 7
A preparation method of a compound polyaluminium chloride water treatment agent comprises the following steps:
adjusting the pH value of a silane coupling agent KH-570 to 4 by using a 5wt% hydrochloric acid solution, hydrolyzing for 12h to obtain a KH-570 coupling agent hydrolysate, placing a polyaluminum chloride solution with the mass fraction of 20% into a reaction kettle, adding the KH-570 coupling agent hydrolysate, uniformly stirring, adjusting the pH value to 10 by using a 0.1mol/L sodium hydroxide solution, stirring for reacting for 6h, then adding the modified octavinyl-POSS of example 2, the modified chitosan of example 4 and a compound emulsifier, stirring for 30min, slowly dropwise adding ammonium persulfate under the protection of nitrogen, sealing the reaction kettle, stirring for reacting for 4h at 65 ℃, after the reaction is finished, precipitating a product by using ethanol, washing by using acetone, and drying at 50 ℃ to constant weight to obtain the composite polyaluminum chloride water treatment agent.
Wherein the dosage of KH-570 is 10% of the mass of the polyaluminium chloride, and the mass ratio of the polyaluminium chloride to the octavinyl-POSS to the modified chitosan is 100:23:10, the dosage of the compound emulsifier is 1 percent of the mass sum of the octavinyl-POSS and the modified chitosan, and the dosage of the ammonium persulfate is 0.7 percent of the mass sum of the octavinyl-POSS and the modified chitosan.
The compound emulsifier is sodium dodecyl benzene sulfonate and fatty alcohol-polyoxyethylene ether according to a mass ratio of 3: 1.
Comparative example 3
In comparison with example 5, the modified octavinyl-POSS from example 5 was replaced with the material from comparative example 1, and the remaining raw materials and preparation were the same as in example 5.
Comparative example 4
Compared with example 5, the modified chitosan in example 5 is compared with the substance in example 2, and the rest raw materials and the preparation process are the same as example 5.
The composite type polyaluminum chlorides prepared in examples 5 to 7 and comparative examples 3 to 4 were subjected to performance tests, the test items being as follows:
collecting the production wastewater of a certain company, wherein the content of each substance in the wastewater is as follows: methylene blue 55.8mg/L, cu 2+ 50.3mg/mL，COD 312.9mg/mL；
(I) aluminum ion dissolution performance test:
adding the composite type polyaluminum chloride of the embodiment and the comparative example into the collected wastewater in a 500mL conical flask (the addition amount is 0.5 g/L), oscillating for 5min, standing for 30min, and taking the supernatant to measure the residual amount of aluminum ions;
(II) purification capacity:
the composite polyaluminium chloride of the examples and the comparative examples was added to the collected wastewater (the amount of the added material was 0.5 g/L) in a 500mL conical flask, shaken for 5min, allowed to stand for 30min, and the supernatant was taken to measure the methylene blue content, COD content, cu content in the treated liquid 2+ Content, and calculating methylene blue removal rate, COD removal rate and Cu removal rate 2+ The removal rate;
the test results are shown in table 1:
TABLE 1
| Item | Example 5 | Example 6 | Example 7 | Comparative example 3 | Comparative example 4 |
| Residual quantity of aluminum ion (mg/L) | 1.2 | 1.1 | 0.9 | 1.7 | 2.4 |
| Methylene blue removal (%) | 96.4 | 96.9 | 97.8 | 95.9 | 94.2 |
| COD removal Rate (%) | 88.1 | 88.7 | 89.2 | 87.1 | 84.2 |
| Cu 2+ Removal Rate (%) | 95.3 | 95.9 | 96.5 | 91.4 | 88.3 |
As can be seen from Table 1, the composite type polyaluminum chlorides prepared in examples 5 to 7 have low aluminum ion residue, high removal rates of pollution dyes, COD and metal ions and very high purification effects after treating wastewater compared with comparative examples 3 to 4.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The preparation method of the compound polyaluminium chloride water treatment agent is characterized by comprising the following steps:
firstly, mixing bifunctional POSS and dimethyl sulfoxide, stirring and dissolving, then dropwise adding dibutyltin dilaurate, then adding 4-carboxyphenyl isothiocyanate, stirring, reacting for 4 hours at 50 ℃, cooling to room temperature, and reacting for 48 hours to obtain modified octavinyl-POSS;
and secondly, adding the KH-570 coupling agent hydrolysate into the polyaluminium chloride solution, stirring uniformly, adjusting the pH to 10 by using 0.1mol/L sodium hydroxide solution, stirring for reacting for 4-6h, then adding the modified octavinyl-POSS, the modified chitosan and the compound emulsifier, stirring, dropwise adding ammonium persulfate under the protection of nitrogen, and stirring for reacting for 3-4h at the temperature of 60-65 ℃ to obtain the compound polyaluminium chloride water treatment agent.
2. The method for preparing the composite polyaluminum chloride water treatment agent according to claim 1, wherein the ratio of the amount of bifunctional POSS, dimethyl sulfoxide, dibutyltin dilaurate and 4-carboxyphenyl isothiocyanate is 10.5-11.3g:80-100mL:0.3g:7.3-8.5g.
3. The preparation method of the composite polyaluminum chloride water treatment agent according to claim 1, wherein the KH-570 coupling agent hydrolysate is obtained by the following steps:
adjusting pH of KH-570 with 5wt% hydrochloric acid solution to 3-4, and hydrolyzing for 12 hr to obtain KH-570 coupling agent hydrolysate.
4. The preparation method of the compound polyaluminium chloride water treatment agent according to claim 1, wherein the mass ratio of the polyaluminium chloride to the octavinyl-POSS to the modified chitosan is 100:20-23:3 to 10 percent, and the dosage of the ammonium persulfate is 0.6 to 0.7 percent of the sum of the mass of the octavinyl-POSS and the mass of the modified chitosan.
5. The preparation method of the compound polyaluminium chloride water treatment agent as claimed in claim 1, wherein the mass fraction of the polyaluminium chloride solution is 10-20%, and the amount of KH-570 is 8-10% of the mass of the polyaluminium chloride.
6. The preparation method of the composite polyaluminum chloride water treatment agent according to claim 1, wherein the bifunctional POSS is prepared by the following steps:
mixing octavinyl-POSS, mercaptoethylamine, benzoin dimethyl ether and DMF, and irradiating the mixture for 1 to 2 hours by ultraviolet light with the wavelength of 365nm to obtain the bifunctional POSS.
7. The preparation method of the compound polyaluminium chloride water treatment agent according to claim 1, wherein the modified chitosan is prepared by the following steps:
step S21, mixing allyl chloride, triethanolamine and deionized water, and stirring and reacting for 24 hours at 40 ℃ to obtain a trihydroxy allyl quaternary ammonium salt compound;
s22, dispersing chitosan and phthalic anhydride in DMF, and stirring and reacting for 8 hours at 120 ℃ under the protection of nitrogen to obtain amino-protected chitosan;
s23, putting pyridine into a flask, adding amino protective polysaccharide at 0 ℃, stirring and dissolving, slowly adding thionyl chloride, and stirring and reacting at 80 ℃ for 0.5h under the protection of nitrogen to obtain an intermediate product; placing tetrahydrofuran in a flask, adding trihydroxy allyl quaternary ammonium salt compound at 0 ℃, uniformly stirring, adding NaH, stirring at 60 ℃ for 1h under the protection of nitrogen, cooling to 0 ℃, adding an intermediate product, stirring for 0.5h, and stirring at 60 ℃ for 12h to obtain quaternary ammonium salt etherified chitosan;
and S24, dissolving quaternary ammonium salt etherified chitosan in N-methyl-2-pyrrolidone, adding a hydrazine hydrate solution with the concentration of 4mol/L, and reacting for 4-6 hours at 100 ℃ under the protection of argon to obtain the modified chitosan.
8. The preparation method of the composite polyaluminum chloride water treatment agent according to claim 7, wherein in step S23, the dosage ratio of the pyridine, the amino-protective chitosan, thionyl chloride, tetrahydrofuran, the trihydroxyallyl quaternary ammonium compound and NaH is 100mL:2g:0.5mL:50-60mL:2.3-2.5g:1g of the total weight of the composition.
9. The composite polyaluminum chloride water treatment agent is characterized by being prepared by the preparation method of any one of claims 1 to 8.
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| CN103739862A (en) * | 2013-07-25 | 2014-04-23 | 天津大学 | Gelatin/carboxymethyl chitosan/POSS (polyhedral oligomeric silsesquioxane) photo-crosslinking hydrogel and preparation method |
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