CN117304632A - Synergistic turbidity-removing and hardness-reducing composite material and preparation method and application thereof - Google Patents
Synergistic turbidity-removing and hardness-reducing composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 54
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 106
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 78
- 230000001276 controlling effect Effects 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 56
- 239000002351 wastewater Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 41
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 23
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 19
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 239000001099 ammonium carbonate Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000004115 Sodium Silicate Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 14
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 11
- 159000000011 group IA salts Chemical class 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 239000001433 sodium tartrate Substances 0.000 claims description 5
- 229960002167 sodium tartrate Drugs 0.000 claims description 5
- 235000011004 sodium tartrates Nutrition 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229960004599 sodium borate Drugs 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 55
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011777 magnesium Substances 0.000 description 71
- 229920000642 polymer Polymers 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 18
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 14
- 229910052749 magnesium Inorganic materials 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000007865 diluting Methods 0.000 description 9
- 238000005189 flocculation Methods 0.000 description 9
- 230000016615 flocculation Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction 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
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/164—Aluminum halide, e.g. aluminium chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a synergistic turbidity-removing and hardness-reducing composite material, and a preparation method and application thereof. The composite material comprises polysilicate aluminum chloride and cationic polyacrylamide with the hydrolysis degree of 15-25%, wherein the mass ratio of the polysilicate aluminum chloride to the cationic polyacrylamide is 1:5-1:2. The composite material is used in wastewater treatment, and can realize suspended matters and Ca 2+ 、Mg 2+ The synergistic removal of the water is good in removal effect, the preparation method is simple and convenient, and secondary pollution of the water body can be avoided.
Description
Technical Field
The invention belongs to the field of environment treatment composite materials, and particularly relates to a synergistic turbidity-removing and hardness-reducing composite material, and a preparation method and application thereof.
Background
Suspended matter and Ca 2+ 、Mg 2+ Is a common pollutant in wastewater. When the granularity of suspended matters in the wastewater is finer, flocculation is difficultThe degree is large, and the high-efficiency removal can be realized by means of destabilization of a large amount of inorganic coagulant and by means of adsorption bridging action of organic flocculant. When Ca is 2+ 、Mg 2+ When the ion concentration is higher (more than 80 mg/L), the scale is easy to form on the surfaces of the inner walls of the pipeline and the equipment, and the stable operation of the system is seriously affected. In addition, fine-grained suspensions and Ca 2+ 、Mg 2+ If the treatment is improper after scaling, the catalyst holes or the membrane holes are easy to be blocked, so that the treatment effect of the subsequent advanced treatment working section is affected. Therefore, the fine particles and Ca are aimed at 2+ 、Mg 2+ Searching for efficient pretreatment means is critical to the stable operation of the whole water treatment process flow.
The traditional pretreatment process for removing turbidity and reducing hardness adopts flocculation (turbidity removal) -Ca 2+ 、Mg 2+ Precipitation + flocculation (de-hardening) ". For suspended matter removal, at present, an inorganic flocculant (polyaluminum chloride (PAC), polymeric Ferric Sulfate (PFS), polymeric aluminum silicate chloride (PSAC) and the like) and an organic flocculant (polyacrylamide (PAM) and the like) are commonly used for treatment in a combined mode, however, at present, suspended matter granularity in wastewater is relatively fine, a large amount of PAC is generally required to be consumed, so that the problems of large medicament consumption, large solid slag production amount, excessive metal ion residues and the like are caused, and the flocculation effect is poor when the suspended matter is combined with the traditional PAM. The inorganic/organic composite flocculant gradually becomes a new generation flocculant with remarkable advantages by playing the synergistic effect of the electric neutralization of the inorganic flocculant and the adsorption bridging effect of the organic flocculant. However, most of reports on inorganic/organic composite flocculants are made by a physical composite method, thereby causing problems of uneven composite of inorganic and organic components, poor use stability of the flocculants, and the like, and thus affecting flocculation efficiency of materials.
For Ca 2+ 、Mg 2+ Ion removal, currently, the lime/soda softening process is mostly used in industry, and the pH is usually adjusted to be above 11 so that Ca 2+ 、Mg 2+ A precipitate is formed which is further removed by flocculation. The method needs to consume a large amount of alkaline precipitant, resulting in higher water treatment cost, and the pH value of the effluent needs to be regulated by adding sulfuric acid, thereby generating a large amount of inorganic salt,the burden of subsequent water treatment is increased.
CN102730888B discloses a method for treating industrial sewage with high hardness and high turbidity, which comprises the steps of firstly taking iron-containing metal as an anode, and generating Fe (OH) by means of electrode reaction 3 And polymer and other high activity flocs, and then adding sodium hydroxide to make Ca in water 2 + 、Mg 2+ Precipitate is formed by Fe (OH) 3 The net capturing, adsorption bridging and the like of the flocs are carried out, and the flocs and colloid and suspended matters in water form large-volume and large-mass flocs which are settled and removed together. The method is still carried out by two steps of flocculation and precipitation, and alkali is added in the precipitation process, so that the secondary pollutant is introduced into the water while the medicament is consumed, and the water treatment load of the subsequent working section is increased.
In conclusion, a new method for removing suspended matters and Ca is developed 2+ 、Mg 2+ Is urgent.
Disclosure of Invention
Aiming at suspended matters and Ca in the wastewater in the prior art 2+ 、Mg 2+ The invention provides a synergistic turbidity-removing and hardness-reducing composite material, a preparation method and application thereof, which are used for solving the problems of step-by-step treatment, complex process, easiness in secondary pollution and the like. The material can realize suspended matters and Ca in wastewater 2+ 、Mg 2+ The synergistic removal of the water is good in removal effect, the preparation method is simple and convenient, and secondary pollution of the water body can be avoided.
The first aspect of the invention provides a synergistic turbidity-removing and hardness-reducing composite material, which comprises polysilicate aluminum chloride and cationic polyacrylamide with the hydrolysis degree of 15-25%, wherein the mass ratio of the polysilicate aluminum chloride to the cationic polyacrylamide is 1:5-1:2.
In the invention, in the polysilicic acid aluminum chloride, silicon is formed by SiO 2 The content of (C) is 0.3-2.0%, preferably 1.6-2.0%, and Al is used as Al 2 O 3 The content of (2-8%).
The second aspect of the invention provides a preparation method of the synergistic turbidity-removing and hardness-reducing composite material, which comprises the following steps:
(1) Preparing sodium silicate solution, regulating the pH value of the solution to 3-6, and carrying out polymerization reaction;
(2) Preparing an aluminum chloride solution, dropwise adding an alkaline salt solution, and controlling the pH value of the end point solution to be 3-6;
(3) Mixing the solutions in the step (1) and the step (2), reacting, and aging to obtain polyaluminum silicate chloride;
(4) Adding acrylamide and quaternary ammonium salt monomer into the polysilicate aluminum chloride obtained in the step (1), adding an initiator under inert atmosphere (such as nitrogen), and performing polymerization reaction to obtain polysilicate aluminum chloride-cationic polyacrylamide;
(5) Slowly dripping strong base or strong base weak acid salt solution into the polyaluminium silicate chloride-cationic polyacrylamide obtained in the step (4) to carry out hydrolysis reaction, thus obtaining the composite material.
In the method of the invention, in the step (1), the concentration of the sodium silicate solution is 0.1-0.5mol/L, and the pH regulator can be at least one of hydrochloric acid and sulfuric acid.
In the method of the invention, in the step (1), the reaction temperature is 25-40 ℃ and the reaction time is 0.5-1.0h.
In the method of the invention, in the step (2), the alkaline salt solution is added under the stirring condition, the stirring speed is 500-1000rpm, the alkaline salt solution can be at least one of sodium carbonate, ammonium carbonate, sodium bicarbonate and ammonium bicarbonate, the concentration of the alkaline salt solution is 0.1-0.4mol/L, and the dropping time of the alkaline salt solution is 0.5-3h.
In the method of the invention, in the step (2), the concentration of the aluminum chloride solution is 0.3-0.8mol/L.
In the method of the invention, in the step (3), the mixing reaction is carried out under the condition of water bath temperature control. The reaction temperature is 30-60 ℃, the reaction stirring speed is 200-400rpm, and the reaction time is 0.5-2h.
In the method, in the step (3), the aging temperature is 20-40 ℃ and the aging time is 2-6h.
In the method of the invention, in the step (4), the polysilicic acid aluminum chloride is diluted 3-15 times before being used.
In the method of the present invention, in the step (4), the quaternary ammonium salt monomer may be at least one of methacryloyloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride.
In the method of the present invention, in the step (4), the concentration of the acrylamide is 0.5 to 4.0mol/L.
In the method, in the step (4), the dripping speed of the acrylamide is 0.3-0.6 mL/min, the dripping speed of the quaternary ammonium salt monomer is 0.2-0.4 mL/min, and the dripping speed ratio of the acrylamide to the quaternary ammonium salt monomer is 1-3.
In the method, in the step (4), the mass ratio of the quaternary ammonium salt monomer to the acrylamide is 1:9-1:1.
In the method of the present invention, in the step (4), the initiator may be at least one of ammonium persulfate, potassium persulfate, ammonium persulfate and sodium bisulfite, potassium persulfate and sodium bisulfite. Wherein the mass ratio of ammonium persulfate to sodium bisulfite is 1:1-2:1, and the mass ratio of potassium persulfate to sodium bisulfite is 1:1-2:1.
In the method of the invention, in the step (4), the total mass ratio of the initiator to the acrylamide and quaternary ammonium salt monomer is 1:1000-1:100.
In the process of the present invention, in step (4), the polymerization reaction is carried out in a thermostatic water bath. Wherein the temperature of the constant-temperature water bath is 40-80 ℃ and the polymerization time is 8-12h.
In the method of the present invention, in the step (5), the strong base or strong base weak acid salt may be at least one of sodium hydroxide, sodium carbonate, sodium phosphate, sodium hypophosphite, sodium pyrophosphate, sodium borate, sodium citrate or sodium tartrate, and the concentration is 0.05-0.20mol/L.
In the method of the present invention, in step (5), the molar ratio of the strong base or the strong base weak acid salt to acrylamide is 0.25:1 to 2:1.
In the method of the present invention, in the step (5), the dropping rate of the strong base or the strong base weak acid salt is 0.5-1.0mL/min.
In the method of the present invention, in step (5), the hydrolysis reaction is performed in a thermostatic water bath. Wherein the water bath temperature is 85-95 ℃, and the hydrolysis reaction time is 0.5-3.0h.
In a third aspect the present invention provides a composite as described aboveUse of a material in wastewater treatment comprising: adding the composite material to a system containing both suspended matter and Ca 2+ 、Mg 2+ The reaction is carried out in the ionic wastewater.
In the invention, the adding amount of the composite material is 10-120mg/L. The particle size of suspended matters in the wastewater is 80-450nm, the concentration of suspended matters is 50-200mg/L, ca 2+ The concentration is 10-100Mg/L, mg 2+ The concentration is 10-100mg/L.
In the invention, the reaction is divided into three stages, wherein the first stage is a rapid mixing stage, the stirring speed is 400-500rpm, the stirring time is 1-3min, the second stage is a coagulation adsorption stage, the stirring speed is 200-300rpm, the stirring time is 25-30min, the third stage is a standing sedimentation stage, and the standing time is 0.5-1.0h.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composite material of the invention comprises polysilicate aluminum chloride and cationic polyacrylamide with the hydrolysis degree of 15-25%, integrates functions of flocculation, adsorption, precipitation and the like, and can realize suspended matters and Ca in wastewater 2+ 、Mg 2+ Thereby degenerating the water treatment process to reduce the equipment footprint and investment; the composite material of the invention can greatly reduce the use of acid, alkali, precipitant and the like, namely Ca can be realized under the condition of not changing the pH of the water body 2+ 、Mg 2+ Effectively removing the water, avoiding secondary pollution of the water body, and effectively reducing the desalting load of the subsequent working section, the solid slag yield and the water treatment cost.
(2) The inventor finds that firstly, inert gas (such as nitrogen) is introduced into the polyaluminum silicate for protection, then an initiator is added, the dripping rates of acrylamide and quaternary ammonium salt monomers are respectively controlled, the mixture is sequentially and alternately dripped into a reaction system for polymerization reaction to obtain polyaluminum silicate-cationic polyacrylamide, finally strong base or strong base weak acid salt solution is added to partially hydrolyze the cationic polyacrylamide, carboxyl adsorption functional groups and precipitation functional anions (carbonate, phosphate, tartrate and the like) are introduced, and simultaneously the adsorption complexing and coagulation effects of the polyaluminum silicate chloride are combined, thereby adsorbingThe precipitation function and the flocculation function are organically combined and simultaneously act on suspended matters, ca 2+ And Mg (magnesium) 2+ And finally, the floccules with larger particle sizes are formed, so that the separation time of pollutants can be effectively shortened, and the water treatment efficiency is improved.
Detailed Description
The synergistic turbidity-removing and hardness-reducing composite material and the effect thereof according to the present invention are further described below with reference to specific examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
In the present invention, the concentration of contaminants is determined gravimetrically, and Ca is determined by means of an ion chromatograph (Aquion-RFIC) 2+ And Mg (magnesium) 2+ Concentration of suspended matter and Ca 2+ 、Mg 2+ The calculation formula of the removal rate of (2) is shown in (1):
wherein R% represents the removal rate of the contaminant, C 0 Representing contaminants (i.e. suspended matter, ca 2+ Or Mg (Mg) 2+ ) C represents the initial concentration of the pollutant (i.e. suspended matter, ca) after coagulation adsorption treatment 2+ Or Mg (Mg) 2+ ) Is a concentration of (3).
The calculation formula of the hydrolysis degree is shown in (2):
wherein H% represents the degree of hydrolysis of the cationic acrylamide, n NaOH Represents the molar mass of sodium hydroxide, n AM Representing the molar mass of acrylamide. For cationic acryl caused by strong alkali weak acid saltThe hydrolysis of amine is firstly carried out according to pH change caused by strong alkali and weak acid salt, and the molar mass of sodium hydroxide is obtained through conversion, so that the degree of hydrolysis is calculated.
Example 1
(1) Preparation of composite materials
Preparing 0.3mol/L sodium silicate solution, regulating the pH value of the solution to 4 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 25 ℃; preparing 0.4mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 1h, and controlling the pH value of the dropwise adding end point to be 4; mixing the two solutions, reacting for 1h at 40 ℃ in a water bath and at a stirring speed of 300rpm, and then aging for 3h at 40 ℃ to obtain polyaluminum silicate chloride; then diluting the mixture for 8 times, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide and dimethyl diallyl ammonium chloride, controlling the dripping rates of the acrylamide and the dimethyl diallyl ammonium chloride to be 0.4mL/min and 0.4mL/min respectively, controlling the concentration of the acrylamide to be 2mol/L, controlling the mass ratio of the dimethyl diallyl ammonium chloride to the acrylamide to be 1:1, placing the mixture in a 60 ℃ constant-temperature water bath, then adding ammonium persulfate and sodium bisulfite composite initiator, controlling the mass ratio of the ammonium persulfate to the sodium bisulfite to be 2:1, controlling the mass ratio of the initiator to the acrylamide to the dimethyl diallyl ammonium chloride to be 1:1000, and performing polymerization reaction for 10h to finally obtain a polymer solution; slowly dripping a sodium carbonate solution with the mass molar ratio of 0.1mol/L to the polymer solution, controlling the mass molar ratio of the sodium carbonate to the acrylamide monomer to be 0.5:1, dripping the sodium carbonate into the polymer solution at the rate of 0.5mL/min, placing the polymer solution into a constant-temperature water bath with the temperature of 90 ℃, and reacting for 2 hours to finally obtain the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 1min at the stirring speed of 500rpm, then reacting for 29min at the stirring speed of 250rpm, and then standing for 0.5h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. At the position ofUnder the above reaction conditions, the removal rate of suspended matters by the composite material is 90%, ca 2+ The removal rate of (2) is 40%, mg 2+ The removal rate of (2) was 40%.
Example 2
(1) Preparation of composite materials
Preparing 0.5mol/L sodium silicate solution, regulating the pH value of the solution to 3 by means of hydrochloric acid, and carrying out polymerization reaction for 0.5h at 40 ℃; preparing 0.6mol/L aluminum chloride solution, slowly dropwise adding 0.4mol/L ammonium carbonate solution under the stirring condition of 1000rpm for 1h, and controlling the pH value of the dropwise adding end point to be 5; mixing the two solutions, reacting for 2 hours at the water bath temperature of 30 ℃ and the stirring speed of 400rpm, and then aging for 3 hours at the temperature of 30 ℃ to obtain polyaluminum silicate chloride; then diluting the mixture for 4 times, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide and dimethyl diallyl ammonium chloride, controlling the dripping rate of the acrylamide and the dimethyl diallyl ammonium chloride to be 0.6mL/min and 0.2mL/min respectively, controlling the concentration of the acrylamide to be 4mol/L, the mass ratio of the dimethyl diallyl ammonium chloride to the acrylamide to be 1:5, placing the mixture in a constant-temperature water bath at 70 ℃, then adding a composite initiator of potassium persulfate and sodium bisulfite, controlling the mass ratio of the ammonium persulfate to the sodium bisulfite to be 1.5:1, controlling the mass ratio of the initiator to the acrylamide to the dimethyl diallyl ammonium chloride to be 1:500, and performing polymerization reaction for 8h to finally obtain a polymer solution; slowly dripping a sodium phosphate solution with the mass molar ratio of 0.1mol/L to the polymer solution, controlling the mass molar ratio of sodium phosphate to acrylamide monomer to be 0.8:1, dripping the sodium phosphate into the acrylamide monomer at the rate of 0.5mL/min, placing the mixture into a constant-temperature water bath with the temperature of 95 ℃ and reacting for 0.5h to finally obtain the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 3min at the stirring speed of 400rpm, then reacting for 27min at the stirring speed of 200rpm, and then standing for 1h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 95%, ca 2+ The removal rate of (2) is 55%, mg 2+ The removal rate of (2) was 60%.
Example 3
(1) Preparation of composite materials
Preparing 0.1mol/L sodium silicate solution, regulating the pH value of the solution to 3 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 30 ℃; preparing 0.8mol/L aluminum chloride solution, slowly dropwise adding 0.4mol/L ammonium carbonate solution under the stirring condition of 500rpm for 1h, and controlling the pH value of the dropwise adding end point to be 6; mixing the two solutions, reacting for 1h at the water bath temperature of 60 ℃ and the stirring speed of 300rpm, and then aging for 4h at the temperature of 40 ℃ to obtain polyaluminum silicate chloride; then diluting the mixture by 8.5 times, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide and methacryloyloxyethyl trimethyl ammonium chloride, controlling the dripping rates of the acrylamide and the methacryloyloxyethyl trimethyl ammonium chloride to be 0.6mL/min and 0.2mL/min respectively, wherein the concentration of the acrylamide is 4mol/L, the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the acrylamide is 1:8, placing the mixture in a constant-temperature water bath at 50 ℃, then adding a potassium persulfate initiator, the mass ratio of the initiator to the acrylamide and the dimethyldiallylammonium chloride monomer is 1:100, and carrying out polymerization reaction for 12h to finally obtain a polymer solution; slowly dripping 0.2mol/L sodium tartrate solution into the polymer solution, controlling the mass molar ratio of sodium tartrate to acrylamide monomer to be 1:1, dripping the sodium tartrate to the acrylamide monomer to be 0.8mL/min, placing the polymer solution into a constant-temperature water bath at 85 ℃, and reacting for 1h to finally obtain the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 3min at the stirring speed of 400rpm, then reacting for 27min at the stirring speed of 300rpm, and then standing for 1h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. At the position ofUnder the above reaction conditions, the removal rate of suspended matters by the composite material is 85%, ca 2+ The removal rate of (2) is 25%, mg 2+ The removal rate of (2) was 25%.
Example 4
Preparing 0.3mol/L sodium silicate solution, regulating the pH value of the solution to 5 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 30 ℃; preparing 0.4mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 2 hours, and controlling the pH value of the dropwise adding end point to be 5; mixing the two solutions, reacting for 2 hours at the water bath temperature of 60 ℃ and the stirring speed of 300rpm, and then aging for 2 hours at the temperature of 40 ℃ to obtain polyaluminum silicate chloride; then diluting the mixture for 9 times, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide and methacryloyloxyethyl trimethyl ammonium chloride, controlling the dripping rate of the acrylamide and the dimethyldiallyl ammonium chloride to be 0.6mL/min and 0.2mL/min respectively, controlling the concentration of the acrylamide to be 3mol/L, the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the acrylamide to be 1:9, placing the mixture in a constant-temperature water bath at 50 ℃, then adding a sodium persulfate initiator, controlling the mass ratio of the initiator to the acrylamide and the dimethyldiallyl ammonium chloride to be 1:200, and carrying out polymerization reaction for 8h to finally obtain a polymer solution; slowly dripping 0.2mol/L sodium hydroxide solution into the polymer solution, controlling the mass mol ratio of sodium hydroxide to acrylamide monomer to be 0.25:1, dripping the sodium hydroxide into the acrylamide monomer at the rate of 0.5mL/min, and placing the mixture into a constant-temperature water bath at the temperature of 85 ℃ to react for 3 hours, thus obtaining the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 2min at the stirring speed of 500rpm, then reacting for 28min at the stirring speed of 300rpm, and then standing for 1h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 90 percent, ca 2+ Is removed by (a)The rate is 42%, mg 2+ The removal rate of (2) was 50%.
Example 5
Preparing 0.3mol/L sodium silicate solution, regulating the pH value of the solution to 5 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 30 ℃; preparing 0.2mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 2 hours, and controlling the pH value of the dropwise adding end point to be 5; mixing the two solutions, reacting for 2 hours at the water bath temperature of 60 ℃ and the stirring speed of 300rpm, and then aging for 2 hours at the temperature of 40 ℃ to obtain polyaluminum silicate chloride; then diluting the mixture for 14 times, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide and methacryloyloxyethyl trimethyl ammonium chloride, controlling the dripping rate of the acrylamide and the dimethyldiallyl ammonium chloride to be 0.5mL/min and 0.3mL/min respectively, controlling the concentration of the acrylamide to be 3mol/L, the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the acrylamide to be 1:9, placing the mixture in a constant-temperature water bath at 50 ℃, then adding a sodium persulfate initiator, controlling the mass ratio of the initiator to the acrylamide and the dimethyldiallyl ammonium chloride to be 1:200, and carrying out polymerization reaction for 8h to finally obtain a polymer solution; slowly dripping sodium pyrophosphate solution with the mass ratio of 0.2mol/L to the polymer solution being controlled to be 1:1, wherein the dripping speed is 0.5mL/min, and placing the polymer solution in a constant-temperature water bath with the temperature of 85 ℃ for 3 hours, thus obtaining the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 2min at the stirring speed of 500rpm, then reacting for 28min at the stirring speed of 300rpm, and then standing for 1h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 92 percent, ca 2+ The removal rate of (2) is 35%, mg 2+ The removal rate of (2) was 40%.
Example 6
Preparing 0.6mol/L sodium silicate solution, regulating the pH value of the solution to 5 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 30 ℃; preparing 0.4mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 2 hours, and controlling the pH value of the dropwise adding end point to be 5; mixing the two solutions, reacting for 2 hours at the water bath temperature of 60 ℃ and the stirring speed of 300rpm, and then aging for 2 hours at the temperature of 25 ℃ to obtain polyaluminum silicate chloride; then diluting for 9 times, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide and methacryloyloxyethyl trimethyl ammonium chloride, controlling the dripping rate of the acrylamide and the dimethyldiallyl ammonium chloride to be 0.3mL/min and 0.2mL/min respectively, controlling the concentration of the acrylamide to be 3mol/L, setting the mass ratio of the methacryloyloxyethyl trimethyl ammonium chloride to the acrylamide to be 1:9 in a constant-temperature water bath at 50 ℃, then adding a sodium persulfate initiator, controlling the mass ratio of the initiator to the acrylamide and the dimethyldiallyl ammonium chloride to be 1:200, and carrying out polymerization reaction for 8h to finally obtain a polymer solution; slowly dripping 0.2mol/L sodium hydroxide solution into the polymer solution, controlling the mass mol ratio of sodium hydroxide to acrylamide monomer to be 0.25:1, dripping the sodium hydroxide into the acrylamide monomer at the rate of 0.5mL/min, and placing the mixture into a constant-temperature water bath at the temperature of 85 ℃ to react for 3 hours, thus obtaining the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 2min at the stirring speed of 500rpm, then reacting for 28min at the stirring speed of 300rpm, and then standing for 1h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 99 percent, ca 2+ The removal rate of (2) is 65%, mg 2+ The removal rate of (2) was 70%.
Comparative example 1
(1) Preparation of composite materials
Preparing 0.3mol/L sodium silicate solution, regulating the pH value of the solution to 4 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 25 ℃; preparing 0.4mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 1h, and controlling the pH value of the dropwise adding end point to be 4; mixing the two solutions, reacting for 1h at 40 ℃ in a water bath and at a stirring speed of 300rpm, and then aging for 3h at 40 ℃ to obtain the polysilicic acid aluminum chloride composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 1min at the stirring speed of 500rpm, then reacting for 29min at the stirring speed of 250rpm, and then standing for 0.5h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 40%, ca 2+ The removal rate of (2) is 3%, mg 2+ The removal rate of (2%).
Comparative example 2
(1) Preparation of composite materials
Preparing 0.3mol/L sodium silicate solution, regulating the pH value of the solution to 4 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 25 ℃; preparing 0.4mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 1h, and controlling the pH value of the dropwise adding end point to be 4; mixing the two solutions, reacting for 1h at 40 ℃ in a water bath and at a stirring speed of 300rpm, and then aging for 3h at 40 ℃ to obtain polyaluminum silicate chloride; then diluting the mixture by 8 times, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide, controlling the dripping rate of the acrylamide to be 0.4mL/min, controlling the concentration of the acrylamide to be 2mol/L, placing the mixture in a constant-temperature water bath at 60 ℃, then adding ammonium persulfate and sodium bisulfite composite initiator, controlling the mass ratio of the ammonium persulfate to the sodium bisulfite to be 2:1, controlling the mass ratio of the initiator to the acrylamide monomer to be 1:1000, and carrying out polymerization reaction for 10h to finally obtain a polymer solution; slowly dripping a sodium carbonate solution with the mass molar ratio of 0.1mol/L to the polymer solution, controlling the mass molar ratio of the sodium carbonate to the acrylamide monomer to be 0.5:1, dripping the sodium carbonate into the polymer solution at the rate of 0.5mL/min, placing the polymer solution into a constant-temperature water bath with the temperature of 90 ℃, and reacting for 2 hours to finally obtain the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 1min at the stirring speed of 500rpm, then reacting for 29min at the stirring speed of 250rpm, and then standing for 0.5h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 62 percent, ca 2+ The removal rate of (2) is 25%, mg 2+ The removal rate of (2) was 20%.
Comparative example 3
(1) Preparation of composite materials
Preparing 0.3mol/L sodium silicate solution, regulating the pH value of the solution to 4 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 25 ℃; preparing 0.4mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 1h, and controlling the pH value of the dropwise adding end point to be 4; mixing the two solutions, reacting for 1h at 40 ℃ in a water bath and at a stirring speed of 300rpm, and then aging for 3h at 40 ℃ to obtain polyaluminum silicate chloride; then diluting the mixture by 8 times, removing oxygen by nitrogen for 0.5h, adding acrylamide and dimethyl diallyl ammonium chloride, controlling the dropping rate of the acrylamide and the dimethyl diallyl ammonium chloride to be 0.4mL/min and 0.4mL/min respectively, controlling the concentration of the acrylamide to be 2mol/L, the mass ratio of the dimethyl diallyl ammonium chloride to the acrylamide to be 1:1, placing the mixture in a constant-temperature water bath at 60 ℃, then adding a compound initiator of ammonium persulfate and sodium bisulfite, controlling the mass ratio of the ammonium persulfate to the sodium bisulfite to be 2:1, controlling the mass ratio of the initiator to the acrylamide to the dimethyl diallyl ammonium chloride to be 1:1000, and performing polymerization reaction for 10h to obtain the final polymer, namely the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding a composite material into wastewater with the concentration of 10mg/L according to the concentration of 100mg/L, reacting for 1min at the stirring speed of 500rpm, then reacting for 29min at the stirring speed of 250rpm, and then standing for 0.5h to determine residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 95%, ca 2+ The removal rate of (2) is 8%, mg 2+ The removal rate of (2) was 20%.
Comparative example 4
(1) Preparation of composite materials
Taking a certain volume of deionized water, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide and dimethyl diallyl ammonium chloride, controlling the dripping rates of the acrylamide and the dimethyl diallyl ammonium chloride to be 0.4mL/min and 0.4mL/min respectively, wherein the concentration of the acrylamide is 2mol/L, the mass ratio of the dimethyl diallyl ammonium chloride to the acrylamide is 1:1, placing the deionized water in a 60 ℃ constant-temperature water bath, then adding ammonium persulfate and sodium bisulfite composite initiator, controlling the mass ratio of the ammonium persulfate to the sodium bisulfite to be 2:1, controlling the mass ratio of the initiator to the acrylamide and the dimethyl diallyl ammonium chloride monomer to be 1:1000, and carrying out polymerization reaction for 10h to finally obtain a polymer solution; slowly dripping a sodium carbonate solution with the mass molar ratio of 0.1mol/L to the polymer solution, controlling the mass molar ratio of the sodium carbonate to the acrylamide monomer to be 0.5:1, dripping the sodium carbonate into the polymer solution at the rate of 0.5mL/min, placing the polymer solution into a constant-temperature water bath with the temperature of 90 ℃, and reacting for 2 hours to finally obtain the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding the composite into the wastewater with the concentration of 10mg/L according to the concentration of 100mg/LThe material was reacted at a stirring rate of 500rpm for 1min, then at 250rpm for 29min, then allowed to stand for 0.5h, and residual suspended matters, ca, in the wastewater were measured 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 65 percent, ca 2+ The removal rate of (2) is 20%, mg 2+ The removal rate of (2) was 15%.
Comparative example 5
(1) Preparation of composite materials
Preparing 0.3mol/L sodium silicate solution, regulating the pH value of the solution to 4 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 25 ℃; preparing 0.4mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 15min, and controlling the pH value of the dropwise adding end point to be 4; mixing the two solutions, reacting for 1h at 40 ℃ in a water bath and at a stirring speed of 300rpm, and then aging for 3h at 40 ℃ to obtain polyaluminum silicate chloride; then diluting the mixture for 8 times, introducing nitrogen to remove oxygen for 0.5h, adding acrylamide and dimethyl diallyl ammonium chloride, controlling the dripping rates of the acrylamide and the dimethyl diallyl ammonium chloride to be 1.0mL/min and 0.1mL/min respectively, controlling the concentration of the acrylamide to be 2mol/L, controlling the mass ratio of the dimethyl diallyl ammonium chloride to the acrylamide to be 1:1, placing the mixture in a 60 ℃ constant-temperature water bath, then adding ammonium persulfate and sodium bisulfite composite initiator, controlling the mass ratio of the ammonium persulfate to the sodium bisulfite to be 2:1, controlling the mass ratio of the initiator to the acrylamide to the dimethyl diallyl ammonium chloride to be 1:1000, and performing polymerization reaction for 10h to finally obtain a polymer solution; slowly dripping a sodium carbonate solution with the mass molar ratio of 0.1mol/L to the polymer solution, controlling the mass molar ratio of the sodium carbonate to the acrylamide monomer to be 0.5:1, dripping the sodium carbonate into the polymer solution at the rate of 0.5mL/min, placing the polymer solution into a constant-temperature water bath with the temperature of 90 ℃, and reacting for 2 hours to finally obtain the composite material.
(2) The composite material is used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ 10mg/L of wastewater according to the following proportionAdding the composite material according to 100mg/L, reacting for 1min at a stirring speed of 500rpm, then reacting for 29min at a stirring speed of 250rpm, then standing for 0.5h, and measuring residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 72 percent, ca 2+ The removal rate of (2) is 30%, mg 2+ The removal rate of (2) was 25%.
Comparative example 6
(1) Preparation of polyaluminum silicate chloride and polyacrylamide
Preparing 0.3mol/L sodium silicate solution, regulating the pH value of the solution to 4 by means of hydrochloric acid, and carrying out polymerization reaction for 1h at 25 ℃; preparing 0.4mol/L aluminum chloride solution, slowly dropwise adding 0.3mol/L ammonium carbonate solution under the stirring condition of 800rpm for 1h, and controlling the pH value of the dropwise adding end point to be 4; mixing the two solutions, reacting for 1h at 40 ℃ in a water bath and at a stirring speed of 300rpm, and then aging for 3h at 40 ℃ to obtain polyaluminum silicate chloride;
preparing 2mol/L acrylamide solution, introducing nitrogen to remove oxygen for 0.5h, placing in a constant-temperature water bath at 60 ℃, then adding ammonium persulfate and sodium bisulfite composite initiator, controlling the mass ratio of the ammonium persulfate to the sodium bisulfite to be 2:1, controlling the mass ratio of the initiator to the acrylamide to be 1:1000, performing polymerization reaction for 10h, and finally obtaining the polyacrylamide solution.
(2) Polyaluminum silicate chloride and polyacrylamide are used for suspended matters and Ca in wastewater 2+ 、Mg 2+ Is removed by (a)
Collecting suspension with concentration of 200mg/L, particle diameter of 80-450nm, ca 2+ The concentration is 100Mg/L and Mg 2+ Adding polyaluminum silicate chloride into wastewater with the concentration of 10mg/L according to the concentration of 75mg/L, adding polyacrylamide with the concentration of 25mg/L, reacting for 1min under the stirring speed of 500rpm, then reacting for 29min under the stirring condition of 250rpm, and then standing for 0.5h, and measuring residual suspended matters and Ca in the wastewater 2+ And Mg (magnesium) 2+ The content is as follows. Under the reaction conditions, the removal rate of suspended matters by the composite material is 65 percent, ca 2+ The removal rate of (2) is 8%, mg 2+ The removal rate of (2) was 10%.
Table 1 physicochemical Properties of the composite Material obtained in each example
Table 1 physicochemical Properties (continuous) of the composite Material obtained in each example
Claims (16)
1. A synergistic turbidity-removing and hardness-reducing composite material comprises polysilicate aluminum chloride and cationic polyacrylamide with a hydrolysis degree of 15-25%, wherein the mass ratio of the polysilicate aluminum chloride to the cationic polyacrylamide is 1:5-1:2.
2. The composite material of claim 1, wherein in the polysilicic acid aluminum chloride, silicon is in the form of SiO 2 The content of Al is 0.3-2.0%, preferably 1.6-2.0% 2 O 3 The content of the components is 2 to 8 percent.
3. A method of preparing the composite material of any one of claims 1-2, comprising the steps of:
(1) Preparing sodium silicate solution, regulating the pH value of the solution to 3-6, and carrying out polymerization reaction;
(2) Preparing an aluminum chloride solution, dropwise adding an alkaline salt solution, and controlling the pH value of the end point solution to be 3-6;
(3) Mixing the solutions in the step (1) and the step (2), reacting, and aging to obtain polyaluminum silicate chloride;
(4) Adding acrylamide and quaternary ammonium salt monomer into the polysilicate aluminum chloride obtained in the step (1), and adding an initiator under inert atmosphere to perform polymerization reaction to obtain polysilicate aluminum chloride-cationic polyacrylamide;
(5) Slowly dripping strong base or strong base weak acid salt solution into the polyaluminium silicate chloride-cationic polyacrylamide obtained in the step (4) to carry out hydrolysis reaction, thus obtaining the composite material.
4. The process according to claim 3, wherein in the step (1), the polymerization temperature is 25 to 40℃and the reaction time is 0.5 to 1.0h.
5. The method according to claim 3, wherein in the step (2), the alkaline salt solution is at least one of sodium carbonate, ammonium carbonate, sodium bicarbonate and ammonium bicarbonate, and the concentration of the alkaline salt solution is 0.1-0.4mol/L.
6. The method according to claim 3, wherein in the step (2), the alkaline salt solution is added dropwise for 0.5 to 3 hours; and/or in the step (4), the rate ratio of the acrylamide to the quaternary ammonium salt monomer is 1-3.
7. The process according to claim 3, wherein in the step (3), the reaction temperature is 30 to 60℃and the reaction time is 0.5 to 2 hours; the aging temperature is 20-40 ℃ and the aging time is 2-6h.
8. The method according to claim 3, wherein in the step (4), the quaternary ammonium salt monomer is at least one of methacryloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride.
9. The method according to claim 3, wherein in the step (4), the mass ratio of the quaternary ammonium salt monomer to the acrylamide is 1:9 to 1:1.
10. The method according to claim 3, wherein in the step (4), the initiator is at least one of ammonium persulfate, potassium persulfate, ammonium persulfate and sodium bisulfate, and potassium persulfate and sodium bisulfate, wherein the mass ratio of ammonium persulfate to sodium bisulfate is 1:1-2:1, and the mass ratio of potassium persulfate to sodium bisulfate is 1:1-2:1.
11. The process according to claim 3, wherein in the step (4), the total mass ratio of the initiator to the acrylamide and quaternary ammonium salt monomer is 1:1000 to 1:100; and/or, in the step (5), the molar ratio of the strong base or the strong base weak acid salt to the acrylamide is 0.25:1-2:1.
12. The process according to claim 3, wherein in the step (4), the polymerization temperature is 40 to 80℃and the polymerization time is 8 to 12 hours; and/or in the step (5), the hydrolysis temperature is 85-95 ℃ and the hydrolysis reaction time is 0.5-3.0h.
13. The method according to claim 3, wherein in the step (5), the strong base or strong base weak acid salt is at least one of sodium hydroxide, sodium carbonate, sodium phosphate, sodium hypophosphite, sodium pyrophosphate, sodium borate, sodium citrate or sodium tartrate, and the concentration is 0.05-0.20mol/L.
14. Use of the composite material of any one of claims 1-2 in wastewater treatment comprising: adding the composite material to a system containing both suspended matter and Ca 2+ 、Mg 2+ The reaction is carried out in the ionic wastewater.
15. The use according to claim 14, wherein the particle size of the suspended matter in the wastewater is 80-450nm, the concentration of suspended matter is 50-200mg/L, ca 2+ The concentration is 10-100Mg/L, mg 2+ The concentration is 10-100mg/L, and the adding amount of the composite material is 10-120mg/L.
16. The use according to claim 14, wherein the reaction is divided into three stages, the first stage being a rapid mixing stage, the stirring rate being 400-500rpm, the stirring time being 1-3min, the second stage being a coagulation adsorption stage, the stirring rate being 200-300rpm, the stirring time being 25-30min, the third stage being a settling stage, the settling time being 0.5-1.0h.
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