CN105036269A - Multi-effect water treatment agent, preparation method thereof and water treatment method - Google Patents
Multi-effect water treatment agent, preparation method thereof and water treatment method Download PDFInfo
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- CN105036269A CN105036269A CN201510361037.1A CN201510361037A CN105036269A CN 105036269 A CN105036269 A CN 105036269A CN 201510361037 A CN201510361037 A CN 201510361037A CN 105036269 A CN105036269 A CN 105036269A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 title abstract description 13
- 238000005189 flocculation Methods 0.000 claims abstract description 55
- 230000016615 flocculation Effects 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 46
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims description 23
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 11
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims description 11
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 claims description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 5
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 230000021523 carboxylation Effects 0.000 abstract description 2
- 238000006473 carboxylation reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- -1 poly(diallyl dimethyl ammonium chloride) Polymers 0.000 abstract description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 abstract 1
- 229910000859 α-Fe Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 230000003311 flocculating effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920000592 inorganic polymer Polymers 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000005111 flow chemistry technique Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a multi-effect water treatment agent, a preparation method thereof and a water treatment method. The multi-effect water treatment agent is prepared from acrylamide oligomer grafting graphene oxide, polyacrylamide, polysilicate aluminum ferrite, poly(diallyl dimethyl ammonium chloride) and sodium bicarbonate, wherein the acrylamide oligomer grafting graphene oxide is prepared by two steps of graphene oxide carboxylation and grafting reaction. The multiple-effect water treatment agent can adapt to multiple complex water qualities, and particularly can effectively remove benzene compounds and heavy metal ions. The water treatment method comprises stages of mixing, preliminary flocculation, secondary flocculation and filtering; the efficient utilization of the water treatment agent is realized by using a lower water backflow step, and the production cost is lowered.
Description
Technical field
The present invention relates to the technical field of water treatment, particularly relate to the water treatment method of a kind of multiple-effect water conditioner and its preparation method and application this multiple-effect water conditioner.
Background technology
In water treatment field, flocculation sediment is a kind of conventional treatment process, it have simple to operate, cost is low, high treating effect.The mechanism of action of flocculation is commonly considered as compression double electric layer and charge neutralization, the adsorption bridging effect of polymer water conditioner, the volume of flco sweep precipitating action etc.The process of flocculation is the process of colloidal solid loss of stability, and colloidalmaterial and little suspension grain are gathered into larger particle, thus are easy to precipitate from liquid.Add water conditioner and can accelerate this mechanism, greatly can improve the absorption of these aggregates to the various impurity dissolved, advantageously in the purification of water quality.
Water conditioner is widely used in former water and sewage treatment area, can reduce the sense indexs such as the turbidity of former water, colourity.Multiple macromolecule organic, some heavy metal and radioactive substance is removed by water conditioner, both independently treatment system can be had of one's own, also can combine with other processing unit process, as pre-treatment, intermediate treatment and final treating processes, also can be used for the concentration process before sludge dewatering, improve the dewatering of mud.
The kind of water conditioner can be divided into inorganic water conditioner, organic water treatment agent and microorganism water conditioner generally, and in actual applications, often according to the difference of water conditioner character by they compounds in addition.
Water after the harmless process of water conditioner can reuse.The annual process water of Present Domestic, city water, sewage disposal demand water conditioner 1,000,000 tons, therefore study water conditioner tool and have very important significance.
Inorganic water conditioner is the water conditioner that in water conditioner, consumption is maximum, has defined based on several large series products of aluminium salt, molysite and polysilicon acid etc. in recent years.Inorganic water conditioner can be divided into low-molecular inorganic water conditioner and inorganic polymer water conditioner by its molecular size range.
Low-molecular inorganic water conditioner mainly contains Tai-Ace S 150, aluminum chloride, ferrous sulfate, ferric sulfate, iron(ic) chloride etc.Although low-molecular inorganic water conditioner is cheap, ample supply and prompt delivery, due to reasons such as coagulation consumption are large, the wadding quantity of slag is many, coagulation effect is poor, in actual waste water process oneself progressively replace by inorganic polymer water conditioner.
Inorganic polymer water conditioner is as the inorganic water conditioner of the s-generation, have that more traditional water conditioner (as Tai-Ace S 150, iron(ic) chloride etc.) efficiency of coagulation is more excellent, price is relatively low again, the advantages such as, economically feasible cheap compared with organic polymer water conditioner, successfully be applied in the various treatment schemees of feedwater, trade effluent and municipal effluent (comprising pre-treatment, intermediate treatment and advanced treatment), become main flow water conditioner gradually.But due to inorganic water conditioner exist hydrolytic instability, relative molecular weight and adsorption bridging ability comparatively organic water treatment agent difference etc. problem.
The more inorganic water conditioner of organic polymer water conditioner have the salt that coexisted affect less, water conditioner consumption is little, settling velocity is fast, produces the advantages such as the quantity of slag is few, easy process.But due to organic polymer water conditioner ubiquity monomer residue toxicity, higher selectivity, the defect such as expensive, limit its widespread use to a certain extent.
Adopt single water conditioner usually cannot obtain satisfied treatment effect to the sewage system of complexity, therefore composite water disposal agent becomes study hotspot in recent years.Facts have proved, composite water disposal agent can overcome the many deficiencies using single water conditioner, shows the effect being better than single water conditioner, is the main trend of water conditioner development.
Summary of the invention
The present invention is intended to for technical problems such as in prior art, the process of composite water disposal agent former water source are single, flocculating effect is not ideal enough, a kind of multiple-effect water conditioner and preparation method thereof is provided, and the water treatment method of this multiple-effect water conditioner of a kind of application is provided, the efficient multiplexing of water conditioner is realized by lower layer of water technique of backflow, reduce production cost, improve water treatment efficiency.
Specifically, first, the invention provides a kind of multiple-effect water conditioner, comprise the following component with weight parts: acrylamide oligomers grafted graphene oxide 2 ~ 10 parts, polyacrylamide 5 ~ 40 parts, poly aluminium iron silicate 20 ~ 40 parts, the rare propyl ammonium chloride of polydimethyl two 3 ~ 25 parts, sodium bicarbonate 1 ~ 5 part.
In the multiple-effect water conditioner that the present invention discloses, have employed acrylamide oligomers grafted graphene oxide first as important component, graphene oxide receives in recent years and pays close attention to widely, wherein most important reason is its high-ratio surface sum extensively adsorption property of excellence, in the present invention, have employed acrylamide oligomers and modification is carried out to it, improve flocculation ability on the one hand, take graphene oxide as base material, the acrylamide oligomers of grafting is stretched out from surface of graphene oxide, form many dentalations, be conducive to the formation of colloid, improve the effect of flocculation, on the other hand, heavy metal ion, poisonous small molecules, especially benzene-like compounds pollutent has extremely strong Adsorption effect, for the water body realizing complicated Pollution System source has efficient detergent power.
Concrete, acrylamide oligomers grafted graphene oxide comprises graphene oxide 3 ~ 10wt% and acrylamide oligomers 90 ~ 97wt%, and described acrylamide oligomers molecular weight is 5000 ~ 20000.
For improving overall flocculating effect, be convenient to the formation of larger micelle, the Molecular Weight for Polyacrylamide simultaneously added is 200 ~ 1,000 ten thousand, and ion degree is 10% ~ 80%.
For realizing segmentation flocculation, the water technology of adapt to repeatedly dosing, repeatedly flocculating, adopt polyacrylamide comprise polyacrylamide 10 ~ 30wt% that molecular weight is 200 ~ 4,000,000, molecular weight be 400 ~ 8,000,000 polyacrylamide 40% ~ 50wt% and molecular weight be 800 ~ 1,000 ten thousand polyacrylamide 20% ~ 40wt%.
Secondly, the invention provides a kind of preparation method of multiple-effect water conditioner, it is characterized in that, comprise the following steps:
(1) graphene oxide is carboxylated:
In the graphene oxide water solution of 1 ~ 10mg/mL, add sodium hydroxide and Mono Chloro Acetic Acid, hybrid reaction 1 ~ 10 hour, be separated, wash, obtain carboxylated graphene oxide;
(2) acrylamide oligomers grafted graphene oxide:
In DMSO, mixed oxidization Graphene and acrylamide oligomers, add EDCI, back flow reaction at 45 DEG C, is separated, washs, obtain acrylamide oligomers grafted graphene oxide;
(3) preparation of multiple-effect water conditioner:
More than 45 DEG C, acrylamide oligomers grafted graphene oxide, polyacrylamide, the rare propyl ammonium chloride of polydimethyl two are mixed in proportion also Temperature fall and, to room temperature, add poly aluminium iron silicate, sodium bicarbonate successively, mix.
The parts by weight of each component are as follows:
Acrylamide oligomers grafted graphene oxide 2 ~ 10
Polyacrylamide 5 ~ 40
Poly aluminium iron silicate 20 ~ 40
The rare propyl ammonium chloride 3 ~ 25 of polydimethyl two
Sodium bicarbonate 1 ~ 5.
According to grafting needs, control carboxylated degree by adjustment carboxylation process, preferably, graphene oxide water solution in step (1): sodium hydroxide: Mono Chloro Acetic Acid=1L:1 ~ 2g:1 ~ 2g.
Same, the control of grafting amount also can by controlling the raw material dosage in grafting process, preferably, and step (2) middle DMSO: graphene oxide: acrylamide oligomers: EDCI=1L:3 ~ 10g:90 ~ 97g:10 ~ 100g.
Finally, the invention provides and a kind ofly apply the method that above-mentioned water conditioner carries out water treatment, it is characterized in that, at least comprise the steps:
A. mix stages: former water is introduced mixing pit, adds above-mentioned multiple-effect water conditioner, mix;
B. the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds multiple-effect water conditioner described above in flow process, again flocculate in the second flocculation basin;
D. filtration stage: the water again flocculated in step C is filtered by filter plant.
Further, for improving the utilising efficiency of water conditioner, step C ' refluxing stage is also comprised: the lower layer of water after initial flocculation in step B is passed back into mixing pit.
According to the particular case of former water, in steps A, multiple-effect water conditioner adds the amount of former water is 10 ~ 500mg/L; In step C, multiple-effect water conditioner adds the amount of water is 1 ~ 100mg/L.
Compared to prior art, beneficial effect of the present invention be following some.
(1) flocculating settling efficiency is high, and turbidity removal, decoloring ability are strong.Employing composite water disposal agent is filled a prescription, combine the feature performance benefit of organic polymer water conditioner, coagulant aids, inorganic polymer water conditioner, through repeatedly verifying, coordinate the electrocharge effect of each water conditioner, accomplish the optimization of flocculating effect, compared to single water conditioner and commercially available composite water disposal agent, just think with regard to same water quality, reduce the treatment time about 10%.
(2) be widely used, especially for benzene class, water quality that heavy metal class content is higher, by adding acrylamide oligomers grafted graphene oxide, realize the specific adsorption removal ability that similar water conditioner in prior art does not possess, experiment shows, to 85%, the pressure of follow-up flow processing can be alleviated to the clearance of benzene class impurity is the highest.
(3) cost effectively reduces, and by being drawn respectively by levels water in flocculation process, improve the effective rate of utilization of water conditioner, the extraction of upper water, decreasing the pressure of subsequent processes; The backflow of lower layer of water, adequately achieves the multiplexing of water conditioner, and through measuring and calculating, with regard to drinking water treatment standard, every cube of cost of water treatment reduces about 5%; With regard to industrial sewage preliminary treatment for regard to middle water quality standard, every cube of cost of water treatment reduces about 7%.
(4) water conditioner secondary pollution is little, the existence of graphene oxide, effectively improves the cohesive force of micelle, the secondary pollution that the diffusion decreasing relevant monomer in the agent of flocculation process sewerage disposing causes.
(5) applicable pH range is wide, generally, without the need to additionally adjusting former water pH, avoiding the process of pH adjustment in inorganic water conditioner use procedure, improve the range of application of product.
Embodiment
(1) preparation of multiple-effect water conditioner.
Embodiment 1-1
(1) graphene oxide is carboxylated
In the graphene oxide water solution of 5mg/mL, add sodium hydroxide and Mono Chloro Acetic Acid, graphene oxide water solution: sodium hydroxide: Mono Chloro Acetic Acid=1L:2g:2g, hybrid reaction 4 hours, be separated, wash, obtain carboxylated graphene oxide;
(2) acrylamide oligomers grafted graphene oxide
In DMSO, mixed oxidization Graphene and acrylamide oligomers, add EDCI, wherein, and DMSO: graphene oxide: acrylamide oligomers: EDCI=1L:8g:90g:50g.Back flow reaction at 45 DEG C, is separated, washs, obtain acrylamide oligomers grafted graphene oxide;
(3) preparation of multiple-effect water conditioner
More than 45 DEG C, acrylamide oligomers grafted graphene oxide, polyacrylamide, the rare propyl ammonium chloride of polydimethyl two are mixed in proportion also Temperature fall and, to room temperature, add poly aluminium iron silicate, sodium bicarbonate successively, mix.
The parts by weight of each component are as follows:
Acrylamide oligomers grafted graphene oxide 10, polyacrylamide 30, poly aluminium iron silicate 40, the rare propyl ammonium chloride 25 of polydimethyl two, sodium bicarbonate 5.
Embodiment 1-2: in the present embodiment, the preparation process of multiple-effect water conditioner, as embodiment 1-1, only adjusts to some extent in the proportioning of each component.
The parts by weight of each component are as follows: acrylamide oligomers grafted graphene oxide 8, polyacrylamide 35, poly aluminium iron silicate 35, the rare propyl ammonium chloride 20 of polydimethyl two, sodium bicarbonate 5.
Embodiment 1-3, in the present embodiment, the preparation process of multiple-effect water conditioner, as embodiment 1-1, only adjusts to some extent in the proportioning of each component.
The parts by weight of each component are as follows: acrylamide oligomers grafted graphene oxide 6, polyacrylamide 40, poly aluminium iron silicate 30, the rare propyl ammonium chloride 25 of polydimethyl two, sodium bicarbonate 5.
Embodiment 1-4, in the present embodiment, the preparation process of multiple-effect water conditioner, as embodiment 1-1, only adjusts to some extent in the proportioning of each component.
The parts by weight of each component are as follows: acrylamide oligomers grafted graphene oxide 4, polyacrylamide 20, poly aluminium iron silicate 40, the rare propyl ammonium chloride 25 of polydimethyl two, sodium bicarbonate 5.
Embodiment 1-5, in the present embodiment, the preparation process of multiple-effect water conditioner, as embodiment 1-1, only adjusts to some extent in the proportioning of each component.
The parts by weight of each component are as follows: acrylamide oligomers grafted graphene oxide 2, polyacrylamide 10, poly aluminium iron silicate 40, the rare propyl ammonium chloride 14 of polydimethyl two, sodium bicarbonate 2.
(2) the former water of multiple-effect water conditioner process.
1. former water parameter: pH:7.51, turbidity (NTU): 75.6; COD(mg/L): 58.05; Colourity: 240 times; Temperature: room temperature.
2. experiment condition: get 5 beakers and contain into former water 1L respectively, 200rpm rapid stirring 30s, 30s terminates to add the water conditioner 200mg configured in embodiment 1-1 to 1-5 respectively in rear 5 beakers, change rotating speed 40rpm, stir 15min, after low rate mixing terminates, stop stirring, liquid leaves standstill, and after flocculation terminates, under getting liquid level, 2cm place water quality detects.
3. experimental result: corresponding to the water sample of the water conditioner process configured in embodiment 1-1 to 1-5, be labeled as result 2-1 to 2-5, design parameter list is see table 1.
Table 1
Known by above-mentioned experimental data, the removal efficiency adopting multiple-effect water conditioner of the present invention can realize turbidity, COD and colourity entirety improves, and wherein, turbidity removal rate is up to the clearance of 92.86%, COD up to 96.38%, and chroma removal rate is up to 93.75%.
(3) impact of original sub-block technique.
In following experiment, the flocculation basin capacity of employing is 100 cubes of standard analog ponds, controls overall water intake velocity 20 cubic meters/hour, and entirety goes out water speed 20 cubic meters/hour.
Embodiment 3-1.
A. mix stages: former water is introduced mixing pit, adds the multiple-effect water conditioner in embodiment 1-1, mix;
B. the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds multiple-effect water conditioner described above in flow process, again flocculate in the second flocculation basin;
C ' refluxing stage: the lower layer of water after initial flocculation in step B is passed back into mixing pit.
D. filtration stage: the water again flocculated in step C is filtered by filter plant.
In steps A, multiple-effect water conditioner adds the amount of former water is 200mg/L; In step c, multiple-effect water conditioner adds the amount of water is 100mg/L.
Embodiment 3-2.
A. mix stages: former water is introduced mixing pit, adds the multiple-effect water conditioner in embodiment 1-1, mix;
B. the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds multiple-effect water conditioner described above in flow process, again flocculate in the second flocculation basin;
D. filtration stage: the water again flocculated in step C is filtered by filter plant.
In steps A, multiple-effect water conditioner adds the amount of former water is 200mg/L; In step c, multiple-effect water conditioner adds the amount of water is 100mg/L.
Embodiment 3-3.
A. mix stages: former water is introduced mixing pit, adds the multiple-effect water conditioner in embodiment 1-1, mix;
B. the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds multiple-effect water conditioner described above in flow process, again flocculate in the second flocculation basin;
C ' refluxing stage: the lower layer of water after initial flocculation in step B is passed back into mixing pit.
D. filtration stage: the water again flocculated in step C is filtered by filter plant.
In steps A, multiple-effect water conditioner adds the amount of former water is 150mg/L; In step c, multiple-effect water conditioner adds the amount of water is 150mg/L.
Embodiment 3-4.
A. mix stages: former water is introduced mixing pit, adds the multiple-effect water conditioner in embodiment 1-1, mix;
B. the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds multiple-effect water conditioner described above in flow process, again flocculate in the second flocculation basin;
C ' refluxing stage: the lower layer of water after initial flocculation in step B is passed back into mixing pit.
D. filtration stage: the water again flocculated in step C is filtered by filter plant.
In steps A, multiple-effect water conditioner adds the amount of former water is 250mg/L; In step c, multiple-effect water conditioner adds the amount of water is 50mg/L.
Comparative example 3-5.
A. mix stages: former water is introduced mixing pit, adds the multiple-effect water conditioner in embodiment 1-1, mix;
B. flocculated stage: the water after mixing in steps A is introduced the first flocculation basin and flocculates;
C. filtration stage: the water flocculated in step B is filtered by filter plant.
In steps A, multiple-effect water conditioner adds the amount of former water is 300mg/L.
Experimental result: corresponding to the water technology of embodiment 3-1 to 3-4, comparative example 3-5, before and after process, the design parameter list of water is see table 2.
Table 2:
Known by above-mentioned experimental data, (1) compared to a flocculating settling technique, adopt secondary flocculating settling technique effectively can improve water treatment capacity, water conditioner addition in suitable adjustment initial flocculation and again flocculation process can realize the adjustment to water treatment efficiency, under former regimen condition complicated situation, be conducive to technique adjustment and realize usefulness raising; (2) under same process step, the lower layer of water technique of backflow clearance to the turbidity of former water, COD, colourity is adopted all to be significantly improved.
Claims (4)
1. a multiple-effect water conditioner, is characterized in that, comprises the following component with weight parts:
Acrylamide oligomers grafted graphene oxide: 2 ~ 10,
Polyacrylamide: 5 ~ 40,
Poly aluminium iron silicate: 20 ~ 40
The rare propyl ammonium chloride of polydimethyl two: 3 ~ 25
Sodium bicarbonate: 1 ~ 5.
2. multiple-effect water conditioner according to claim 1, it is characterized in that, described acrylamide oligomers grafted graphene oxide comprises graphene oxide 3 ~ 10wt% and acrylamide oligomers 90 ~ 97wt%, and described acrylamide oligomers molecular weight is 5000 ~ 20000.
3. a preparation method for the multiple-effect water conditioner according to claim 1-2, is characterized in that, comprise the following steps:
(1) graphene oxide is carboxylated
In the graphene oxide water solution of 1 ~ 10mg/mL, add sodium hydroxide and Mono Chloro Acetic Acid, hybrid reaction 1 ~ 10 hour, be separated, wash, obtain carboxylated graphene oxide;
(2) acrylamide oligomers grafted graphene oxide
In DMSO, mixed oxidization Graphene and acrylamide oligomers, add EDCI, back flow reaction at 45 DEG C, is separated, washs, obtain acrylamide oligomers grafted graphene oxide;
(3) preparation of multiple-effect water conditioner
More than 45 DEG C, acrylamide oligomers grafted graphene oxide, polyacrylamide, the rare propyl ammonium chloride of polydimethyl two are mixed in proportion also Temperature fall and, to room temperature, add poly aluminium iron silicate, sodium bicarbonate successively, mix.
4. a method for water treatment, is characterized in that, at least comprises the steps:
A. mix stages: former water is introduced mixing pit, adds the multiple-effect water conditioner as described in claim 1-3, mix;
B. the initial flocculation stage: the water after mixing in steps A is introduced the first flocculation basin and carries out initial flocculation;
C. flocculated stage again: the upper water after initial flocculation in step B is introduced the second flocculation basin, adds the multiple-effect water conditioner as described in claim 1-3 in flow process, again flocculate in the second flocculation basin;
D. filtration stage: the water again flocculated in step C is filtered by filter plant.
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| CN201710655860.2A CN107265529A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710656407.3A CN107487820A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201510361037.1A CN105036269B (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710656005.3A CN107265530A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710655820.8A CN107337297A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710656408.8A CN107487821A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
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| CN201710656407.3A Division CN107487820A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710656408.8A Division CN107487821A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710656005.3A Division CN107265530A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710655820.8A Division CN107337297A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
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| CN201710656408.8A Withdrawn CN107487821A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710656407.3A Withdrawn CN107487820A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710656005.3A Withdrawn CN107265530A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
| CN201710655820.8A Pending CN107337297A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
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| CN201710656407.3A Withdrawn CN107487820A (en) | 2015-06-27 | 2015-06-27 | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water |
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| CN109516535A (en) * | 2017-09-19 | 2019-03-26 | Tcl集团股份有限公司 | Flocculant and preparation method thereof |
| CN109439298A (en) * | 2018-10-15 | 2019-03-08 | 中国石油集团工程技术研究院有限公司 | The water-base drilling fluid sealing agent and its drilling fluid of a kind of anticalcium resistant to high temperatures protection oil and gas reservoir and application |
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Also Published As
| Publication number | Publication date |
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| CN105036269B (en) | 2017-09-29 |
| CN107487821A (en) | 2017-12-19 |
| CN107265530A (en) | 2017-10-20 |
| CN107265529A (en) | 2017-10-20 |
| CN107337297A (en) | 2017-11-10 |
| CN107487820A (en) | 2017-12-19 |
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