CN104556335A - Graft modified natural polymer flocculant as well as preparation method and applications thereof - Google Patents
Graft modified natural polymer flocculant as well as preparation method and applications thereof Download PDFInfo
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- CN104556335A CN104556335A CN201510043052.1A CN201510043052A CN104556335A CN 104556335 A CN104556335 A CN 104556335A CN 201510043052 A CN201510043052 A CN 201510043052A CN 104556335 A CN104556335 A CN 104556335A
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- acrylamide
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- sodium alginate
- ammonium chloride
- dimethyl diallyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920005615 natural polymer Polymers 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 46
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 38
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 38
- 239000000661 sodium alginate Substances 0.000 claims abstract description 38
- 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 abstract description 27
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims description 26
- 238000012986 modification Methods 0.000 claims description 25
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000008394 flocculating agent Substances 0.000 claims description 22
- 229920002521 macromolecule Polymers 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- 238000005189 flocculation Methods 0.000 claims description 15
- 230000016615 flocculation Effects 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000000701 coagulant Substances 0.000 description 12
- 239000005995 Aluminium silicate Substances 0.000 description 11
- -1 dimethyl diene Chemical class 0.000 description 7
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000004021 humic acid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000003311 flocculating effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- 241000199919 Phaeophyceae Species 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
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 relates to a graft modified natural polymer flocculant as well as a preparation method and applications thereof. The flocculant is prepared by graft copolymerization of sodium alginate (SA), acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC), wherein the mass ratio of sodium alginate (SA), acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) is 1:(1-5) (1-5). The flocculant applied to a water treatment field has the advantages of simple production process, economy, wide application scope, safety and no toxicity, and has a good water treatment effect.
Description
Technical field:
The present invention relates to composite natural polymeric flocculant (SA-AM-DMDAAC) of graft acrylamide and dimethyl diene third class ammonium chloride and preparation method thereof and application, belong to environmental chemistry water conditioner technical field.
Background technology:
Developing rapidly of industrial or agricultural, population increase, the water resources that the mankind depend on for existence is day by day poor.Water resources crisis has become the important factor of restriction China Economic development.At present, China's water resources receives pollution in various degree, and has increasing trend.In order to saving water resource, improve the utilization ratio of water, alleviate waste water pollution on the environment, we must strengthen the improvement to trade effluent and sanitary sewage.In water technology, coagulating sedimentation to apply the most generally, the most extensively and lower-cost key technique, it decides the operation condition of follow-up flow process, final outflow water water quality and running cost, thus becomes one of research contents important in field of environment engineering.The quality of coagulating treatment effect depends on the quality of coagulating agent to a great extent.Therefore, novel, efficient flocculation agent is the mainstay industry given priority in water treatment environmental technology field all the time, is also the basic industry that water and wastewater industry and water pollution control engineering and develop develop.Although can improve coagulation effect by increasing added amount of chemical, interpolation coagulant aids etc., still there is all many-sided restrictions to pollutant removal in it, therefore development of new coagulant is very necessary.
Inorganic coagulant mainly comprises aluminium system and ferric flocculant, its applicating history is long, be widely used in the desliming process etc. of water purification process and sewage, there is turbidity removal decoloring ability strong, to removal efficiency advantages of higher, but low-molecular inorganic coagulating agent cost is higher, and corrodibility is larger, also there is toxicity problem in Al-based coagulant, undesirable at some occasion purifying water effect.Compared with inorganic coagulant, organic coagulants consumption is few, and coagulation speed is fast, salt, medium and the ambient temperature effect of being coexisted is little, treating processes is short, and the sludge quantity of generation is few, is at home and abroad widely used in the process of the waste water such as oil, printing and dyeing, food, chemical industry, papermaking.But it is worth costliness, and mostly coagulating agent itself or its be hydrolyzed, degraded product is poisonous, application is subject to certain restrictions.
Sodium alginate is a kind of compound of polysaccharide extracted from the sea-tangle or sargassun of phaeophyta, has that raw material is easy to get, the feature of cheap and safety non-toxic.When being used alone sodium alginate, the Ca in water body
2+concentration must reach more than finite concentration, the superperformance of sodium alginate could effectively play, and when in water body, Pollutant levels are lower, its effect is unsatisfactory, the shortcoming of existence is used alone for sodium alginate, utilize the amido group with positive electricity to carry out modification to the hydroxyl on sodium alginate molecule, modified sodium alginate will have stronger coagulability.In current bibliographic data base at home and abroad, report there are no pertinent literature.
Summary of the invention:
In order to overcome the deficiency of existing organic natural polymer coagulating agent technology, the invention provides natural macromolecule flocculating agent of a kind of graft modification and preparation method thereof and application.The present invention is graft acrylamide (AM) and dimethyl diene third class ammonium chloride (DMDAAC) on the basis of existing natural polymer coagulant aids sodium alginate (SA), modification is carried out to existing SA, obtains a kind of macromolecular grafted acrylamide of composite natural and dimethyl diallyl ammonium chloride flocculation agent (SA-AM-DMDAAC) of high efficiency low cost.
Raw material illustrates:
One of the raw material that the present invention adopts sodium alginate (SA) is a kind of polysaccharide carbohydrate extracted from the sea-tangle or sargassun of phaeophyta, and itself does not possess flocculating effect, in water treatment, be often used as coagulant aids.SA is a kind of polysaccharose substance, containing great amount of hydroxy group and carboxyl in molecule, with-COO
-form exist, therefore itself is with negative charge.Sodium alginate (SA) can utilize conventional commercial products, also can extract by prior art and obtain.
Technical scheme of the present invention is as follows:
A kind of graft modification natural macromolecule flocculating agent, this flocculation agent is obtained by sodium alginate (SA), acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) graft copolymerization, and the mass ratio of sodium alginate (SA), acrylamide (AM) and dimethyl diallyl ammonium chloride (DMDAAC) is 1:(1 ~ 5): (1 ~ 5).
According to the present invention, preferably, described graft modification natural macromolecule flocculating agent has following structure:
Acrylamide substituted for the hydroxyl in sodium alginate, then dimethyl diallyl ammonium chloride again with the acrylamide graft in grafting, material is thus formed terpolymer.
According to the present invention, the preparation method of above-mentioned graft modification natural macromolecule flocculating agent, comprises step as follows:
(1) by sodium alginate and deionized water mixing, then add the acrylamide of dimethyl diallyl ammonium chloride and half reacting weight, mix, maintaining nitrogen purge 15 ~ 30min removes the oxygen in mixture;
In 40 ~ 60 DEG C and maintaining nitrogen purge, in mixture, add ammonium persulfate initiator initiation reaction 10 ~ 20min, then remaining half acrylamide to be dissolved in deionized water and dropwise to join in mixture; After having added, stop logical nitrogen and seal stirring reaction 2 ~ 6h;
In whole process, the quality of described sodium alginate, dimethyl diallyl ammonium chloride, acrylamide and the volume ratio of deionized water are 1g:(1 ~ 5) g:(1 ~ 5) g:(80 ~ 150) ml;
Described ammonium persulfate initiator add-on is 2 ~ 10mmol/L;
(2) after reaction terminates, product is cooled to room temperature, adds excessive propanone and stir and separate out precipitation, filter, by solid drying, to obtain final product.
According to the present invention, acrylamide adds at twice, and this method claims batch addition method, and after adding initiator, remaining acrylamide instills with the speed of 1 ~ 5mL/min.When highly active acrylamide monomer adds continuously, graft copolymerization is easier, and therefore the amount of the homopolymer of acrylamide can reduce, and adds speed by what control acrylamide, can obtain the composition that SA-AM-DMDAAC is constant.
According to the present invention, preferably, the temperature of reaction in step (1) is 45 ~ 50 DEG C, more preferably 45 DEG C;
Preferably, the described reaction times is 3 ~ 5h, more preferably 4h;
Preferably, in whole process, the quality of described sodium alginate, dimethyl diallyl ammonium chloride, acrylamide and the volume ratio of deionized water are 1g:(2 ~ 4) g:(2 ~ 4) g:100ml, more preferably 1g:3g:3g:100ml;
Preferably, described ammonium persulfate initiator add-on is 4 ~ 8mmol/L, more preferably 6mmol/L;
Preferably, second time acrylamide add rate-controlling at 1 ~ 5mL/min.
According to the present invention, preferably, in step (2), drying temperature is 45 ~ 55 DEG C, and time of drying is 12 hours.
According to the present invention, the application in the coagulating treatment of described graft modification natural macromolecule flocculating agent waste water, preferred dosage is 4 ~ 24mg/L.
Principle of the present invention:
Graft modification natural macromolecule flocculating agent of the present invention is acrylamide and dimethyl diallyl ammonium chloride in grafting in sodium alginate, and reaction process is as follows:
Graft modification polymeric flocculant is the dual function of charge neutrality and adsorption bridging to removal dominant mechanism organic in humic acid-Kaolin water sample, SA by the acrylamide of grafting positively charged and dimethyl diallyl ammonium chloride itself with certain positive charge, can with simulated water sample in be with the organism generation charge neutrality effect of negative point, thus realize organic removal, SA-AM-DMDAAC has molecular weight larger comparatively speaking, its hydrolysate can be good with group in humic acid combination, thus improve the clearance to Organic substance in water.
Technical characterstic of the present invention and excellent results:
1, the present invention utilize natural polymer sodium alginate (SA) with hydroxyl (-OH group) and carboxyl (-COO
-polar group), by graft copolymerization acrylamide and dimethyl diallyl ammonium chloride, modification is carried out to SA, prepare the SA-AM-DMDAAC flocculation agent that not only there is good storage stability but also there is good flocculating effect, provide a kind of new and effective, nontoxic, inexpensive modified natural polymer flocculation agent.
2, graft modification natural macromolecule flocculating agent of the present invention, acrylamide and dimethyl diallyl ammonium chloride due to grafting, overcome sodium alginate electronegativity to a certain extent strong, water treatment efficiency is not good enough, and polyacrylamide flocculant (PAM) and Poly Dimethyl Diallyl Ammonium Chloride (PDMDAAC) is on the high side, the pollution of residual monomer, use by the shortcoming such as various condition restrictions.
3, graft modification natural macromolecule flocculating agent of the present invention, have more excellent flocculating property, and the current potential of SA-AM-DMDAAC increases than homopolymerization PAM and PDMDAAC of same molecular amount, when coagulating treatment waste water, presents good coagulation effect.
4, to have product stability good for graft modification natural macromolecule flocculating agent of the present invention, and flocculating effect is good, and water treatment efficiency is high, and use range is wide, the features such as mud generation is little, can be widely used in feedwater, wastewater treatment have good water treatment efficiency.
5, graft modification natural macromolecule flocculating agent of the present invention toxicological harmless, production method technique is simple, and reaction conditions is gentle, is easy to realize suitability for industrialized production.
Embodiment:
Below in conjunction with specific embodiment, the present invention will be further described, but institute of the present invention protection domain is not limited thereto.
Raw material used in embodiment is conventional commercial products.Wherein: sodium alginate, Tianjin great Mao chemical reagent factory, range of viscosities 1.05-1.15Pa.s; Ammonium persulphate, Tianjin Guang Cheng chemical reagent company limited, purity >99.5% is analytical pure; Acrylamide, Chemical Reagent Co., Ltd., Sinopharm Group, purity >=98.0%, chemical pure; Dimethyl diallyl ammonium chloride, Aladdin reagent company limited, the 60wt% aqueous solution; Acetone, Tianjin Fu Yu Fine Chemical Co., Ltd is on sale, is analytical pure.
Initiator ammonium persulfate in embodiment is mixed with the ammonium persulfate solution of 20g/L, according to the concentration of ammonium persulphate in reaction soln, is added in reaction system by the ammonium persulfate solution of certain volume.
The preparation of graft modification natural macromolecule flocculating agent SA-AM-DMDAAC under embodiment 1, different initiator amount condition, comprises step as follows:
(1) natural sea sodiun alginate SA1.0g is taken, and add 100mL deionized water at the temperature of 50 DEG C and fully stir, after sodium alginate is completely water-soluble, add and be equipped with in the reactor of whipping appts, nitrogen protection, after in question response device, oxygen drains, add 1.5g acrylamide (participating in the half of reaction mass) and the acrylonitrile-chlorinated ammonium mixing solutions of 3mL dimethyl diene, continue logical nitrogen 15min, oxygen in removing reactor, add initiator ammonium persulfate, the concentration of initiator in reaction system is made to be respectively 2, 4, 6, 8, 10mmol/L, 15min is caused under the condition of maintaining nitrogen purge, then by water-soluble for the acrylamide of remaining 1.5g, dropwise add in reactor, then logical nitrogen 30min, at 50 DEG C, continue reaction 4 hours.
(2) reaction terminates, and product is cooled to room temperature, adds excessive propanone and stirs, and product is separated out, and suction filtration gets filter residue, then washes three times with acetone, vacuum-drying 12 hours at 45 DEG C, obtains five products that initiator dosage is different.
The structure of the graft modification natural macromolecule flocculating agent that the present embodiment obtains is as follows:
The preparation of the graft modification natural macromolecule flocculating agent (SA-AM-DMDAAC) of embodiment 2, different acrylamide addition:
Identical with described in embodiment 1, difference is that the amount of initiator is fixed as 6mmol/L, and in whole process, the amount of acrylamide is respectively 1g, 2g, 3g, 4g, 5g, obtains the flocculant product that acrylamide addition is different.
The preparation of the graft modification natural macromolecule flocculating agent (SA-AM-DMDAAC) of embodiment 3, different dimethyl diallyl ammonium chloride addition:
Identical with described embodiment 2, difference is that the amount of acrylamide in whole process is fixed as 3g, the addition of the acrylonitrile-chlorinated ammonium of dimethyl diene is respectively 1mL, 2mL, 3mL, 4mL, 5mL, obtains the flocculant product that dimethyl diallyl ammonium chloride addition is different.
The preparation of graft modification natural macromolecule flocculating agent (SA-AM-DMDAAC) under embodiment 4, differing temps:
Identical with described embodiment 3, difference is that the addition of the acrylonitrile-chlorinated ammonium of dimethyl diene is fixed as 3mL, and temperature of reaction is respectively 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, obtains the flocculant product under differing temps.
Embodiment 5, the preparation of graft modification natural macromolecule flocculating agent (SA-AM-DMDAAC) under the differential responses time:
Identical with described embodiment 4, difference is that the temperature of reaction is fixed as 45 DEG C, and the reaction times is respectively 2h, 3h, 4h, 5h, 6h, obtains the flocculant product under the differential responses time.
Application test: the preparation of humic acid-Kaolin water sample:
Humic acid storing solution: take 1.0g humic acid and 0.4g sodium hydroxide, add in the deionized water of about about 800ml, Keep agitation 0.5h, is settled to 1L, is namely made into the humic acid storing solution of 1g/L.
Aqueous suspension ofkaolin: take 5g kaolin, adds Keep agitation 0.5h in the deionized water of 1L, has stirred and be transferred in the graduated cylinder of 1L, static 0.5h, and sucking-off top 500ml suspension liquid is with for subsequent use.
The preparation of coagulation experiment humic acid-Kaolin water sample: get deionized water and tap water that volume ratio is 1:1, add above-mentioned humic acid storing solution and aqueous suspension ofkaolin wherein, make humic acid concentration be 10mg/L, turbidity is 15.0 ± 0.5NTU.
The product prepared with embodiment 1-5 does flocculation agent process humic acid-Kaolin water sample, finally goes out water treatment efficiency with UV
254clearance (%) and DOC clearance (%) represent.
By the SA-AM-DMDAAC flocculant product process humic acid-Kaolin water sample in embodiment 1-5, experiment effect is as follows:
Application example 1: SA-AM-DMDAAC flocculation agent embodiment 1 prepared is used for the process of humic acid-Kaolin water sample, treatment effect is listed in the table below 1-1 and 1-2.
Table 1-1.UV
245clearance (%)
The clearance (%) of table 1-2.DOC
As can be seen from table 1-1 and 1-2, the coagulation effect of amount on product of initiator ammonium persulfate has impact, take 6mmol/L as optimum.
Application example 2, SA-AM-DMDAAC flocculation agent embodiment 2 prepared are used for the process of humic acid-Kaolin water sample, and treatment effect is listed in the table below 2-1 and 2-2.
Table 2-1.UV
245clearance (%)
The clearance (%) of table 2-2.DOC
As can be seen from table 2-1 and 2-2, the quality of the amount energy remarkably influenced sintetics of monomeric acrylamide, UV
254clearance is to add the flocculation agent best results of 4g acrylamide synthesis, and DOC clearance is to add the flocculation agent best results of 3g acrylamide.Because SA-AM-DMDAAC flocculant product of the present invention is originally as larger molecular organics matter, when reaction monomers concentration increases in certain limit, the polymerization degree also increases thereupon, also certain limit can be reached to clearance organic in Simulated Water, but the flocculation agent of the remainder do not played a role can have certain contribution to the organism in water, therefore, after the dosage of reaction monomers arrives certain value, the clearance of DOC reduces on the contrary.
Application example 3, SA-AM-DMDAA flocculation product embodiment 3 prepared are used for the process of humic acid-Kaolin water sample, and treatment effect sees following table 3-1 and 3-2.
Table 2-1.UV
245clearance (%)
The clearance (%) of table 2-2.DOC
As can be seen from table 3-1 and 3-2, the amount of monomer diallyldimethylammonChloride Chloride can affect the coagulation effect of product, effect with monomeric acrylamide is the same, add and the flocculation agent of the remainder do not played a role too much can be caused to have certain contribution to the organism in water, same after reaction monomers exceedes certain value, the clearance of DOC reduces on the contrary.As can be seen from table 3-1 and 3-2, the addition of the acrylonitrile-chlorinated ammonium of best dimethyl diene is 3mL.
Application example 4, SA-AM-DMDAA flocculation product embodiment 4 prepared are used for the process of humic acid-Kaolin water sample, and treatment effect sees following table 4-1 and 4-2.
Table 4-1.UV
245clearance (%)
The clearance (%) of table 4-2.DOC
Can find out too low the carrying out being unfavorable for reacting of temperature of reaction by table 4-1 and 4-2, but when temperature also can affect quality product higher than certain limit, the present invention is optimum with 45 DEG C.
Application example 5, the SA-AM-DMDAAC flocculant product embodiment 5 prepared are for the treatment of humic acid-Kaolin water sample, and treatment effect is listed in the table below 5-1 and 5-2.
Table 5-1UV
245clearance (%)
The clearance (%) of table 5-2.DOC
Can find out that the reaction times of the present invention should not be too short by table 5-1 and 5-2, take 4h as optimum, reaction times long quality product has decline by a small margin.
Claims (10)
1. a graft modification natural macromolecule flocculating agent, it is characterized in that, this flocculation agent is obtained by sodium alginate, acrylamide and dimethyl diallyl ammonium chloride graft copolymerization, and the mass ratio of sodium alginate, acrylamide and dimethyl diallyl ammonium chloride is 1:(1 ~ 5): (1 ~ 5).
2. graft modification natural macromolecule flocculating agent according to claim 1, is characterized in that, described graft modification natural macromolecule flocculating agent has following structure:
n＝2～10，m＝5～25。
3. a preparation method for the graft modification natural macromolecule flocculating agent described in claim 1 or 2, comprises step as follows:
(1) by sodium alginate and deionized water mixing, then add the acrylamide of dimethyl diallyl ammonium chloride and half reacting weight, mix, maintaining nitrogen purge 15 ~ 30min removes the oxygen in mixture;
In 40 ~ 60 DEG C and maintaining nitrogen purge, in mixture, add ammonium persulfate initiator initiation reaction 10 ~ 20min, then remaining half acrylamide to be dissolved in deionized water and dropwise to join in mixture; After having added, stop logical nitrogen and seal stirring reaction 2 ~ 6h;
In whole process, the quality of described sodium alginate, dimethyl diallyl ammonium chloride, acrylamide and the volume ratio of deionized water are 1g:(1 ~ 5) g:(1 ~ 5) g:(80 ~ 150) ml;
Described ammonium persulfate initiator add-on is 2 ~ 10mmol/L;
(2) after reaction terminates, product is cooled to room temperature, adds excessive propanone and stir and separate out precipitation, filter, by solid drying, to obtain final product.
4. preparation method according to claim 3, is characterized in that, the temperature of reaction in step (1) is 45 ~ 50 DEG C.
5. preparation method according to claim 3, is characterized in that, the reaction times described in step (1) is 3 ~ 5h.
6. preparation method according to claim 3, it is characterized in that, in step (1), in whole process, the quality of described sodium alginate, dimethyl diallyl ammonium chloride, acrylamide and the volume ratio of deionized water are 1g:(2 ~ 4) g:(2 ~ 4) g:100ml.
7. preparation method according to claim 3, is characterized in that, the ammonium persulfate initiator add-on described in step (1) is 4 ~ 8mmol/L.
8. preparation method according to claim 3, is characterized in that, in step (1), second time acrylamide adds rate-controlling at 1 ~ 5mL/min.
9. preparation method according to claim 3, is characterized in that, in step (2), drying temperature is 45 ~ 55 DEG C.
10. the application of graft modification natural macromolecule flocculating agent in the coagulating treatment of waste water described in claim 1 or 2.
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