CN104556335B - A kind of graft modification natural macromolecule flocculating agent and preparation method and application - Google Patents
A kind of graft modification natural macromolecule flocculating agent and preparation method and application Download PDFInfo
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- CN104556335B CN104556335B CN201510043052.1A CN201510043052A CN104556335B CN 104556335 B CN104556335 B CN 104556335B CN 201510043052 A CN201510043052 A CN 201510043052A CN 104556335 B CN104556335 B CN 104556335B
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- 230000004048 modification Effects 0.000 title claims abstract description 22
- 238000012986 modification Methods 0.000 title claims abstract description 22
- 239000008394 flocculating agent Substances 0.000 title claims abstract description 20
- 229920002521 macromolecule Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 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 38
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 37
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 37
- 239000000661 sodium alginate Substances 0.000 claims abstract description 37
- 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 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- 239000003999 initiator 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 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000004044 response Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010926 purge Methods 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
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 210000005056 cell body Anatomy 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 239000005995 Aluminium silicate Substances 0.000 description 10
- 239000000701 coagulant Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- -1 dimethyl diene Chemical class 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 6
- 230000016615 flocculation Effects 0.000 description 6
- 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 5
- 239000004021 humic acid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000001112 coagulating effect Effects 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000003311 flocculating effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920005615 natural polymer Polymers 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
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000003863 ammonium salts Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000199919 Phaeophyceae Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 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
- 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
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing 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
- 238000012545 processing Methods 0.000 description 1
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 description 1
- PYNUOAIJIQGACY-UHFFFAOYSA-N propylazanium;chloride Chemical compound Cl.CCCN PYNUOAIJIQGACY-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 239000010865 sewage Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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 present invention relates to a kind of graft modification natural macromolecule flocculating agent and preparation method and application, this flocculant is to be prepared 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).Being applied to water treatment field, to have production technology simple and direct, economical, applied widely, and the advantage of safety non-toxic has good water treatment efficiency.
Description
Technical field:
The present invention relates to graft acrylamide and the composite natural high polymer coagulant of dimethyl diene third class ammonium chloride
(SA-AM-DMDAAC) and preparation method and application, belong to Environmental Chemistry water treatment agent technical field.
Background technology:
Developing rapidly of industrial or agricultural, population increase, the water resource that the mankind depend on for existence is the poorest.Water resources crisis has become system
The about key factor of China's economic development.At present, China's water resource receives pollution in various degree, and have increasing become
Gesture.For saving water resource, improving the utilization rate of water, alleviate waste water pollution on the environment, we must strengthen industry
Waste water and the improvement of sanitary sewage.In water treatment technology, coagulating sedimentation is to apply the most generally, the most extensively and cost is relatively low
Key technique, it decides the operating condition of follow-up flow process, final outflow water water quality and operating cost, thus becomes environment
One of research contents important in engineering field.The quality of coagulating treatment effect depends greatly on the quality of coagulant.
Therefore, flocculant novel, efficient is that water processes the pillar industry given priority in environmental technology field all the time, is also water and wastewater industry
Basic industry with water pollution control engineering Yu equipment innovation and development.Although by increasing added amount of chemical, adding flocculation aid
Etc. can improve coagulation effect, but still there is all many restrictions in it to pollutant removal, therefore develops new and effective mixed
Solidifying agent is the most necessary.
Inorganic coagulant mainly includes aluminum system and ferric flocculant, and its applicating history is long, is widely used in water purification and processes and dirty
The desliming process etc. of water, has turbidity removal decoloring ability strong, and to removal efficiency advantages of higher, but low-molecular inorganic coagulant becomes
This is higher, and corrosivity is relatively big, and Al-based coagulant there is also toxicity problem, undesirable at some occasion purifying water effect.Mixed with inorganic
Solidifying agent is compared, and organic coagulants consumption is few, and coagulation speed is fast, and the salt that coexisted, medium and ambient temperature effect are little, process
Journey 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 coagulant itself or its hydrolyze, catabolite poisonous, application is subject to certain restrictions.
Sodium alginate be the Thallus Laminariae (Thallus Eckloniae) from Brown algae or Alga Sgrgassi Enerves extract a kind of compound of polysaccharide, have raw material be easy to get, price low
The honest and clean feature with safety non-toxic.Ca when being used alone sodium alginate, in water body2+Concentration must reach more than finite concentration,
The superperformance of sodium alginate could effectively play, and when in water body, pollutant levels are relatively low, its effect is unsatisfactory, pin
The shortcoming that sodium alginate is used alone existence, utilizes the amido group with positive electricity to change the hydroxyl on sodium alginate molecule
Property, modified sodium alginate will have higher coagulability.The most at home and abroad in bibliographic data base, there are no relevant literary composition
Offer report.
Summary of the invention:
In order to overcome the deficiency of existing organic natural polymer coagulant technology, the present invention provides the natural of a kind of graft modification
High polymer coagulant and preparation method and application.The present invention is existing natural polymer flocculation aid sodium alginate (SA)
On the basis of graft acrylamide (AM) and dimethyl diene third class ammonium chloride (DMDAAC), existing SA is carried out
Modified, it is thus achieved that the macromolecular grafted acrylamide of composite natural of a kind of high efficiency low cost and dimethyl diallyl ammonium chloride wadding
Solidifying agent (SA-AM-DMDAAC).
Raw material illustrates:
One of the raw material that the present invention uses sodium alginate (SA) is the one extracted the Thallus Laminariae (Thallus Eckloniae) from Brown algae or Alga Sgrgassi Enerves
Polysaccharide carbohydrate, itself does not possess flocculating effect, is often used as flocculation aid in water processes.SA is a kind of polysaccharide
Class material, containing great amount of hydroxy group and carboxyl in molecule, with-COO-Presented in, therefore per se with negative charge.Sea
The available conventional commercial products of sodium alginate (SA), it is possible to extract by prior art and obtain.
Technical scheme is as follows:
A kind of graft modification natural macromolecule flocculating agent, this flocculant is by sodium alginate (SA), acrylamide (AM)
Prepare with dimethyl diallyl ammonium chloride (DMDAAC) graft copolymerization, sodium alginate (SA), acrylamide (AM)
It is 1:(1～5 with the mass ratio of dimethyl diallyl ammonium chloride (DMDAAC)): (1～5).
According to the invention it is preferred to, described graft modification natural macromolecule flocculating agent has a following structure:
N=2～10, m=5～25.
Acrylamide substituted for the hydroxyl in sodium alginate, then dimethyl diallyl ammonium chloride again with the propylene in grafting
Acid amide-grafted, material is thus formed terpolymer.
According to the present invention, the preparation method of above-mentioned graft modification natural macromolecule flocculating agent, comprise the following steps that
(1) sodium alginate and deionized water are mixed, add dimethyl diallyl ammonium chloride and the third of half response magnitude
Acrylamide, mix homogeneously, maintaining nitrogen purge 15～30min removes the oxygen in mixed material；
In 40～60 DEG C and maintaining nitrogen purge, in mixed material, add ammonium persulfate initiator initiation reaction 10～20min,
Then remaining half acrylamide is dissolved in deionized water and is added dropwise in mixed material；After having added,
Stop logical nitrogen and seal stirring reaction 2～6h；
During whole, described sodium alginate, dimethyl diallyl ammonium chloride, the quality of acrylamide and deionization
The volume ratio of water is 1g:(1～5) g:(1～5) g:(80～150) ml；
Described ammonium persulfate initiator addition is 2～10mmol/L；
(2) after reaction terminates, product is cooled to room temperature, adds excessive propanone and stir precipitation precipitation, filtering, will be solid
Soma is dry, to obtain final product.
According to the present invention, acrylamide adds at twice, and this method claims batch addition method, after adding initiator, surplus
Under acrylamide with 1～5mL/min speed instill.When highly active acrylamide monomer is continuously added to, graft copolymerization
Reaction is easier to, and therefore the amount of the homopolymer of acrylamide can reduce, and by controlling the addition speed of acrylamide,
The constant composition of SA-AM-DMDAAC can be obtained.
According to the invention it is preferred to, the reaction temperature in step (1) is 45～50 DEG C, more preferably 45 DEG C；
Preferably, the described response time is 3～5h, more preferably 4h；
Preferably, whole during, described sodium alginate, dimethyl diallyl ammonium chloride, the quality of acrylamide
It is 1g:(2～4 with the volume ratio of deionized water) g:(2～4) g:100ml, more preferably 1g:3g:3g:100ml；
Preferably, described ammonium persulfate initiator addition is 4～8mmol/L, more preferably 6mmol/L；
Preferably, for the second time the addition rate controlled of acrylamide 1～5mL/min.
According to the invention it is preferred to, in step (2), baking temperature is 45～55 DEG C, and drying time is 12 hours.
According to the present invention, the application in the coagulating treatment of described graft modification natural macromolecule flocculating agent waste water, preferably
Dosage is 4～24mg/L.
The principle of the present invention:
The graft modification natural macromolecule flocculating agent of the present invention is to be grafted acrylamide and dimethyl diene in sodium alginate
Propyl ammonium chloride, course of reaction is as follows:
N=2～10, m=5～25.
Graft modification high polymer coagulant is in electricity to removal dominant mechanism organic in humic acid-Kaolin water sample
With and the dual function of adsorption bridging, SA is by the grafting acrylamide of positively charged and dimethyl diallyl ammonium chloride itself
With certain positive charge, it is possible to the Organic substance generation charge neutrality effect of point negative with band in simulated water sample, thus realize having
The removal of machine thing, SA-AM-DMDAAC has the biggest molecular weight, its hydrolyzate can and rotten
Grow the combination that group in acid is good, thus improve the clearance to Organic substance in water.
The 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, SA is modified, both prepares
There is good bin stability there is again the SA-AM-DMDAAC flocculant of good flocculating effect, it is provided that Yi Zhongxin
The modified natural polymer flocculant that type is efficient, nontoxic, inexpensive.
2, the graft modification natural macromolecule flocculating agent of the present invention, owing to being grafted acrylamide and dimethyl diallyl chlorine
Changing ammonium, overcome sodium alginate elecrtonegativity to a certain extent strong, water treatment efficiency is not good enough, and polyacrylamide flocculation
Agent (PAM) and PDDA (PDMDAAC) is on the high side, the pollution of residual monomer, make
With by shortcomings such as various conditions are limited.
3, the graft modification natural macromolecule flocculating agent of the present invention, than homopolymerization PAM and PDMDAAC of same molecular amount
There is more excellent flocculating property, and the current potential of SA-AM-DMDAAC increases, when coagulating treatment waste water, in
Reveal preferable coagulation effect.
4, to have product stability good for the graft modification natural macromolecule flocculating agent of the present invention, and flocculating effect is good, and water processes effect
Rate is high, and range is wide, the features such as mud generation amount is little, is widely portable to feedwater, waste water processes and has good water
Treatment effect.
5, the graft modification natural macromolecule flocculating agent nonhazardous of the present invention, production method technique is simple, and reaction condition is gentle,
It is easily achieved industrialized production.
Detailed description of the invention:
Below in conjunction with specific embodiment, the present invention will be further described, but institute of the present invention protection domain is not limited to this.
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 persulfate., Tianjin Guang Cheng chemical reagent company limited, purity > 99.5%, for dividing
Analyse pure；Acrylamide, Chemical Reagent Co., Ltd., Sinopharm Group, purity >=98.0%, chemical pure；Dimethyl two allyl
Ammonium chloride, Aladdin reagent company limited, 60wt% aqueous solution；Acetone, Tianjin Fu Yu Fine Chemical Co., Ltd
On sale, for analytical pure.
Initiator ammonium persulfate in embodiment is configured to the ammonium persulfate solution of 20g/L, molten in reaction according to Ammonium persulfate.
Concentration in liquid, adds the ammonium persulfate solution of certain volume in reaction system.
Graft modification natural macromolecule flocculating agent SA-AM-DMDAAC under the conditions of embodiment 1, different initiator amount
Preparation, comprise the following steps that
(1) weigh natural sea sodium alginate SA1.0g, and add 100mL deionized water and fully stir at a temperature of 50 DEG C
Mixing, after sodium alginate is completely soluble, be equipped with in the reactor of agitating device, nitrogen is protected, in question response device
After oxygen drains, add 1.5g acrylamide (participating in the half of reaction mass) and 3mL dimethyl diene is acrylonitrile-chlorinated
Ammonium mixed solution, continues logical nitrogen 15min, removes the oxygen in reactor, add initiator ammonium persulfate so that be anti-
Answer the concentration of initiator in system to be respectively 2,4,6,8,10mmol/L, under conditions of maintaining nitrogen purge, cause 15min,
Then the acrylamide of remaining 1.5g is dissolved in water, is added dropwise in reactor, then lead to 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, making product separate out, and sucking filtration takes filter
Slag, then wash three times with acetone, it is vacuum dried 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 prepares is as follows:
N=2～10, m=5～25.
Embodiment 2, the graft modification natural macromolecule flocculating agent (SA-AM-DMDAAC) of different acrylamide addition
Preparation:
Identical with described in embodiment 1, except that the amount of initiator is fixed as 6mmol/L, whole during acryloyl
The amount of amine is respectively 1g, 2g, 3g, 4g, 5g, obtains the flocculant product that acrylamide addition is different.
Embodiment 3, the graft modification natural macromolecule flocculating agent of different dimethyl diallyl ammonium chloride addition
(SA-AM-DMDAAC) preparation:
It is identical with described embodiment 2, except that the amount of acrylamide is fixed as 3g, dimethyl two during whole
The addition of allyl alkene ammonium chloride is respectively 1mL, 2mL, 3mL, 4mL, 5mL, obtains dimethyl diallyl chlorine
Change the flocculant product that ammonium addition is different.
The preparation of graft modification natural macromolecule flocculating agent (SA-AM-DMDAAC) under embodiment 4, different temperatures:
It is identical with described embodiment 3, except that the addition of the acrylonitrile-chlorinated ammonium of dimethyl diene is fixed as 3mL, instead
Answer temperature to be respectively 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, obtain the flocculant product under different temperatures.
Embodiment 5, the system of graft modification natural macromolecule flocculating agent (SA-AM-DMDAAC) under the differential responses time
Standby:
Identical with described embodiment 4, except that reaction temperature be fixed as 45 DEG C, the response time be respectively 2h,
3h, 4h, 5h, 6h, obtain the flocculant product under the differential responses time.
Application test: the preparation of humic acid-Kaolin water sample:
Humic acid storing solution: weigh 1.0g humic acid and 0.4g sodium hydroxide, adds in the deionized water of about about 800ml,
Continuously stirred 0.5h, is settled to 1L, is i.e. made into the humic acid storing solution of 1g/L.
Aqueous suspension ofkaolin: weigh 5g Kaolin, adds continuously stirred 0.5h in the deionized water of 1L, has stirred and has turned
Moving in the graduated cylinder of 1L, static 0.5h, sucking-off top 500ml suspension is with standby.
The preparation of coagulation experiment humic acid-Kaolin water sample: take deionized water and tap water that volume ratio is 1:1, to
Wherein adding above-mentioned humic acid storing solution and aqueous suspension ofkaolin, making humic acid concentration is 10mg/L, and turbidity is
15.0±0.5NTU。
The product prepared with embodiment 1-5 makees flocculant and processes humic acid-Kaolin water sample, finally goes out water treatment efficiency
With UV254Clearance (%) and DOC clearance (%) represent.
SA-AM-DMDAAC flocculant product in embodiment 1-5 is processed humic acid-Kaolin water sample, real
Test effect as follows:
Application example 1: SA-AM-DMDAAC flocculant embodiment 1 prepared is used for humic acid-Kaolin
The process of water sample, treatment effect is listed in the table below 1-1 and 1-2.
Table 1-1.UV245Clearance (%)
The clearance (%) of table 1-2.DOC
By table 1-1 and 1-2 it can be seen that the coagulation effect of product is had an impact by the amount of initiator ammonium persulfate, with 6
Mmol/L is optimum.
Application example 2, SA-AM-DMDAAC flocculant embodiment 2 prepared are used for humic acid-Kaolin
The process of water sample, treatment effect is listed in the table below 2-1 and 2-2.
Table 2-1.UV245Clearance (%)
The clearance (%) of table 2-2.DOC
By table 2-1 and 2-2 it can be seen that the quality of the amount energy appreciable impact sintetics of monomeric acrylamide, UV254Remove
Rate is to add the flocculant best results of 4g acrylamide synthesis, and DOC clearance is to add the flocculant of 3g acrylamide
Best results.Because the SA-AM-DMDAAC flocculant product of the present invention is originally as larger molecular organics matter, when reaction is single
Bulk concentration is when certain limit increases, and the degree of polymerization is consequently increased, and the clearance of simulation Organic substance in water also can be reached a fixed limit
Degree, but the flocculant of the remainder not played a role can have certain contribution to the Organic substance in water, therefore single when reaction
After the dosage of body arrives certain value, the clearance of DOC reduces on the contrary.
Application example 3, SA-AM-DMDAA embodiment 3 prepared flocculation product is used for humic acid-Kaolin water sample
Process, treatment effect sees table 3 below-1 and 3-2.
Table 2-1.UV245Clearance (%)
The clearance (%) of table 2-2.DOC
By table 3-1 and 3-2 it can be seen that the amount of monomer diallyldimethylammonChloride Chloride can affect the coagulation effect of product,
Effect with monomeric acrylamide is the same, adds and too much can cause the flocculant of the remainder not played a role can be to water
In Organic substance have certain contribution, equally after reaction monomers exceedes certain value, the clearance of DOC reduces on the contrary.By
Table 3-1 and 3-2 is it can be seen that the addition of the optimal acrylonitrile-chlorinated ammonium of dimethyl diene is 3mL.
Application example 4, SA-AM-DMDAA embodiment 4 prepared flocculation product is used for humic acid-Kaolin
The process of water sample, treatment effect sees table 4 below-1 and 4-2.
Table 4-1.UV245Clearance (%)
The clearance (%) of table 4-2DOC
Too low the carrying out being unfavorable for reaction of reaction temperature is can be seen that by table 4-1 and 4-2, but when temperature is higher than certain limit
Also can affect product quality, the present invention is with 45 DEG C for optimum.
Application example 5, SA-AM-DMDAAC flocculant product embodiment 5 prepared are used for processing humic acid-kaolinite
Soil simulated water sample, treatment effect is listed in the table below 5-1 and 5-2.
Table 5-1.UV245Clearance (%)
The clearance (%) of table 5-2.DOC
Be can be seen that the present invention response time should not be the shortest by table 5-1 and 5-2, with 4h as optimum, the response time crosses long products
Quality has decline by a small margin.
Claims (7)
1. a preparation method for graft modification natural macromolecule flocculating agent, described graft modification natural macromolecule flocculating agent
There is following structure:
Comprise the following steps that
(1) sodium alginate and deionized water are mixed, add dimethyl diallyl ammonium chloride and the third of half response magnitude
Acrylamide, mix homogeneously, maintaining nitrogen purge 15～30min removes the oxygen in mixed material；
In 40～60 DEG C and maintaining nitrogen purge, in mixed material, add ammonium persulfate initiator initiation reaction 10～20min,
Then remaining half acrylamide is dissolved in deionized water and is added dropwise in mixed material；After having added,
Stop logical nitrogen and seal stirring reaction 2～6h；
During whole, described sodium alginate, dimethyl diallyl ammonium chloride, the quality of acrylamide and deionization
The volume ratio of water is 1g:(1～5) g:(1～5) g:(80～150) ml；
Described ammonium persulfate initiator addition is 2～10mmol/L；
(2) after reaction terminates, product is cooled to room temperature, adds excessive propanone and stir precipitation precipitation, filtering, will be solid
Soma is dry, to obtain final product.
Preparation method the most according to claim 1, it is characterised in that the reaction temperature in step (1) is 45～50 DEG C.
Preparation method the most according to claim 1, it is characterised in that the response time described in step (1) is
3～5h.
Preparation method the most according to claim 1, it is characterised in that in step (1), whole during, institute
The volume ratio of sodium alginate, dimethyl diallyl ammonium chloride, the quality of acrylamide and the deionized water stated is 1g:
(2～4) g:(2～4) g:100ml.
Preparation method the most according to claim 1, it is characterised in that the Ammonium persulfate. described in step (1) draws
Sending out agent addition is 4～8mmol/L.
Preparation method the most according to claim 1, it is characterised in that second time acrylamide in step (1)
Add rate controlled 1～5mL/min.
Preparation method the most according to claim 1, it is characterised in that in step (2), baking temperature is 45～55 DEG C.
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