CN110092458A - A kind of preparation method and applications of modified starch-polysilicon acid composite flocculation agent - Google Patents
A kind of preparation method and applications of modified starch-polysilicon acid composite flocculation agent Download PDFInfo
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- CN110092458A CN110092458A CN201910364448.4A CN201910364448A CN110092458A CN 110092458 A CN110092458 A CN 110092458A CN 201910364448 A CN201910364448 A CN 201910364448A CN 110092458 A CN110092458 A CN 110092458A
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/148—Combined use of inorganic and organic substances, being added in the same treatment step
Abstract
The invention belongs to water treatment fields, more particularly to a kind of modified starch-polysilicon acid composite flocculation agent preparation method and applications, this method is modified to obtain cationic modified starch to native starch using cationic etherifying agent, then cationic modified starch is polymerize to obtain modified starch-polysilicon acid composite flocculation agent with polysilicon acid through ultraviolet initiation, the preparation method is with nontoxic, biodegradable starch is raw material, pass through modified starch and the flocculant for polymerizeing polysilicon acid preparation is positively charged, charge neutrality effect can not only be played, and large specific surface area, molecular weight is big, stability is high, adsorption bridging effect can be played simultaneously.
Description
Technical field
The invention belongs to water treatment fields, and in particular to a kind of preparation method of modified starch-polysilicon acid composite flocculation agent
And its application.
Background technique
Water is Source of life, and water pollution is the most important aspect of environmental pollution, and directly or indirectly leads to water
The dead major reason of shortage of resources or even people and other biological.Water environment pollution increasingly increases with global sewage yield
It is closely bound up with the unprocessed discharge of waste water.Current numerous water treatment technologies such as absorption, flocculation, precipitating, oxidation, ion exchange,
Reverse osmosis and membrane technology etc., in these methods, flocculence is easy to operate, and effect is good, at low cost, in sewage, paper waste, contains
Preferable effect is obtained in terms of the water process such as oily waste water, dyeing waste water, is a kind of method being most widely used at present.It is common
Flocculant can be divided into inorganic flocculating agent, organic flocculant, biological flocculant three categories, and traditional inorganic flocculating agent mainly includes aluminium
The macromoleculars such as salt, molysite or small molecule class flocculant have dosage big, there is metal ion residual in water body；It is organic
Flocculant is using synthetic polymeric flocculant polyacrylamide and its derivative as representative, and disadvantage is that price is higher, after water process
Residual has bio-toxicity and is difficult biodegradable small molecule；The biological flocculant production cycle is long.Therefore, current wadding is solved
These problems existing for solidifying agent, research and development multifunctional flocculants new product have a very important significance water process.
Starch is the natural polymer that distributed in nature is extensive, cheap, and insoluble in cold water, swellable in hot water is glue
Fill substance.Great amount of hydroxy group is had on starch segment, and there is stronger reactivity, it can be by etherificate, oxidation, esterification and grafting altogether
The chemical modifications means such as poly-, obtain the modification biological macromolecular flocculant with very strong flocculating property, biodegradable, nontoxic nothing
Evil, is the excellent raw material for preparing flocculant.The etherification modified cationic starch of most study at present, degree ofacationic substitution and
Molecular weight is the key factor for limiting its flocculating property, class modified starch is grafted based on acrylamide, polyacrylamide, with third
There are same drawbacks for acrylamide derivative.
Polysilicon acid is activated by waterglass, is the high molecular polymer of tetrahedral, can develop into linear, branch
The shapes such as chain or particle.A kind of anionic inorganic high polymer coagulant, in practice often with aluminium salt, molysite and inorganic height
Molecular flocculant poly-aluminium, Polyferric Sulfate salt are used cooperatively, or as flocculation aid, but it is easily precipitated silica gel in storage and loses flocculation
Performance, thus cannot store for a long time, to limit its application.
Summary of the invention
The present invention provides a kind of preparation method of modified starch-polysilicon acid composite flocculation agent, and the preparation method is with nontoxic nothing
Evil, biodegradable starch are raw material, prepare flocculant by cation-modified and polysilicon acid copolymerization, the flocculant band is just
Electricity can not only play charge neutrality effect, and large specific surface area, and molecular weight is big, and stability is high, can play adsorption bridging work simultaneously
With.
Modified starch-polysilicon acid composite flocculation agent preparation method, changes native starch using cationic etherifying agent
Property obtains cationic modified starch, then polymerize cationic modified starch under ultraviolet initiation with polysilicon acid to obtain modified starch-
Polysilicon acid composite flocculation agent.
Preferably, the mass ratio of the native starch and cationic etherifying agent is 4:3~4:7.5.
The study found that the cationic modified starch degree of substitution of preparation is not high when quality very few cationic etherifying agent is added,
Modified effect is poor；When the substance of addition is excessive, the water solubility of modified starch is very poor, it is difficult to it is uniformly mixed with polysilicon acid, it is sufficiently poly-
It closes, it is secondly also uneconomical.
More preferably, the cationic etherifying agent be 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, native starch and sun from
When the mass ratio of sub- etherifying agent is 4:3, modified starch-polysilicon acid composite flocculation agent degree of substitution of preparation is suitable for.
Preferably, above-mentioned native starch is potato starch, tapioca or cornstarch, more preferably, above-mentioned day
Right starch is cornstarch, and cornstarch retrogradation is higher, and moisture content is lower (11.39%).
Preferably, the mass ratio of the native starch and polysilicon acid is 4:1~4:4.
Preferably, ultraviolet ray intensity is 7.67~30.70mW/cm in the ultraviolet initiation2。
Ultraviolet initiation can promote the activation of cationic starch and polysilicon acid group and polymerization reaction occurs, and cause intensity
Low, the free radical quantity of initiation is few, and polymerization rate is slow；And cause intensity it is excessive when, it is uneconomical, be difficult to control, when ultraviolet
Cause the range of luminous intensity in 7.67~30.70mW/cm2When interior, the rate of polymerization reaction both can guarantee, also can guarantee that polymerization is anti-
The economy and controllability answered.
Preferably, the specific steps of the preparation method are as follows:
(1) native starch is evenly dispersed in water, inorganic base is added, is gelatinized 0.5~2h at 60~80 DEG C, is then added
Cationic etherifying agent is etherified 1~4h under ultraviolet light, and cationic modified starch is made；
(2) cationic modified starch and polysilicon acid are mixed, under inert nitrogen gas atmosphere, is polymerize through ultraviolet initiation
Product.
Preferably, the inorganic base refers to the hydroxide of the alkali metal such as sodium hydroxide, potassium hydroxide or cesium hydroxide.
Preferably, the inorganic base is sodium hydroxide, and the mass ratio of sodium hydroxide and native starch is 1~3:4~6.More
To be preferred, the mass ratio of the sodium hydroxide and native starch is 1:4.
Preferably, the native starch is native starch of the water content less than 12%.
Preferably, in the step (1), gelatinization point is 70 DEG C, and it is 7.67~30.70mW/ that ultraviolet light, which is etherified intensity,
cm2.Under this condition, the flocculating property of composite flocculation agent can be significantly improved.
Preferably, the ultraviolet time for causing polymerization described in the step (2) is 2~8h, the ultraviolet initiation polymerization
Ultraviolet ray intensity is 7.67~30.70mW/cm2。
Preferably, the polysilicon acid is the preparation method comprises the following steps: by NaSiO3·9H2O is molten for 1g:10~20mL with mass volume ratio
Yu Shui adjusts pH to 6~7 with 0.5~2mol/L sulfuric acid and sodium hydroxide solution.More preferably, NaSiO3·9H2O is dissolved in water
Additional amount be 1g/10mL.
The study found that polysilicon acid seldom arrives closely knit glue, and the degree of polymerization is lower when sodium metasilicate is dissolved in excessive water, reduce
The molecular weight of composite flocculation agent；When sodium metasilicate is dissolved in very few water, indissoluble solution, operation is not easy.And the concentrated sulfuric acid and sodium hydroxide are dense
When spending too high or too low, terminal pH jump is larger, and terminal adjusts difficult.The preferred mass volume ratio that the present invention prepares polysilicon acid is
1g:10mL, polysilicon acid obtained is closely knit to be easy to get.
Protection model of the invention is also belonged to by modified starch-polysilicon acid composite flocculation agent prepared by above-mentioned side's preparation method
It encloses.
Since above-mentioned modified starch-polysilicon acid composite flocculation agent is tested in the flocculating setting flocculating property of sewage and sludge
Excellent effect therefore above-mentioned modified starch-polysilicon acid composite flocculation agent preparation method and exist directly as flocculant
Application in processing sewage and/or sludge also belongs to protection scope of the present invention.
The beneficial effects of the present invention are:
The present invention obtains high substituted degree cation and changes by the way that gelatinization and cation two stages of etherificate are modified to native starch
Property starch, then obtain composite flocculation agent of the invention by ultraviolet initiation polymerizing cationically modified starch and polysilicon acid.Gained
The degree of substitution of composite flocculation agent is high, can give full play to charge neutrality effect, keeps the colloidal solid in water process de- steady；Molecular weight and ratio
Surface area is larger, can make to take off steady particle in water and pass through adsorption bridging rapid subsidence；Stability is good, easy to maintain.Meanwhile this compound wadding
Agent is coagulated using polysilicon acid as framework material, can be constructed three-dimensional porous channel for sludge, can be effectively improved dewatering performance of sludge, realize dirty
The high-efficiency dehydration of mud；Using starch as raw material, acrylamide toxic monomers are substituted with polysilicon acid, conventional gold is substituted with this flocculant
Belong to salt flocculant, has the characteristics that energy saving and environmental-friendly.
Detailed description of the invention
Fig. 1 is modified starch-polysilicon acid composite flocculation agent infrared spectroscopy prepared by starch, polysilicon acid and embodiment 1
Figure；
Fig. 2 is starch-polysilicon acid composite flocculation agent scanning electron microscope (SEM) photograph prepared by embodiment 1, and a.2k b.40k times FESEM schemes
Times FESEM figure；
Fig. 3 is starch-polysilicon acid composite flocculation agent Kaolin floc test and sludge flocculation prepared by embodiment 1
Dehydrating effect test, a. Kaolin floc test, CS-PSi dosage is respectively 5mg/L, 10mg/L, 20mg/L,
30mg/L, 40mg/L, 60mg/L；B. sludge flocculation dehydration test, CS-PSi dosage are respectively 5mg/L, 10mg/L, 20mg/
L, 30mg/L, 40mg/L, 60mg/L；C. the mud granule after conditioning flocculation.
Fig. 4 is starch-polysilicon acid composite flocculation agent characteristic viscosity determining result figure prepared by embodiment 1.
Specific embodiment
The present invention is further detailed below in conjunction with drawings and examples.Agents useful for same in the present invention, material and
It is obtained if instrument can lead to commercially available channel without spy's explanation.
Embodiment 1
The present embodiment modified starch-polysilicon acid flocculant preparation method, includes the following steps:
1) preparation of cationic modified starch
By 2g native starch (corn remembers St) even particulate dispersion in 10mL distilled water, 40%NaOH dissolution stirring is added
Uniformly, the gelatinization pretreatment 1h in 70 DEG C of water-baths.Then by 3mL3- chloro-2-hydroxypropyl-trimethyl ammonium chloride (65%wt, ρ
=1.154, remember GTA) be added, it stirs evenly, 2h (intensity 30.7mW/cm under ultraviolet light2), obtain cation-modified shallow lake
Powder.
2) preparation of polysilicon acid
By 1gNaSiO3.9H2O is dissolved in 20mL distilled water, with the sulfuric acid of 2mol/L, 0.5mol/L, the NaOH of 0.5mol/L,
The pH=6.0 of lysate is adjusted, static 2~3h obtains light blue colloid substance at room temperature, places spare.
3) modified starch-polysilicon acid composite flocculation agent preparation
2) polysilicon acid of preparation is poured into cationic modified starch made from step 1), leads to nitrogen 5min, stirs evenly,
It is put into ultraviolet trigger box, through uv-light polymerization 2h (intensity 30.7mW/cm2), products therefrom precipitates clear through dehydrated alcohol
It washes 3 times, washing precipitate is put into 50 DEG C of baking ovens and is dried, be ground into fine grained up to modified starch-polysilicon acid composite flocculation
Agent particle.
In order to verify the really compound success of composite flocculation agent rather than simple mixing, prepared by step described in embodiment 1
Cationic starch, polysilicon acid, modified starch-polysilicon acid composite flocculation agent carried out infrared spectrum characterization and comparative analysis.Sun
Ionic starch, polysilicon acid, modified starch-polysilicon acid composite flocculation agent infrared spectrogram are respectively such as a, b, c infrared absorption of Fig. 1
Shown in curve.
It can be seen that cationic starch in 3400cm from a curve of Fig. 1-1Peak value at left and right is-OH on starch backbone
The absorption peak that stretching vibration generates；Belong to the absorption peak that saturation C-H stretching vibration generates at 2933；1150cm-1Left and right is C-O；
It is CH2-O-CH2 at 1020 and 1080；The absorption peak occurred at 1417 is-N+ (CH3)3Quaternary ammonium group.It can be obtained from the b curve of Fig. 1
Polysilicon acid is in 1112cm-1、900cm-1It is respectively Si-O-Si, Si-O that characteristic group is obtained at absorption peak, must be inhaled with cationic starch
Group is received to differ widely.And the c curve for observing Fig. 1 can find that not only there is cationic starch to obtain characteristic group on this figure is also equipped with
The characteristic group of polysilicon acid, and in 1112cm-1Slightly weaken.Above analysis all surface composite flocculation agents are successfully prepared, product
There are some groups of the two simultaneously.
Further, it for the exterior appearance of the more intuitive made novel composite flocculating agent of observation, is scanned using Flied emission
Electronic Speculum has carried out scanning to the starch prepared under optimal preparation condition-polysilicon acid composite flocculation agent.Scanning result is shown in attached drawing
2, a, b is illustrated respectively in the scanning electron microscopic picture under 2000 times and 40000 times.The prepared shallow lake it can be seen from attached drawing 2-a
There are many " salient points " on powder-polysilicon acid composite flocculation agent surface, are in fine and closely woven distribution shape, are further amplified and see attached drawing 2-b, as a result table
These bright particulate materials are distributed layer by layer, and centre forms many holes, can preferably play adsorption bridging effect.Meanwhile newly
The hole shape structure of product is the substance of polysilicon acid and cationic starch polymerization and formation, and property is similar to polysilicon acid, stablizes
Property it is preferable, have longer branch, and in rigidity, can be played in sludge flocculation dehydration skeletal support act on, prevent hair
Pore blocking, dehydration is difficult, meanwhile, play the charge neutrality effect of cationic starch and the adsorption bridging of complex macromolecular flocculant
Effect.Thus, it can be used as the good dehydration flocculant of conditioning effect.
Next, passing through its inherent viscosity of measurement to modified starch-polysilicon acid composite flocculation agent particle prepared by embodiment 1
Characterize high polymer relative molecular mass, main experimental instrument is Ubbelohde viscometer (specification: 0.5~0.6mm) and water bath with thermostatic control
Slot (HH series, Shanghai Jiang Xing Instrument Ltd.).
Test method and process: using ultrapure water as solvent, the modified starch of preparation-polysilicon acid composite flocculation agent is matched respectively
The solution that concentration is 0.5,0.75,1.00,1.25,1.50g/dL is made, 20mL solution is taken to be transferred to Ubbelohde viscometer, and by Ubbelohde
Viscosmeter is perpendicularly fixed in constant temperature water bath, and set water temperature is 30 DEG C, is kept the temperature 15min, is flowed through with stopwatch accurate recording solution
It the time of two red graduation marks, is repeated three times, measured value difference is no more than 0.02s, is averaged and is denoted as t.Same side
Method surveys pure water flow time, remembers t0, then specific viscosity nsp(dL/g) are as follows:
After calculating specific viscosity, concentration is obtained divided by corresponding flocculant solution with increasing specific concentration and obtains reduced viscosity, then
Using reduced viscosity as y-axis, concentration is x-axis mapping, obtains straight line, when the regression coefficient of straight line is greater than 98.0%, by straight line
It is extrapolated to intercept when concentration is zero, as flocculant characteristic viscosity ηi.As a result such as Fig. 4, composite flocculation agent viscosity is larger, by crow
Family name's viscosimeter institute's sample inherent viscosity is 1.37dL/g；Secondly, surveyed inherent viscosity and increase specific concentration it is negatively correlated, with sun from
The inherent viscosity curve of sub- starch flocculant is on the contrary, illustrate that this makees flocculant with the new material, its lower viscosity of concentration after dissolution
Coefficient is bigger, and molecular weight is bigger, i.e., lower product throwing amount can obtain good flocculating effect, and flocculating property is lower, is conducive to
Reduce flocculation cost.
The relationship of inherent viscosity and molecular weight are as follows:
[η]=KMα
Wherein [η] is inherent viscosity, and K and α are two constants, and M is molecular weight, has this formula that can obtain inherent viscosity and molecular weight
It is positively correlated, thus, molecular weight is not surveyed in this test directly, but passes through the size of inherent viscosity reaction molecular amount.
The measurement of Moire technique degree of substitution is carried out to modified starch polysilicon acid composite flocculation agent particle prepared by embodiment 1, specifically
With reference to:
Laboratory apparatus: pipette 50mL1 branch, acid buret 25mL1 branch；Conical flask 250mL4.
Drug: chlorination sodium standard solution 0.1mol/L, silver nitrate standard solution 0.1mol/L, 5%K2CrO4Indicator.
It is 23.03% by measuring the method being averaged three times to measure degree of substitution, degree of substitution is higher, and flocculating property tries
It tests and shows that new product flocculating effect is good.Analysis reason may be: negatively charged in conventional sewage or sludge, flocculant institute is positively charged
Lotus can give full play to charge neutrality effect, then the characteristics of be aided with product macromolecule, long-chain can adsorption bridging and net catch suspended particulate,
Therefore, the flocculating property test effect done is good, and wadding body is also larger.To exclude the inaccurate generation of inherent viscosity molecular weight determination
Error, experimental evidence simulate the floc test further progress of kaolin and sludge verifying (being specifically shown in embodiment 2), and discovery should
The Flocculating Effect of Flocculant of method preparation is excellent, and kaolin turbidity removal rate is up to 98.67%, and sludge turbidity removal rate is up to 99.12%, sludge
Filter cake solid content is 14.93% after suction filtration, and activated sludge solid content 2%~4% before relatively improving, sludge dewatering effect has obtained greatly
It is big to improve, it is significant to sludge flocculation conditioning effect.
Inventor has carried out further with regard to each material proportion, reaction temperature and reaction time in the preparation method of embodiment 1
Research, be prepared for multiple samples, wherein sample 7 be embodiment 1 prepare modified starch-composite flocculation agent flocculant.And
The degree of substitution and intrinsic viscosity and sludge dewatering effect of these samples are measured, as a result letter is shown in Table 1 and 2.
Each material proportion of table 1 is to the influence of modified starch-composite flocculation agent flocculant
Note: preparing the preparation method of the sample in this table in addition to the charge ratio in table, other preparation sides with embodiment 1
Method is identical.Dosage component starch, sodium metasilicate mass ratio are just mainly prepared, etherifying agent and starch quality ratio are optimized.
By single factor experiment shown in table 1, show optimum fillings ratio are as follows: starch: sodium metasilicate mass ratio is 2:1, starch: ether
Agent mass ratio is 2:2.25 .mW/cm2Ultraviolet ray intensity, under the premise of optimum fillings ratio, to pair of composite flocculation agent preparation
The optimization of etherification time and polymerization time is tested as shown in list 2.
Each etherification time and polymerization time are to the influence of modified starch-composite flocculation agent flocculant in 2 preparation method of table
Note: preparing the preparation method of the sample in this table in addition to the reaction condition in table, other preparations with embodiment 1
Method is identical.
It is final to determine by the optimization of reaction condition, prepare starch-polysilicon acid composite flocculation agent optimum condition are as follows: form sediment
Powder: sodium metasilicate mass ratio is 2:1, and starch: etherifying agent mass ratio is 2:2.25,30.7mW/cm2Under ultraviolet ray intensity be etherified 3h and
Cause polymerization 2h, i.e. sample 11, the cationic starch prepared under this condition-polysilicon acid flocculant degree ofacationic substitution is
22.40%, preferable to the removal effect of simulation kaolin solution, turbidity removal rate is up to 98% or so, and supernatant transparent lightness is with flocculation
The variation of agent dosage is smaller, but throwing amount is higher, and wadding body is bigger, and flocculating setting is faster；In addition, being imitated to degree ofacationic substitution and flocculation
Researching and analysing for fruit shows: the degree ofacationic substitution of composite flocculation agent is smaller and flocculating effect is not simple positive correlation or negative
Close, can the quality of flocculating effect be not the simple height depending on degree ofacationic substitution, also with the molecular weight of composite flocculation agent
Or other factors are related.
Embodiment 2
To verify modified starch-polysilicon acid composite flocculation agent flocculating effect of the invention, sample prepared by Example 1
11 carry out flocculation treatment comparative study to simulation kaolin water sample, sewage plant activated sludge respectively.
Flocculating setting experiment to simulation kaolin water sample: the kaolin solution of 1g/L is prepared, takes 6 parts of 250mL's respectively
Kaolin water sample, former turbid 983NTU, 989,932NTU, 953NTU, 999NTU, 988NTU of being followed successively by pour into 6 burnings respectively
Cup is prepared polysilicon acid and modified starch-polysilicon acid composite flocculation agent (sample 11) weighs 0.1g for above-mentioned, is dissolved in
100mL distilled water, the flocculant of compound concentration 1g/L, every kind of flocculant is by not same amount 5mg/L, 10mg/L, 20mg/L, 30mg/
L, 40mg/L, 60mg/L are sequentially added in 6 parts of kaolin solutions, and 300r/min quickly stirs 1min, then in the slow of 100r/min
3min, static 10min are stirred under fast speed of agitator, measurement flocculation front and back supernatant fluid turbidity, wherein modified starch-polysilicon acid is compound
Flocculant is up to 98.07% to the turbidity removal rate of simulation kaolin water sample.
According to experimentation and Fig. 3 a it is found that the wadding body of simulation kaolin floc test is larger, sinking speed is very fast.Finally
Discovery turbidity removal efficiency is measured 97% or more by nephelometer, and flocculation turbidity removal effect is preferable.When low flocculant dosage, flocculation
Effect is obvious as flocculant dosage changes, and turbidity removal effect is gradually increased；But flocculant dosage flocculates when being 10mg/L
Effect reaches best 98.07%, and flocculating effect variation is smaller when being further added by flocculant throwing amount, and turbidity removal rate of flocculating has becoming for decline
Gesture.The reason of analyzing the above phenomenon may be that adsorption bridging and charge neutrality effect are weaker when flocculant throwing amount is less, cause to flocculate
Turbidity removal rate is lower, and as flocculant throwing amount increases, adsorption bridging effect enhancing, flocculating effect enhances and variation is obvious.And when wadding
After solidifying agent dosage reaches a certain amount of, being further added by flocculant dosage may make suspension surface reach saturation, generate again steady existing
As, thus flocculating effect declines instead.
Sewage water factory excess sludge dewatering is tested: taking 100mL original excess sludge, moisture content 98.34% adds water dilute
It releases to 250mL and stirs evenly, be inverted the beaker of 6 250mL respectively；The flocculant of compound concentration 1g/L, by different dosages
6 beakers are sequentially added, two stages flocculation is set on six blenders, a stage 120r/min quickly stirs 20s, two-stage
40r/min stirs 60s, static 10min, surveys supernatant fluid turbidity, is centrifuged to sludge and surveys sludge solid content.Wherein modified starch-is poly-
Silicic acid composite flocculation agent is up to 98.99% to the turbidity removal rate of sludge, and sludge solid content is under low centrifugal speed after flocculation conditioning
18.22%, reach maximum, sludge solid content only 4.52% after PAM conditioning under the same terms.Analysis may be the born of the same parents because of sludge
Outer polymer (EPS) is decomposed under the conditioning of modified starch-polysilicon acid composite flocculation agent, makes the microbial cell in sludge
It is crushed and releases internal water, thus show dehydrating effect preferably after improving.
According to Fig. 3 b, 3c and experimentation it is found that when processing sludge, flocculating setting significant effect, after flocculating setting,
Sludge floc particle is more closely knit, and by centrifugal dehydration, solid content may be up to 18.82%, experiments have shown that, change composite flocculation agent pair
The dehydrating and conditioning of sludge works well.
Claims (10)
1. a kind of modified starch-polysilicon acid composite flocculation agent preparation method carries out native starch using cationic etherifying agent
Modified cationic modified starch, then mixes cationic modified starch with polysilicon acid, is modified through ultraviolet initiation polymerization
Starch-polysilicon acid composite flocculation agent.
2. preparation method according to claim 1, which is characterized in that the quality of the native starch and cationic etherifying agent
Than being 1~2: 1.5~4.5.
3. preparation method according to claim 2, which is characterized in that the cationic etherifying agent is the chloro- 2- hydroxypropyl of 3-
The mass ratio of trimethyl ammonium chloride, the native starch and cationic etherifying agent is 4:3 ~ 4:7.5.
4. preparation method according to claim 1, which is characterized in that the mass ratio of the native starch and polysilicon acid is 2:
0.5~2.
5. preparation method according to claim 1, which is characterized in that in the ultraviolet initiation ultraviolet ray intensity be 7.67 ~
30.70mW/cm2。
6. preparation method according to claim 1-5, which is characterized in that the specific steps of the preparation method
Are as follows:
(1) native starch is evenly dispersed in water, inorganic base is added, 0.5 ~ 2h is gelatinized at 60~80 DEG C, be then added sun from
Sub- etherifying agent is etherified 1~4h under ultraviolet light, and cationic modified starch is made；
(2) cationic modified starch and polysilicon acid are mixed, under atmosphere of inert gases, polymerize to produce through ultraviolet light initiation
Object.
7. preparation method according to claim 6, which is characterized in that the native starch is day of the water content less than 12%
Right starch.
8. preparation method according to claim 6, which is characterized in that in the step (1), gelatinization point is 70 DEG C, purple
Outer light etherificate intensity is 7.67 ~ 30.70mW/cm2；In the step (2), the ultraviolet time for causing polymerization is 2~8h, institute
The ultraviolet ray intensity for stating ultraviolet light initiation is 7.67 ~ 30.70mW/cm2。
9. modified starch-polysilicon acid composite flocculation agent of any one of the claim 1-8 preparation method preparation.
10. application of modified starch described in the claim 9-polysilicon acid composite flocculation agent in processing sewage and/or sludge.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862131A (en) * | 2019-11-25 | 2020-03-06 | 广西大学 | Method for treating nitrogen and phosphorus-containing wastewater by applying polysilicate iron/cationic starch composite flocculant |
| CN111233114A (en) * | 2020-01-19 | 2020-06-05 | 吉林化工学院 | Polysilicate aluminum-cationic starch composite flocculant and preparation method thereof |
| CN112661249A (en) * | 2020-12-22 | 2021-04-16 | 成都诺德源环保科技有限公司 | Degradable flocculant and preparation method thereof |
| CN114835229A (en) * | 2022-05-06 | 2022-08-02 | 兰州交通大学 | Polyferric aluminum silicate/cationic starch composite flocculant and preparation method thereof |
| WO2022236964A1 (en) * | 2021-05-14 | 2022-11-17 | 南京大学 | Enhanced coagulation method for removing micro-plastics in water |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862131A (en) * | 2019-11-25 | 2020-03-06 | 广西大学 | Method for treating nitrogen and phosphorus-containing wastewater by applying polysilicate iron/cationic starch composite flocculant |
| CN111233114A (en) * | 2020-01-19 | 2020-06-05 | 吉林化工学院 | Polysilicate aluminum-cationic starch composite flocculant and preparation method thereof |
| CN112661249A (en) * | 2020-12-22 | 2021-04-16 | 成都诺德源环保科技有限公司 | Degradable flocculant and preparation method thereof |
| CN112661249B (en) * | 2020-12-22 | 2023-12-15 | 成都诺德源环保科技有限公司 | Degradable flocculant and preparation method thereof |
| WO2022236964A1 (en) * | 2021-05-14 | 2022-11-17 | 南京大学 | Enhanced coagulation method for removing micro-plastics in water |
| CN114835229A (en) * | 2022-05-06 | 2022-08-02 | 兰州交通大学 | Polyferric aluminum silicate/cationic starch composite flocculant and preparation method thereof |
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