CN105384231B - A kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent and preparation method thereof - Google Patents
A kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent and preparation method thereof Download PDFInfo
- Publication number
- CN105384231B CN105384231B CN201510971055.1A CN201510971055A CN105384231B CN 105384231 B CN105384231 B CN 105384231B CN 201510971055 A CN201510971055 A CN 201510971055A CN 105384231 B CN105384231 B CN 105384231B
- Authority
- CN
- China
- Prior art keywords
- paper mill
- mill sludge
- based polyalcohol
- ferric chloride
- flocculation agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
Abstract
The present invention relates to a kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agents and preparation method thereof, including paper mill sludge raw material slightly directly is carried lignin with lye dissolving, graft modification prepares cationic paper mill sludge based polyalcohol, and hybrid reaction is carried out with polyaluminum ferric chloride, prepare new and effective composite flocculation agent.When gained flocculant is for handling simulation dyestuff water sample, dosage to the chroma removal rate stabilization of disperse yellow water sample more than 95%, while to the water sample under the conditions of different pH values and other a variety of water samples, is respectively provided with good coagulation effect in 5mg/L.Present invention process is simple, and device requirement is few, is conducive to industrialized production and application, not only realizes the recycling of waste, but also the flocculant flocculation efficiency prepared is high, applied widely, and good treatment effect is respectively provided with to common water pollutant.
Description
Technical field
The present invention relates to a kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agents and preparation method thereof, belong to
In changing waste into resources utilization and water treatment flocculant technical field.
Background technology
Coagulation sedimentation is current water and wastewater industry both at home and abroad, water pollution control, sea water desalination and water-saving reuse purified treatment work
In journey technical field, it is commonly used to improve a kind of not only economic but also easy water treatment method for the treatment of effeciency.Water technology
Innovation and development, the simplification of technological process, operating cost reduces and purification of water quality Quality advance, depend greatly on
The performance of coagulant.Most widely used coagulant is water-disintegrable metal salt, and such as aluminium salt and molysite, but Al-based coagulant is using
In there are problems that residual Al neurotoxicity, molysite is then strong with respect to its corrosivity, to equipment requirement height.Thus, it is special in water process
It is during drinking water treatment, reducing the dosage of inorganic coagulant is necessary.In recent years, natural polymer and people
Work synthetic organic polymer due to organic matter treatment effeciency height, dosage is low, and sludge output is few, influenced by pH variations it is smaller, thus
It is rapidly developed, but higher operating cost inhibits the application of product.It is research shows that organic polymer is solidifying as helping
Agent is used in combination with inorganic coagulant, can substantially reduce the dosage of inorganic coagulant, while improves coagulation effect.State at present
The inside and outside main direction of studying in relation to chemical coagulation process concentrates on new and effective, cheap, environmentally friendly, compound flocculant exploitation, this
To administering life, industrial wastewater has highly important actual application value.
Paper mill sludge is the end product of wastewater treatment in paper-making process.Since with complicated component, water content is high, handles
The features such as difficulty is big, disposal costs are high (account for about pulping wastewater treatment expense more than 50%), so sludge treatment has become tired
Disturb the problem of papermaking enterprise operation.The domestic general mode for selecting burning, landfill is handled, but be easy to cause secondary pollution,
Aggravate environmental problem.Paper mill sludge biomass content is enriched, and organic matter contains 50%-65%, mainly contains cellulose, hemicellulose
With the organic matters and filler, flocculant etc. such as lignin, how paper mill sludge is carried out biomass as resources comprehensive utilization has
Highly important realistic meaning.
At present, the recycling of domestic paper mill sludge is mainly for the preparation of activated carbon, production organic fertilizer, Building wood
Material, chemical dispersant etc., Chinese patent literature CN102205964A, CN102249745A, CN102503361A and CN1614142
Individually disclose the related art scheme of paper mill sludge recycling.
In relation to less for the report of Material synthesis flocculant using paper mill sludge, such as Chinese patent literature CN103265106A
A kind of method that flocculant is prepared using paper mill sludge is disclosed, including the use of the paper mill sludge generated during alkali paper-making is
Then raw material dissolves lignin therein with lye, mixed liquor is moved to reactor, after reactor is warming up to certain temperature, is added
Enter anhydrous sodium sulfite, react certain time, then add in hydrogen peroxide and formaldehyde thereto successively, after being stirred to react a period of time,
Sodium sulfite is added, the reaction was continued after a certain period of time, and temperature of reactor is reduced, and adds urea and is reacted, by supernatant
Floccule in liquid is filtered up to flocculant.When gained flocculant product is used for pretreated soybean albumen actual water sample, effectively produce
The dosage of product is in 370-375mg/L, and COD removal rates are up to 35%, and nitrogen removal rate is up to more than 50%.The flocculant pairing
It is higher into temperature requirement, its large-scale industrial production is limited, and only under the conditions of high dosage, counterweight pollution water sample has one
Fixed coagulation effect, to the removal effect unobvious of low molecule organic matter in water body, therefore the product is relatively low there are coagulation efficiency,
Operating cost is higher, using the drawbacks such as water body range is relatively narrow.
Through retrieval, prepare cationic flocculant using paper mill sludge as raw material and prepare composite flocculation agent with inorganic coagulant
There is not yet pertinent literature is reported.
Invention content:
In view of the deficiencies of the prior art, the present invention provides a kind of polyaluminum ferric chloride-compound wadding of paper mill sludge based polyalcohol
Solidifying agent is that the paper mill sludge of paper industry realizes changing waste into resources, realizes the sustainable development of paper industry, alleviate environment pressure
Power.
The present invention also provides a kind of preparation methods of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent.
Raw material explanation：
The raw material paper mill sludge that the present invention uses for alkali paper-making production process in the paper mill sludge that generates, be dried
Afterwards, 40~45wt% of content of lignin is measured, cellulose is 5~10wt%, moisture content 5wt%, remaining is soil, the grains of sand and more
Kind inorganic salt impurities.
Cationic high-molecular paper mill sludge based polyalcohol abbreviation LBF, polyaluminum ferric chloride abbreviation PFACl.
Summary of the invention：
The present invention uses the paper mill sludge generated in paper industry as raw material, and it is organic poly- first to synthesize a kind of cation high molecular
Object is closed, a kind of compound, obtained novel composite flocculating agent is then carried out with inorganic coagulant polyaluminum ferric chloride.
Technical scheme is as follows：
A kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent, the composite flocculation agent are molten to clarify
Liquid is by after paper mill sludge elder generation synthesizing cationic type macromolecule paper mill sludge based polyalcohol, is mixed with aluminium polychloride ferrous solution
It is prepared, the total mass concentration of Fe and Al is 8~12g/L in aluminium polychloride ferrous solution；Wherein, paper mill sludge based polyalcohol
Total mass ratio with Fe and Al in aluminium polychloride ferrous solution is 1：(1~8), the current potential of composite flocculation agent is+25~35mV, is glued
It spends for 1.10~1.25mPas, molecular weight is 500~1000KDa.
The cationic high-molecular paper mill sludge based polyalcohol cationic degree of the present invention is 28~35%, is mixed with
More than composite flocculation agent storage life 30d.
The preparation method of above-mentioned polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent is as follows including step：
(1) preparation of polyaluminum ferric chloride
Weigh FeC13·6H20 and A1C13·6H20 solid is dissolved in deionized water, controls Fe：The mass ratio of Al is
(0.8~1.2)：1, Na is added dropwise2CO3Solution controls OH-：(Fe3++Al3+) molar ratio be (0.5~1.5)：1, stirring
It is completely dissolved to solid, is (0.06~0.09) according to phosphorus, iron molar ratio：1 ratio adds in stabilizer Na2HPO4·12H20 powder
Stirring is continued to being completely dissolved in end, and the total mass concentration for being diluted with water to Fe and Al is 8~12g/L；Polyaluminum ferric chloride is made
Solution；
(2) preparation of cationic high-molecular paper mill sludge based polyalcohol
The paper mill sludge is dissolved in deionized water, the mass volume ratio of paper mill sludge and deionized water is 2: (50
~60) g/ml；Stirring is lower to be added dropwise NaOH solution, and control pH takes mixture to centrifuge, take in 11.0~12.0,10~30min of stirring
Supernatant is poured into reactor, and it is 7.0~8.0 to adjust pH；
Reactor is heated to 70 DEG C~80 DEG C, adds in the mass ratio of potassium persulfate, paper mill sludge and potassium persulfate
It is 2:(0.05~0.07) after leading to 10~15min of nitrogen, adds in disodium ethylene diamine tetraacetate, paper mill sludge and ethylenediamine tetrem
The mass ratio of acid disodium is 2:(0.05~0.07) leads to nitrogen the reaction was continued 3~5min；Add in acrylamide and dimethyl diene
The mass ratio of the mixed liquor of propyl ammonium chloride, paper mill sludge and acrylamide is 2:(1.5~2.5), paper mill sludge quality and two
The ratio of methyl diallyl ammonium chloride volume is 2:(6~10), unit g/ml after leading to 3~5min of nitrogen reaction, are stirred to react
3~4h, 70 DEG C~80 DEG C of reaction temperature；
Reaction terminates products obtained therefrom being cooled to room temperature, and adds in acetone evolution reaction product, staticly settles, take filter residue vacuum
It is dry, obtain cationic high-molecular paper mill sludge based polyalcohol；
(3) preparation of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent
Cationic high-molecular paper mill sludge based polyalcohol made from step (2) is added in into step (1) polymerization chlorine obtained
Change in ferro-aluminum solution, the mass ratio control of LBF and (Fe+Al) are 1：(1~8) is stirred to react 1~5h to get polymerization under room temperature
Aluminium chloride ferrum-paper mill sludge based polyalcohol composite flocculation agent.
According to currently preferred, FeC1 in step (1)3·6H20 and A1C13·6H20 addition is in terms of Fe, Al, matter
Amount is than being 1.0：1.
According to currently preferred, in step (1), FeC13·6H20 and A1C13·6H20 solid is simultaneously dissolved in deionization
In water, ferro-aluminum gross mass is 1 with deionized water volume ratio：20~35, unit g/ml.
According to currently preferred, OH in step (1)-：(Fe3++Al3+) molar ratio be 1.0：1.
According to currently preferred, stabilizer Na in step (1)2HPO4·12H20 addition in terms of phosphorus with iron molar ratio
It is 0.08：1.
According to currently preferred, the mass ratio of paper mill sludge and potassium persulfate is 2 in step (2):0.05.
According to currently preferred, the mass ratio of paper mill sludge and disodium ethylene diamine tetraacetate is 2 in step (2):0.06.
According to currently preferred, the mass ratio of paper mill sludge and acrylamide is 2 in step (2):2.0, paper mill sludge
The ratio of quality and dimethyl diallyl ammonium chloride volume is 2:(6~8), unit g/ml.
According to currently preferred, reaction temperature is 70 DEG C in step (2), reaction time 3h.
According to currently preferred, the mass concentration of dimethyl diallyl ammonium chloride is 50~70wt% in step (2),
It is preferred that the mass concentration of dimethyl diallyl ammonium chloride is 60wt%.
According to currently preferred, vacuum drying temperature is 40~60 DEG C in step (2), and drying time is 7~9h, vacuum
It spends for 130~140Pa, the preferred 133Pa of vacuum degree.
According to currently preferred, the mass ratio control of LBF and (Fe+Al) are 1 in step (3)：(4~6), are stirred to react
Time is 1~3h.
A currently preferred technical solution, the system of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent
Preparation Method, it is as follows including step：
(1) preparation of aluminium polychloride
Weigh the A1C1 of 9.9~12.4g3·6H2The FeC1 of 0 and 5.3~6.7g3·6H20 solid is simultaneously dissolved in deionization
In water, Na is added dropwise2CO3Solution controls OH-：(Fe3++Al3+) molar ratio for 0.5~1.5, under magnetic agitation effect
To being completely dissolved, after lather collapse, add in 0.56~0.70g's of stabilizer according to phosphorus, the ratio that iron molar ratio is 0.08
Na2HPO412H20 powder continues stirring to being completely dissolved, and is finally settled to 250ml with distilled water dilution, is made (Fe+Al)
Mass concentration be 10g/L aluminium polychloride ferrous solution；
(2) preparation of cationic high-molecular paper mill sludge based polyalcohol
The paper mill sludge for weighing 2.0g is dissolved in the deionized water of 150ml, under magnetic stirring, it is molten that NaOH is added dropwise dropwise
Liquid, control pH in 11.0~12.0, be stirred for 15min to be uniformly mixed, by mixture under 8000rpm high speed 15min, take
Supernatant is poured into reactor, and it is 7.0~8.0 to adjust supernatant pH；
Reactor water-bath is heated to 70 DEG C~80 DEG C, adds in the potassium persulfate of 0.05~0.07g, logical nitrogen 10~
After 15min, the disodium ethylene diamine tetraacetate of 0.05~0.07g is added in, leads to nitrogen the reaction was continued 3~5min；Add in 1.5~2.5g
Acrylamide and 6~10ml dimethyl diallyl ammonium chloride, continue under 70 DEG C~80 DEG C water bath conditions reaction 3~
4h；
Reaction terminates to cool down products obtained therefrom room temperature, adds in 200ml acetone, and reaction product is precipitated in stirring, and vacuum is taken out
Filter, takes filter residue to be dried in vacuo, 50~60 DEG C of vacuum drying temperature, and dry 6~12h is to get cationic high-molecular paper mill sludge
Based polyalcohol；
(3) preparation of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent
The cationic high-molecular paper mill sludge based polyalcohol of 0.125~1g made from step (2) is added in step (1) to make
In the aluminium polychloride ferrous solution of the 100ml obtained, 1~5h is stirred to react under room temperature to get polyaluminum ferric chloride-paper mill sludge
Based polyalcohol composite flocculation agent.
The application of above-mentioned polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent, water supply, wastewater treatment
Field, flocculant dosage are 1~20mg/L, it is preferred that flocculant dosage 5mg/L, applicable pH are 5~10.
Product prepared by the method for the present invention belongs to polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent, through surveying
Fixed, current potential is+25~35mV, and performance is stablized, and retention cycle is long, and coagulation efficiency is high, suitable for fields such as feedwater, wastewater treatments.
Through handling disperse yellow simulated water sample experiment test, when the flocculant dosage of present invention gained is 5mg/L, percent of decolourization stabilization exists
More than 95%.And to the water sample under the conditions of different pH values and other a variety of water samples, it is respectively provided with good coagulation effect.More
Detailed content will be illustrated in the examples below.
What the present invention utilized is the alkali lignin in paper mill sludge, and graft copolymerization occurs, and it is high to synthesize a kind of cation
Molecule organic polymer, and carry out with inorganic coagulant polyaluminum ferric chloride compound preparing a kind of novel flocculant and the prior art
It compares, excellent results of the invention are：
1. the method for the present invention has achieved the effect that changing waste into resources, the discharge of solid waste is not only reduced, and
The treatment of wastes with processes of wastes against one another, the sound development for paper industry provide new thinking.
2. the flocculant product flocculation efficiency of the present invention is higher, dosage is in 5mg/l or so, so that it may make decoloration removal rate steady
More than 95% is scheduled on, and to the water sample under the conditions of different pH values and other a variety of water samples, is respectively provided with good coagulation effect；
3. the flocculant product nonhazardous of the present invention, simple production process, device requirement is few, and use scope is wide, can drop
The capital construction cost and operating cost of low practical water process, it is easy to accomplish industrialized production.
4. flocculant product electropositive itself is high, binding site is more, molecular chain length, can effectively combine various in water body
The pollutant of molecular weight is simultaneously further reunited, is removed, and coagulation efficiency is high.The storage time of product is long, is unlikely to deteriorate.
Specific embodiment
With reference to embodiment, the invention will be further described, but not limited to this.
The raw material paper mill sludge used in embodiment is the paper mill sludge generated in alkali paper-making production process, is dried
Afterwards, 40~45wt% of content of lignin is measured, cellulose is 5~10wt%, moisture content 5wt%, remaining is soil, the grains of sand and more
Kind inorganic salt impurities.
1. different aluminum weight of iron of embodiment than composite flocculation agent (PFACl-LBF) preparation
(1) weigh three groups of different aluminum weight of iron than A1C13·6H20 and FeC13·6H20 solid is simultaneously dissolved in deionization
In water, respectively first group, A1C13·6H20：9.9g、FeC13·6H20：6.7g；Second group, A1C13·6H20：11.2g、
FeC13·6H20：6.0g；Third group, A1C13·6H20：12.4g、FeC13·6H20：5.3g.Na is added dropwise2CO3Solution, control
Basicity OH processed-：(Fe3++Al3+) molar ratio for 1.0, to being completely dissolved under the action of magnetic stirring apparatus.Treat lather collapse
Afterwards, the Na of stabilizer 0.60g is added according to phosphorus, the ratio that iron molar ratio is 0.082HPO4·12H20 powder continues to stir to complete
Fully dissolved.250ml finally is settled to distilled water dilution, the mass concentration that (Fe+Al) is made is the polyaluminum ferric chloride of 10g/L
Solution；
(2) paper mill sludge for weighing 2.0g is dissolved in the deionized water of 150ml, under magnetic stirring, NaOH is added dropwise dropwise
Solution, control pH in 11.5, be stirred for 15min to be uniformly mixed.By mixture under 8000rpm high speed 15min, take supernatant
Liquid is poured into three-necked flask, and it is 7.5 to adjust thick liquid pH；
By three-necked flask heating water bath to 70 DEG C, the potassium persulfate of 0.50mg is added in, after leading to nitrogen 15min, is added in
The disodium ethylene diamine tetraacetate of 60mg leads to nitrogen the reaction was continued 3min；Add in the acrylamide of 2.0g and the dimethyl diene of 6ml
Propyl ammonium chloride continues to react 3h under 70 DEG C of water bath conditions；
Reaction terminates to cool down products obtained therefrom room temperature, adds in 200ml acetone, and reaction product is precipitated in stirring, and vacuum is taken out
Filter, takes filter residue to be dried in vacuo, 50 DEG C of vacuum drying temperature, and dry 6h is to get product.
(3) the paper mill sludge based polyalcohol (abbreviation LBF) of 0.25g made from step (2) is added in made from step (1)
In the aluminium polychloride ferrous solution of 100ml, 2h is stirred to react under room temperature to get different aluminum weight of iron than polyaluminum ferric chloride-make
Three products of paper sludge based polyalcohol composite flocculation agent.
The preparation of the composite flocculation agent (PFACl-LBF) of the different basicities of embodiment 2.
It is identical with described in embodiment 1, except that A1C13·6H20 dosage is 11.2g, FeC13·6H20 throwing
Dosage 6.0g, the additive amount of natrium carbonicum calcinatum is respectively 7.3g, 14.6g, 21.9g answering to get different basicities in step (1)
Close flocculant product.
The preparation of the composite flocculation agent (PFACl-LBF) of the different acrylamide additive amounts of embodiment 3.
It is identical with described in embodiment 2, except that the additive amount of natrium carbonicum calcinatum is fixed as 14.6g, third in step (2)
The additive amount of acrylamide is respectively that 1.0g, 2.0g, 3.0g, 4.0g produce to get the composite flocculation agent of different acrylamide additive amounts
Product.
The preparation of the composite flocculation agent (PFACl-LBF) of the different dimethyl diallyl ammonium chloride additive amounts of embodiment 4.
It is identical with described in embodiment 3, except that the additive amount of acrylamide is fixed as 2.0g, diformazan in step (2)
The additive amount of base diallyl ammonium chloride additive amount is respectively 4ml, 6ml, 8ml, 10ml to get different dimethyl diallyl chlorine
Change the composite flocculation agent product of ammonium additive amount.
The preparation of the composite flocculation agent (PFACl-LBF) of the different hybrid reaction times of embodiment 5.
It is identical with described in embodiment 4, except that dimethyl diallyl ammonium chloride additive amount is fixed as 6ml, step
(3) the hybrid reaction time in is 1h, 2h, 3h, 4h to get the composite flocculation agent product of different hybrid reaction times.
Application test：
Simulate the preparation of dyestuff water sample：
The disperse yellow dye of 0.1g is weighed, is added in into the tap water of 1L, dyestuff is continued stirring until and is completely dissolved, that is, be made into
The simulation disperse yellow water sample of 100mg/L.The emerald green blue dyestuff of activity of 0.1g is weighed, adds in into the tap water of 1L, continues stirring until
Dyestuff is completely dissolved, that is, is made into the emerald green blue water sample of simulation activity of 100mg/L.
The preparation of humic acid-Kaolin water sample：
Humic acid storing solution：1.0g humic acid and 0.4g sodium hydroxides are weighed, adds in the deionized water of about 800ml or so
In, 0.5h is persistently stirred, is settled to 1L, that is, is made into the humic acid storing solution of 1g/L；Aqueous suspension ofkaolin：Weigh 5.0g kaolinites
Soil adds in the deionized water of 1L and persistently stirs 0.5h, is transferred in the graduated cylinder of 1L, static 0.5h, takes top 500ml suspensions
With spare.
The preparation of coagulation experiment humic acid-Kaolin water sample：It is 1 to take volume ratio:1 deionized water and tap water,
Add in above-mentioned humic acid storing solution and aqueous suspension ofkaolin thereto, make humic acid concentration for 10mg/L, turbidity for 15.0 ±
0.5NTU。
With the present invention product do flocculant process simulated water sample, dosage in terms of the mass concentration (mg/L) of (Al+Fe),
Finally go out water treatment efficiency to represent with coloration (absorbance) removal rate (%) and dissolved organic carbon (DOC) removal rate (%).
Application example 1：Polyaluminum ferric chloride prepared by above-described embodiment 1-paper mill sludge based polyalcohol (PFACl-
LBF) processing applied to simulation disperse yellow dye water sample, treatment effect are listed in the table below 1.
Table 1 simulates the chroma removal rate (%) of disperse yellow dye water sample
To sum up table it is found that ferro-aluminum mass ratio has a certain impact to the quality of composite flocculation agent PFACl-LBF, come by totality
It sees, is 1 in ferro-aluminum mass ratio:When 1, coagulation effect is best.Increase aluminium content or increase iron content, can suitably weaken coagulation and take off
Color rate, and increase the risk of residual Al and remaining coloration in water, therefore preferably ferro-aluminum mass ratio is 1:1.
Application example 2：Polyaluminum ferric chloride prepared by above-described embodiment 2-paper mill sludge based polyalcohol (PFACl-
LBF) processing applied to simulation disperse yellow dye water sample, treatment effect are listed in the table below 2.
Table 2 simulates the chroma removal rate (%) of disperse yellow dye water sample
The change of basicity can influence the hydrolyzation morphology of aluminium, iron ion in water, with the rising of basicity, aluminium, iron from
Son is more easy to be hydrolyzed to the hydrolysate of polymeric form, and convolution and charge neutrality effect are caught so as to improve net.Therefore, basicity 1.0
When, the coagulation effect of PFACl-LBF is substantially better than the composite flocculation agent that basicity is 0.5.But when basicity continues to increase, coagulation
Efficiency changes little.With reference to the problems such as the storage duration of financial cost and flocculant, basicity is preferably 1.0.
Application example 3：Polyaluminum ferric chloride prepared by above-described embodiment 3-paper mill sludge based polyalcohol (PFACl-
LBF) processing applied to simulation disperse yellow dye water sample, treatment effect are listed in the table below 3.
Table 3 simulates the chroma removal rate (%) of disperse yellow dye water sample
The main function of acrylamide is to be combined to form polymeric form substance with the lignin molecule in paper mill sludge, is improved
The molecular weight of flocculant, so as to improve the effect of the adsorption bridging of product.When increasing with acrylamide as 2.0g, coagulation efficiency has
It is apparent to improve, when the amount of acrylamide further increases, the growth trend unobvious of percent of decolourization.And when the amount mistake of acrylamide
Gao Shi can further influence the hybrid reaction time in step (3), so as to increase operating cost.Therefore, the amount of acrylamide is excellent
It is selected as 2.0g.
Application example 4：Polyaluminum ferric chloride prepared by above-described embodiment 4-paper mill sludge based polyalcohol (PFACl-
LBF) processing applied to simulation disperse yellow dye water sample, treatment effect are listed in the table below 4.
Table 4 simulates the chroma removal rate (%) of disperse yellow dye water sample
Dimethyl diallyl ammonium chloride can be with the lignin molecule graft copolymerization in paper sludge so as to introduce cation
Quaternary ammonium group, prepare the paper mill sludge based polyalcohol of cationic.Cation group can be with the negative pollutant in water body
Charge neutrality effect occurs, further reunites, precipitate and remove, achieve the purpose that water body purification.From the point of view of comprehensive upper table, dimethyl
When the amount of diallyl ammonium chloride maintains 6-8ml, coagulation effect is preferable, too high or too low all to reduce coagulation effect.With reference to
Financial cost, the amount of dimethyl diallyl ammonium chloride is preferably 6ml.
Application example 5：Polyaluminum ferric chloride prepared by above-described embodiment 5-paper mill sludge based polyalcohol (PFACl-
LBF) processing applied to simulation disperse yellow dye water sample, treatment effect are listed in the table below 5.
Table 5 simulates the chroma removal rate (%) of disperse yellow dye water sample
Since paper mill sludge base flocculant is compared to conventional polymer flocculant, dissolubility is preferable, can effectively drop
The low hybrid reaction time with inorganic salts.When incorporation time is too short, mixing is not thorough, and influences coagulation effect；Work as incorporation time
How long when, be easy to cause the decomposition of the hydrolysate or paper mill sludge based polyalcohol of inorganic salts, it is comprehensive so as to reduce coagulation efficiency
Upper table data are it is found that the hybrid reaction time is preferably 2h.
Application example 6：By above example 1 prepare it is preferred after polyaluminum ferric chloride-paper mill sludge based polyalcohol
(PFACl-LBF) for the processing of condition of different pH Imitating dyestuff water sample, dosage is fixed as 5mg/L, and with PFACl and
LBF carries out comparison coagulation efficiency, and treatment effect is listed in the table below 6.
Table 6 simulates the chroma removal rate (%) of disperse yellow dye water sample
From upper table can, between pH ranges 5-10, the coagulation effect of PFACl is influenced maximum by pH.PFACl-LBF and
LBF is influenced smaller by pH.And the percent of decolourization of PFACl-LBF is far above other two kinds of chemical agents, this is also to a certain extent
Expand the application range of PFACl-LBF.
Application example 7：By above example 1 prepare it is preferred after polyaluminum ferric chloride-paper mill sludge based polyalcohol
(PFACl-LBF) for the processing of the emerald green blue dyestuff water sample of condition of different pH Imitating activity, dosage is fixed as 5mg/L, and with
PFACl and LBF carries out comparison coagulation efficiency, and treatment effect is listed in the table below 7.
Table 7 simulates the chroma removal rate (%) of active emerald green blue dyestuff water sample
As can be seen from the above table, comparison and two kinds of medicaments of PFACl and LBF, PFACl-LBF still have active dye wastewater
Good decolorizing effect, percent of decolourization highest also improve more than 50%, and in the pH conditions section of experiment, the fluctuation model of percent of decolourization
Enclose small, stable height.
Application example 8：By above example 1 prepare it is preferred after polyaluminum ferric chloride-paper mill sludge based polyalcohol
(PFACl-LBF) for the processing of condition of different pH Imitating humic acid-kaolin water sample, dosage is fixed as 3mg/L, and with
PFACl and LBF carries out comparison coagulation efficiency, and treatment effect is listed in the table below 8.
Table 8 simulates the DOC removal rates (%) of humic acid-kaolin water sample
As can be known from the above table, PFACl-LBF also has good removal effect to low molecular weight pollutant humic acid, also compares
For PFACl and LBF, coagulation effect is smaller with the constant interval of pH, and significantly improves DOC removal rates up to 20% or so.
Claims (5)
1. a kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent, the composite flocculation agent is clear solution,
Be by after paper mill sludge elder generation synthesizing cationic type macromolecule paper mill sludge based polyalcohol, it is standby with polyaluminum ferric chloride solution mixing system
It forms, the total mass concentration of Fe and Al is 8~12 g/L in aluminium polychloride ferrous solution；Wherein, paper mill sludge based polyalcohol with
The total mass ratio of Fe and Al is 1 in aluminium polychloride ferrous solution：（1~8）, the current potential of composite flocculation agent is+25~35mV, viscosity
For 1.10~1.25 mPa s, molecular weight is 500~1000 KDa；
Preparation method is as follows including step：
（1）The preparation of polyaluminum ferric chloride
Weigh FeC13•6H20 and A1C13•6H20 solid is simultaneously dissolved in deionized water, controls Fe：The mass ratio of Al is 1.0：1,
Na is added dropwise2CO3Solution controls OH-：（Fe3++Al3+）Molar ratio be 1.0：1, it stirs to solid and is completely dissolved, according to
Phosphorus, iron molar ratio are 0.08：1 ratio adds in stabilizer Na2HPO4•12H20 powder continues stirring to being completely dissolved, adds water dilute
It is 8~12 g/L to release to the total mass concentration of Fe and Al；Aluminium polychloride ferrous solution is made；The gross mass and deionized water of ferro-aluminum
Volume ratio is 1：20~35, unit g/ml；
（2）The preparation of cationic high-molecular paper mill sludge based polyalcohol
The paper mill sludge is dissolved in deionized water, the mass volume ratio of paper mill sludge and deionized water is 2: (50~
60) g/ml ；Stirring is lower to be added dropwise NaOH solution, and control pH takes mixture to centrifuge, take in 11.0~12.0,10~30min of stirring
Supernatant is poured into reactor, and it is 7.0~8.0 to adjust pH；
Reactor is heated to 70 DEG C~80 DEG C, adds in potassium persulfate, the mass ratio of paper mill sludge and potassium persulfate is 2:
（0.05~0.07）, after leading to 10~15min of nitrogen, add in disodium ethylene diamine tetraacetate, paper mill sludge and ethylenediamine tetra-acetic acid two
The mass ratio of sodium is 2:（0.05~0.07）, lead to nitrogen the reaction was continued 3~5min；Add in acrylamide and dimethyl diallyl
The mass ratio of the mixed liquor of ammonium chloride, paper mill sludge and acrylamide is 2:（1.5~2.5）, paper mill sludge quality and dimethyl
The ratio of diallyl ammonium chloride volume is 2:（6~10）, unit g/ml leads to after nitrogen reacts 3~5min, it is stirred to react 3~
4h, 70 DEG C~80 DEG C of reaction temperature；
Reaction terminates products obtained therefrom being cooled to room temperature, and adds in acetone evolution reaction product, staticly settles, filter residue vacuum is taken to do
It is dry, obtain cationic high-molecular paper mill sludge based polyalcohol；
（3）The preparation of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent
By step（2）Cationic high-molecular paper mill sludge based polyalcohol obtained adds in step（1）Aluminium polychloride obtained
In ferrous solution, cationic high-molecular paper mill sludge based polyalcohol with（Fe+Al）Mass ratio control for 1：（4-6）, under room temperature
1~3h is stirred to react to get polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent.
2. polyaluminum ferric chloride according to claim 1-paper mill sludge based polyalcohol composite flocculation agent, which is characterized in that
Step（2）The mass ratio of middle paper mill sludge and potassium persulfate is 2:0.05, the matter of paper mill sludge and disodium ethylene diamine tetraacetate
Amount is than being 2:0.06.
3. polyaluminum ferric chloride according to claim 1-paper mill sludge based polyalcohol composite flocculation agent, which is characterized in that
Step（2）The mass ratio of middle paper mill sludge and acrylamide is 2:2.0, paper mill sludge quality and dimethyl diallyl ammonium chloride
The ratio of volume is 2:（6~8）, unit g/ml, reaction temperature is 70 DEG C, 3 h of reaction time.
4. polyaluminum ferric chloride according to claim 1-paper mill sludge based polyalcohol composite flocculation agent, which is characterized in that
Step（2）The mass concentration of middle dimethyl diallyl ammonium chloride is 50~70wt%, and vacuum drying temperature is 40~60 DEG C, is done
The dry time is 7~9 h, and vacuum degree is 130~140 Pa.
5. the application of polyaluminum ferric chloride described in claim 1-paper mill sludge based polyalcohol composite flocculation agent, water supply,
Field of waste water treatment, flocculant dosage are 1~20mg/L, and applicable pH is 5~10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971055.1A CN105384231B (en) | 2015-12-22 | 2015-12-22 | A kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971055.1A CN105384231B (en) | 2015-12-22 | 2015-12-22 | A kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105384231A CN105384231A (en) | 2016-03-09 |
| CN105384231B true CN105384231B (en) | 2018-06-29 |
Family
ID=55417073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510971055.1A Active CN105384231B (en) | 2015-12-22 | 2015-12-22 | A kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384231B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946438A (en) * | 2017-04-27 | 2017-07-14 | 郑州轻工业学院 | The organic composite sludge dehydration conditioner and preparation method prepared using paper mill sludge |
| CN107162383B (en) * | 2017-05-09 | 2020-08-21 | 同济大学 | High-efficiency low-chlorine conditioner and application thereof in dehydration of high-solid digested sludge |
| CN108455713B (en) * | 2018-03-19 | 2021-06-04 | 南阳中昊科技有限公司 | Waste paper deinking wastewater flocculant and preparation method thereof |
| CN108394976B (en) * | 2018-03-30 | 2020-11-03 | 浙江大学 | Floating type flocculating agent and preparation method thereof |
| CN108585155A (en) * | 2018-03-30 | 2018-09-28 | 浙江大学 | Polyaluminum ferric chloride-（Chitose-acrylic amide-magnesium lignosulfonate graft copolymer）Composite flocculation agent and preparation method thereof |
| CN110002557A (en) * | 2019-04-17 | 2019-07-12 | 山东大学 | A kind of preparation method of the high grafting rate paper mill sludge base Inorganic whisker water treatment agent of inorganic coagulant- |
| FI129034B (en) * | 2019-06-14 | 2021-05-31 | Kemira Oyj | Use of a treatment system comprising wood-based organic material for removing dissolved organic compounds from wastewater |
| CN114369968A (en) * | 2020-10-14 | 2022-04-19 | 刘耀红 | Special agent for sludge papermaking and preparation method thereof |
| CN113896306B (en) * | 2021-10-26 | 2023-08-29 | 广州市芦苇环保科技有限责任公司 | Polymeric aluminum ferric chloride flocculant and preparation method thereof |
| CN114590877B (en) * | 2022-03-10 | 2023-02-07 | 华北水利水电大学 | Construction method of compound coagulation system for efficiently removing bromate and application of compound coagulation system in water treatment |
| CN114573082A (en) * | 2022-03-10 | 2022-06-03 | 华北水利水电大学 | Construction and application method of inorganic-organic compound coagulation system for synchronously removing nitrate radicals and organic matters |
| CN114455685A (en) * | 2022-03-22 | 2022-05-10 | 衡阳市建衡实业有限公司 | Poly aluminum ferric chloride liquid product and preparation method and application thereof |
| CN114804315B (en) * | 2022-06-06 | 2023-07-14 | 中国铁工投资建设集团有限公司 | Polyaluminium ferric chloride prepared from municipal sludge drying pyrolysis residues and composite flocculant |
| CN115010231B (en) * | 2022-07-07 | 2023-12-29 | 江苏富淼科技股份有限公司 | Stabilizer of polyiron coagulant and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6491827B1 (en) * | 1999-02-12 | 2002-12-10 | Steen Research, Llc | Process for reducing true color in waste liquids |
| CN102583684A (en) * | 2012-03-14 | 2012-07-18 | 山东大学 | Method for preparing flocculating agent from paper mill sludge |
| CN103964557A (en) * | 2014-05-21 | 2014-08-06 | 山东大学 | Method for preparing cationic organic flocculant by using paper-making sludge |
-
2015
- 2015-12-22 CN CN201510971055.1A patent/CN105384231B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6491827B1 (en) * | 1999-02-12 | 2002-12-10 | Steen Research, Llc | Process for reducing true color in waste liquids |
| CN102583684A (en) * | 2012-03-14 | 2012-07-18 | 山东大学 | Method for preparing flocculating agent from paper mill sludge |
| CN103964557A (en) * | 2014-05-21 | 2014-08-06 | 山东大学 | Method for preparing cationic organic flocculant by using paper-making sludge |
Non-Patent Citations (1)
| Title |
|---|
| Floc characterization and membrane fouling of polyferric-polymer dual/composite coagulants in coagulation/ultrafiltration hybrid process;Hongyan Rong等;《Journal of Colloid and Interface Science》;20130917;第142卷;第39页摘要，第40-45页第1-4节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105384231A (en) | 2016-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105384231B (en) | A kind of polyaluminum ferric chloride-paper mill sludge based polyalcohol composite flocculation agent and preparation method thereof | |
| CN102774947B (en) | Biological compound flocculant and application thereof | |
| CN105621742B (en) | Desulfurization wastewater sofening treatment device and method | |
| CN104261530B (en) | Dephosphorization flocculating agent and preparation method thereof | |
| CN105523620B (en) | A kind of ferric sulfate of polymerized silica base inorganic-organic composite flocculating agent and preparation method thereof | |
| CN104556331B (en) | PAC (polyaluminium chloride)-modified sodium alginate inorganic-organic composite flocculant and preparation method thereof | |
| CN104478050B (en) | A kind of preparation method and applications of the improved PFS for processing industrial wastewater | |
| CN103964557B (en) | A kind of method utilizing paper mill sludge to prepare positively charged ion organic floculant | |
| CN108176403B (en) | Co-loaded activated carbon fiber3O4Method for preparing catalytic material | |
| CN105565459B (en) | A kind of poly-ferric chloride-paper mill sludge base aminated polymer composite flocculation agent and preparation method thereof | |
| CN106430495A (en) | Preparation method of composite decolorizing flocculating agent for wastewater treatment | |
| CN110117149A (en) | A kind of Opsonizing method of catalysis oxidation type sludge conditioner and sludge | |
| CN107226599A (en) | The preparation method and the recycling processing method of heavy metal sewage sludge of a kind of ferric-polysilicate flocculant using iron content heavy metal sewage sludge as raw material | |
| CN105060444A (en) | Papermaking wastewater treatment agent and manufacturing method thereof | |
| CN107324468A (en) | A kind of preparation method and application of polyaluminium sulfate titanium | |
| CN102211804B (en) | Preparation method of starch-based flocculating agent | |
| CN110316800A (en) | A kind of method of preparation and use of the flocculant for Treatment of Coking Effluent | |
| CN102351993B (en) | Preparation method for flocculant starch of grafted acryl oxyethyl trimethyl ammonium chloride | |
| CN104386793A (en) | Magnetic polyacrylamide cationic flocculant with super-high molecular weight and method for preparing magnetic polyacrylamide cationic flocculant with super high molecular weight | |
| CN105001381B (en) | A kind of preparation method of paper mill sludge base Amphiphatic high polymer coagulant | |
| CN109354314B (en) | Combined biological bed treatment process for low-carbon-source high-ammonia-nitrogen high-organophosphorus wastewater | |
| CN108164124A (en) | A kind of deep dehydration conditioner and its application suitable for advanced anaerobically digested sludge | |
| CN106587314A (en) | Efficient phosphorus removal agent and preparation method thereof | |
| CN107324466A (en) | Method is prepared in situ in a kind of river course water treatment coagulant | |
| CN109231387A (en) | A kind of compound material for water treatment of stalk/aluminium polychloride and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |