CN107758826B - A kind of preparation method of sewage treatment flocculating agent - Google Patents
A kind of preparation method of sewage treatment flocculating agent Download PDFInfo
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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
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Abstract
The invention belongs to water treatment engineering technology fields, and in particular to a kind of preparation method of sewage treatment flocculating agent.The invention discloses a kind of preparation methods of sewage treatment flocculating agent, include the following steps：S1. the extraction of wheat-bran fiber element；S2. the modification of cellulose is hidden；S3. the modification of konjaku glucomannan；S4. the preparation of graft copolymer；S5. graft copolymer ionizes.Solvent recovery is used in preparation process of the present invention, reduces the pollution to environment, modified cellulose is directly dissolved, the complexity of preparation is reduced.There is flocculant safety and environmental protection produced by the present invention simultaneously good degradability and flocculating effect, wherein turbidity removal rate to be up to 99.7%, COD removal rates and be up to 94.3%, and degradation rate is up to 68.2% within 30 days.
Description
Technical field
The invention belongs to water treatment engineering technology fields, and in particular to a kind of preparation method of sewage treatment flocculating agent.
Background technology
It coagulates as one of the important operation being separated by solid-liquid separation in sewage disposal, it is typically essential in sewage disposal process
A part.Compared to other water technologies, flocculation treatment is more inexpensive, low power consuming and easily operated.Currently, flocculant master
It is divided into three kinds of inorganic flocculating agent, organic flocculant and microbial flocculant, wherein organic flocculant can be divided into organic synthesis again
Two kinds of class and natural polymer subclass.Natural polymer subclass flocculant due to its have selectivity is big, derive from a wealth of sources, it is cheap,
The advantages that biodegradable, environmentally friendly, nontoxic, by the more and more concerns of academia and society.But existing natural height
Molecule class flocculant has that degradability is poor, safety is low, of high cost and flocculating effect is poor, so providing a kind of peace
Quan Xinggao, degradable, the good flocculant of flocculating effect is necessary.
Chinese patent CN104017136B discloses a kind of cellulose modified flocculant, it is that cellulose is dispersed in ethyl alcohol
And in sodium hydroxide mixed solution, after alkalization, monoxone is added in alkalization, and above-mentioned system pH is finally adjusted to using acid by reaction
Carboxymethyl cellulose is made in neutrality；In above-mentioned solution, initiator is added, then by methylacryoyloxyethyl trimethyl chlorine
Change ammonium（DMC）Solution is slowly added dropwise into cmc soln, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride（DMC）With
The mass ratio of cellulose is：0.1-10 reacts 1-4h at 45-75 DEG C, is eventually adding acetone precipitation, and carboxymethyl obtained is fine
Dimension element grafting polymethyl acyloxyethyl trimethyl ammonium chloride, but cellulose modified flocculant flocculation effect made from the invention
Fruit and degradability are to be improved.
Chinese patent CN103980367B discloses a kind of preparation method of carboxycellulose flocculant, by cellulosic material
By the abundant dissolving of sodium hydroxide and urea, oxidant is added, generates aldocellulose, recycles schiff bases path and residue
Solvent is reacted, and a kind of carboxycellulose flocculant is generated, although this method is simple, raw material are easy to get, production cost is low, easily
In popularization and application, but its flocculating effect and degradability are to be improved.
Invention content
In order to solve the problems in the existing technology, the purpose of the present invention is to provide a kind of systems of water treatment flocculant
Preparation Method.Flocculant safety and environmental protection produced by the present invention has good degradability and flocculating effect.Simultaneously prepared by the present invention
Solvent recovery is used in the process, reduces the pollution to environment, modified cellulose is directly dissolved, the complexity of preparation is reduced
Property.
The present invention provides a kind of preparation methods of sewage treatment flocculating agent, include the following steps：
S1 washes 10-20g wheat bran pulp waters 4-5 times, is added in 200-250mL acid mixed liquors after natural air drying, water-bath extraction
1-2h, cooling and standings, filtering obtain filter residue；The filter residue is washed to neutrality, is added in 100-200mL alkali mixed liquors, 1- is extracted
2h is filtered, and is washed, dry, obtains cellulose；
Cellulose obtained by 5g steps S1 is added into 5-10mL alkali ionic liquids S2, and stirs and 15-25mL hydrogen is added
Sodium hydroxide solution stirs evenly, and obtains cellulose solution；The cellulose solution is added into vacuum sealing Fu, 4-8g is added
Etherifying agent reacts 1-2h at 50-70 DEG C, recycles etherifying agent, hot water washing, and hydrochloric acid is adjusted to neutrality, washs, obtain hydroxypropyl methyl
Cellulose ether；
S3 takes 1-2g konjaku glucomannans to be placed in 10-20mL water, and 1-5mL sodium hydroxide solutions, stirring is added in stirring
After 10-20min, 2-3g sodium tripolyphosphates are added, 60-80 DEG C of water-bath 8-12h is washed, dry, and it is sweet poly- to obtain modified konjaku Portugal
Sugar；
S4 by hydroxypropyl methyl cellulose ether obtained by step S2 with modified konjac glucomannan obtained by step S3 by weight
5:1 mixing, is uniformly mixed, obtains modified mixture；The modified mixture 1-2g is taken, is added into 20-30mL water, is passed through nitrogen
And 20-40min is stirred, initiator is added at 50-70 DEG C, stirs 10-20min, adds acrylamide, reacts 40-
60min, it is cooling, it washs, it is dry, obtain graft copolymer；
The formaldehyde and diethylamine of S5 amount of substance such as addition into graft copolymer obtained by step S4, are stirred to react 1-2h, i.e.,
.
Further, in the step S1 sour mixed liquor by acetic acid and dilute sulfuric acid by weight 1:2 composition, alkali mixed liquor by
0.5M sodium hydroxides and ammonium hydroxide are by weight 3:2 compositions.
Further, the preparation method of the step S2 neutral and alkali ionic liquids is：
（1）By N- methylimidazoles and allyl chloride in molar ratio 1:1.1 are added into three-necked flask, 120 DEG C of magnetic agitations
Device, cooling for reflux 1.5h, ethyl acetate washing are evaporated under reduced pressure, crystallize, dry, obtain -3 methylimidazole villaumite of 1- allyls；
（2）By equimolar step（1）- 3 methylimidazole villaumite of gained 1- allyls is mixed with the sodium hydroxide solution of 1M,
Microwave reaction 25min at 100 DEG C, cooling, rotary evaporation, it is dry to get.
Further, in the step S2 etherifying agent by chloromethanes and propylene oxide by weight 1:(3-4) is formed.
Further, initiator is manganese pyrophosphate-oxalic acid system in the step S4, by weight by manganese pyrophosphate and oxalic acid
Than 3:2 compositions.
Further, the addition of initiator is 0.1-0.2 times of modified mixture weight in the step S4, acryloyl
The addition of amine is 1.5-2.5 times of modified mixture weight.
The present invention is dissolved in using the wheat-bran fiber of environment-friendly degradable as skeleton in alkali ionic liquid, passes through chloromethanes
It is modified with propylene oxide, improves water solubility, to reduce the complexity of its preparation, simplifies technique.The present invention uses
Homemade alkali ionic liquid is not only effectively increased the dissolubility of cellulose, also improves the etherificate degree of cellulose, into
And the modification conversion ratio of cellulose is improved, save cost.In addition, modification is added in the present invention on the basis of modified cellulose
Konjaku glucomannan can not only play antibacterial effect, also significantly improve flocculating effect；Finally use manganese pyrophosphate-
Oxalic acid system initiator is grafted modified mixture, which improves the conversion ratio of grafting rate and monomer, reduce material
Waste, saved cost, sewage treatment flocculating agent produced by the present invention has good flocculating effect and biological degradability.
Compared with prior art, the present invention has the advantage that：
（1）The present invention is directly natural high to take preparation into account with cellulose using alkali ionic liquid dissolving wheat-bran fiber element
Molecular flocculant, to reduce the complexity of preparation and improve the economic benefit of production process；
（2）The present invention carries out graft reaction using manganese pyrophosphate-oxalic acid system initiator, not only increases grafting rate and list
The conversion ratio of body, also effectively reduces cost；
（3）Sewage treatment flocculating agent safety and environmental protection produced by the present invention, it is antibacterial degradable, there is good effect of flocculating
Fruit, wherein turbidity removal rate are up to 99.7%, COD removal rates and are up to 94.3%, and degradation rate is up to 68.2% within 30 days.
Specific implementation mode
Explanation is further explained to the present invention below by specific embodiment, these embodiments are only used for the mesh of illustration
, it is not intended to limit protection scope of the present invention.
A kind of preparation method of 1 sewage treatment flocculating agent of embodiment
S1 washes 10g wheat bran pulp waters 4 times, is added in 200mL acid mixed liquors after natural air drying, and the acid mixed liquor is by vinegar
Acid and dilute sulfuric acid are by weight 1:2 compositions, water-bath extract 1h, cooling and standings, and filtering obtains filter residue；During the filter residue is washed to
Property, it is added in 100mL alkali mixed liquors, the alkali mixed liquor is by 0.5M sodium hydroxides and ammonium hydroxide by weight 3:2 compositions, extraction
1h is filtered, and is washed, dry, obtains cellulose；
Cellulose obtained by 5g steps S1 is added into 5mL alkali ionic liquids S2, and stirs and 15mL sodium hydroxides are added
Solution stirs evenly, and obtains cellulose solution；The cellulose solution is added into vacuum sealing Fu, 4g etherifying agents, institute is added
Etherifying agent is stated by chloromethanes and propylene oxide by weight 1:3 compositions, react 1h at 50 DEG C, recycle etherifying agent, and hot water washs,
Hydrochloric acid is adjusted to neutrality, and washing obtains hydroxypropyl methyl cellulose ether；
S3 takes 1g konjaku glucomannans to be placed in 10mL water, and 1mL sodium hydroxide solutions are added in stirring, after stirring 10min,
2g sodium tripolyphosphates are added, 60 DEG C of water-bath 8h are washed, dry, obtain modified konjac glucomannan；
S4 by hydroxypropyl methyl cellulose ether obtained by step S2 with modified konjac glucomannan obtained by step S3 by weight
5:1 mixing, is uniformly mixed, obtains modified mixture；The modified mixture 1g is taken, is added into 20mL water, is passed through nitrogen and stirs
20min is mixed, initiator manganese pyrophosphate-oxalic acid system of 0.1 times of modified mixture weight, the pyrophosphoric acid are added at 50 DEG C
Manganese-oxalic acid system is by manganese pyrophosphate and oxalic acid by weight 3:2 compositions, stir 10min, add modified mixture weight 1.5
Acrylamide again reacts 40min, cooling, washs, dry, obtains graft copolymer；
The formaldehyde and diethylamine of S5 amount of substance such as addition into graft copolymer obtained by step S4, are stirred to react 1h, i.e.,
.
The preparation method of the step S2 neutral and alkali ionic liquids is：
（1）By N- methylimidazoles and allyl chloride in molar ratio 1:1.1 are added into three-necked flask, 120 DEG C of magnetic agitations
Device, cooling for reflux 1.5h, ethyl acetate washing are evaporated under reduced pressure, crystallize, dry, obtain -3 methylimidazole villaumite of 1- allyls；
（2）By equimolar step（1）- 3 methylimidazole villaumite of gained 1- allyls is mixed with the sodium hydroxide solution of 1M,
Microwave reaction 25min at 100 DEG C, cooling, rotary evaporation, it is dry to get.
A kind of preparation method of 2 sewage treatment flocculating agent of embodiment
S1 washes 15g wheat bran pulp waters 5 times, is added in 225mL acid mixed liquors after natural air drying, and the acid mixed liquor is by vinegar
Acid and dilute sulfuric acid are by weight 1:2 compositions, water-bath extract 1.5h, cooling and standings, and filtering obtains filter residue；The filter residue is washed to
Neutrality is added in 150mL alkali mixed liquors, and the alkali mixed liquor is by 0.5M sodium hydroxides and ammonium hydroxide by weight 3:2 compositions, extraction
1.5h is filtered, and is washed, dry, obtains cellulose；
Cellulose obtained by 5g steps S1 is added into 8mL alkali ionic liquids S2, and stirs and 20mL sodium hydroxides are added
Solution stirs evenly, and obtains cellulose solution；The cellulose solution is added into vacuum sealing Fu, 6g etherifying agents, institute is added
Etherifying agent is stated by chloromethanes and propylene oxide by weight 1:3.5 compositions, react 1.5h at 60 DEG C, recycle etherifying agent, hot water
Washing, hydrochloric acid are adjusted to neutrality, wash, obtain hydroxypropyl methyl cellulose ether；
S3 takes 1.5g konjaku glucomannans to be placed in 15mL water, and 3mL sodium hydroxide solutions are added in stirring, stirs 15min
Afterwards, 2.5g sodium tripolyphosphates are added, 70 DEG C of water-bath 10h are washed, dry, obtain modified konjac glucomannan；
S4 by hydroxypropyl methyl cellulose ether obtained by step S2 with modified konjac glucomannan obtained by step S3 by weight
5:1 mixing, is uniformly mixed, obtains modified mixture；The modified mixture 1.5g is taken, is added into 25mL water, is passed through nitrogen simultaneously
30min is stirred, initiator manganese pyrophosphate-oxalic acid system of 0.15 times of modified mixture weight, the coke phosphorus are added at 60 DEG C
Sour manganese-oxalic acid system is by manganese pyrophosphate and oxalic acid by weight 3:2 compositions, stir 15min, add modified mixture weight 2
Acrylamide again reacts 50min, cooling, washs, dry, obtains graft copolymer；
The formaldehyde and diethylamine of S5 amount of substance such as addition into graft copolymer obtained by step S4, are stirred to react 1-2h, i.e.,
.
The preparation method of the step S2 neutral and alkali ionic liquids is similar to Example 1.
A kind of preparation method of 3 sewage treatment flocculating agent of embodiment
S1 washes 20g wheat bran pulp waters 5 times, is added in 250mL acid mixed liquors after natural air drying, and the acid mixed liquor is by vinegar
Acid and dilute sulfuric acid are by weight 1:2 compositions, water-bath extract 2h, cooling and standings, and filtering obtains filter residue；During the filter residue is washed to
Property, it is added in 200mL alkali mixed liquors, the alkali mixed liquor is by 0.5M sodium hydroxides and ammonium hydroxide by weight 3:2 compositions, extraction
2h is filtered, and is washed, dry, obtains cellulose；
Cellulose obtained by 5g steps S1 is added into 10mL alkali ionic liquids S2, and stirs and 25mL hydroxides are added
Sodium solution stirs evenly, and obtains cellulose solution；The cellulose solution is added into vacuum sealing Fu, 8g etherifying agents are added,
The etherifying agent is by chloromethanes and propylene oxide by weight 1:4 compositions, react 2h at 70 DEG C, recycle etherifying agent, hot water wash
It washs, hydrochloric acid is adjusted to neutrality, and washing obtains hydroxypropyl methyl cellulose ether；
S3 takes 2g konjaku glucomannans to be placed in 20mL water, and 5mL sodium hydroxide solutions are added in stirring, after stirring 20min,
3g sodium tripolyphosphates are added, 60-80 DEG C of water-bath 12h is washed, dry, obtains modified konjac glucomannan；
S4 by hydroxypropyl methyl cellulose ether obtained by step S2 with modified konjac glucomannan obtained by step S3 by weight
5:1 mixing, is uniformly mixed, obtains modified mixture；The modified mixture 2g is taken, is added into 30mL water, is passed through nitrogen and stirs
40min is mixed, initiator manganese pyrophosphate-oxalic acid system of 00.2 times of modified mixture weight, the pyrophosphoric acid are added at 70 DEG C
Manganese-oxalic acid system is by manganese pyrophosphate and oxalic acid by weight 3:2 compositions, stir 20min, add modified mixture weight 2.5
Acrylamide again reacts 60min, cooling, washs, dry, obtains graft copolymer；
The formaldehyde and diethylamine of S5 amount of substance such as addition into graft copolymer obtained by step S4, are stirred to react 1-2h, i.e.,
.
The preparation method of the step S2 neutral and alkali ionic liquids is similar to Example 1.
A kind of preparation method of 1 sewage treatment flocculating agent of comparative example
S1 washes 15g wheat bran pulp waters 5 times, is added in 225mL acid mixed liquors after natural air drying, and the acid mixed liquor is by vinegar
Acid and dilute sulfuric acid are by weight 1:2 compositions, water-bath extract 1.5h, cooling and standings, and filtering obtains filter residue；The filter residue is washed to
Neutrality is added in 150mL alkali mixed liquors, and the alkali mixed liquor is by 0.5M sodium hydroxides and ammonium hydroxide by weight 3:2 compositions, extraction
1.5h is filtered, and is washed, dry, obtains cellulose；
Cellulose obtained by 5g steps S1 is added into -3 methylimidazole villaumite ionic liquid of 8mL 1- allyls S2, and
20mL sodium hydroxide solutions are added in stirring, stir evenly, obtain cellulose solution；The cellulose solution is added to vacuum sealing
In Fu, 6g etherifying agents are added, the etherifying agent is by chloromethanes and propylene oxide by weight 1:3.5 compositions, react at 60 DEG C
1.5h, recycles etherifying agent, hot water washing, and hydrochloric acid is adjusted to neutrality, washs, obtain hydroxypropyl methyl cellulose ether；
S3 takes 1.5g konjaku glucomannans to be placed in 15mL water, and 3mL sodium hydroxide solutions are added in stirring, stirs 15min
Afterwards, 2.5g sodium tripolyphosphates are added, 70 DEG C of water-bath 10h are washed, dry, obtain modified konjac glucomannan；
S4 by hydroxypropyl methyl cellulose ether obtained by step S2 with modified konjac glucomannan obtained by step S3 by weight
5:1 mixing, is uniformly mixed, obtains modified mixture；The modified mixture 1.5g is taken, is added into 25mL water, is passed through nitrogen simultaneously
30min is stirred, initiator manganese pyrophosphate-oxalic acid system of 0.15 times of modified mixture weight, the coke phosphorus are added at 60 DEG C
Sour manganese-oxalic acid system is by manganese pyrophosphate and oxalic acid by weight 3:2 compositions, stir 15min, add modified mixture weight 2
Acrylamide again reacts 50min, cooling, washs, dry, obtains graft copolymer；
The formaldehyde and diethylamine of S5 amount of substance such as addition into graft copolymer obtained by step S4, are stirred to react 1-2h, i.e.,
.
The difference from example 2 is that the alkali ionic liquid in S2 is replaced with -3 methylimidazole villaumite of 1- allyls
Ionic liquid.
A kind of preparation method of 2 sewage treatment flocculating agent of comparative example
S1 washes 15g wheat bran pulp waters 5 times, is added in 225mL acid mixed liquors after natural air drying, and the acid mixed liquor is by vinegar
Acid and dilute sulfuric acid are by weight 1:2 compositions, water-bath extract 1.5h, cooling and standings, and filtering obtains filter residue；The filter residue is washed to
Neutrality is added in 150mL alkali mixed liquors, and the alkali mixed liquor is by 0.5M sodium hydroxides and ammonium hydroxide by weight 3:2 compositions, extraction
1.5h is filtered, and is washed, dry, obtains cellulose；
Cellulose obtained by 5g steps S1 is added into 8mL alkali ionic liquids S2, and stirs and 20mL sodium hydroxides are added
Solution stirs evenly, and obtains cellulose solution；The cellulose solution is added into vacuum sealing Fu, 6g etherifying agents, institute is added
Etherifying agent is stated by chloromethanes and propylene oxide by weight 1:3.5 compositions, react 1.5h at 60 DEG C, recycle etherifying agent, hot water
Washing, hydrochloric acid are adjusted to neutrality, wash, obtain hydroxypropyl methyl cellulose ether；
S3 takes hydroxypropyl methyl cellulose ether 1.5g obtained by step S2, is added into 25mL water, is passed through nitrogen and stirs
Initiator manganese pyrophosphate-oxalic acid system of 0.15 times of modified mixture weight, the manganese pyrophosphate-is added in 30min at 60 DEG C
Oxalic acid system is by manganese pyrophosphate and oxalic acid by weight 3:2 compositions, stir 15min, add the third of 2 times of modified mixture weight
Acrylamide reacts 50min, cooling, washs, dry, obtains graft copolymer；
The formaldehyde and diethylamine of S4 amount of substance such as addition into graft copolymer obtained by step S3, are stirred to react 1-2h, i.e.,
.
The preparation method of the step S2 neutral and alkali ionic liquids is similar to Example 1.
The difference from example 2 is that being not added with modified konjac glucomannan in step S3.
A kind of preparation method of 3 sewage treatment flocculating agent of comparative example
S1 washes 15g wheat bran pulp waters 5 times, is added in 225mL acid mixed liquors after natural air drying, and the acid mixed liquor is by vinegar
Acid and dilute sulfuric acid are by weight 1:2 compositions, water-bath extract 1.5h, cooling and standings, and filtering obtains filter residue；The filter residue is washed to
Neutrality is added in 150mL alkali mixed liquors, and the alkali mixed liquor is by 0.5M sodium hydroxides and ammonium hydroxide by weight 3:2 compositions, extraction
1.5h is filtered, and is washed, dry, obtains cellulose；
Cellulose obtained by 5g steps S1 is added into 8mL alkali ionic liquids S2, and stirs and 20mL sodium hydroxides are added
Solution stirs evenly, and obtains cellulose solution；The cellulose solution is added into vacuum sealing Fu, 6g etherifying agents, institute is added
Etherifying agent is stated by chloromethanes and propylene oxide by weight 1:3.5 compositions, react 1.5h at 60 DEG C, recycle etherifying agent, hot water
Washing, hydrochloric acid are adjusted to neutrality, wash, obtain hydroxypropyl methyl cellulose ether；
S3 takes 1.5g konjaku glucomannans to be placed in 15mL water, and 3mL sodium hydroxide solutions are added in stirring, stirs 15min
Afterwards, 2.5g sodium tripolyphosphates are added, 70 DEG C of water-bath 10h are washed, dry, obtain modified konjac glucomannan；
S4 by hydroxypropyl methyl cellulose ether obtained by step S2 with modified konjac glucomannan obtained by step S3 by weight
5:1 mixing, is uniformly mixed, obtains modified mixture；The modified mixture 1.5g is taken, is added into 25mL water, is passed through nitrogen simultaneously
30min is stirred, the initiator manganese pyrophosphate of 0.15 times of modified mixture weight is added at 60 DEG C, 15min is stirred, adds and change
Property 2 times of mixture weight acrylamide, react 50min, it is cooling, wash, it is dry, obtain graft copolymer；
The formaldehyde and diethylamine of S5 amount of substance such as addition into graft copolymer obtained by step S4, are stirred to react 1-2h, i.e.,
.
The preparation method of the step S2 neutral and alkali ionic liquids is similar to Example 1.
The difference from example 2 is that initiator manganese pyrophosphate-oxalic acid system in step S4 is replaced with pyrophosphoric acid
Manganese.
Test example one, grafting rate test
Graft copolymer in Example 1-3 and comparative example 1,3 in step S4, is fitted into filter paper packet, is put into Soxhlet pumping
It carries in device, is 60 with volume ratio:40 glacial acetic acid-ethylene glycol mixture reflux extracting for 24 hours, removes acrylate homopolymer, extracting
Residue is washed with acetone, and 55 DEG C of drying obtain pure graft copolymer, calculate grafting rate G and monomer conversion fs.Calculation formula：
Result of calculation is shown in Table 1.
1 grafting rate of table and monomer conversion
| Group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 3 |
| Grafting rate G/% | 300 | 320 | 310 | 270 | 255 |
| Monomer conversion fs/% | 96.1 | 99.6 | 97.8 | 87.5 | 83.1 |
As shown in Table 1, the grafting rate of the graft copolymer in the preparation method step S4 of sewage treatment flocculating agent of the present invention
It is higher with monomer conversion.Compared with comparative example 1,3, using the fiber of alkali ionic liquid modification in 1-3 of the embodiment of the present invention
Element and manganese pyrophosphate-oxalic acid system are preferable as the effect of initiator graft copolymerization, illustrate the fiber that alkali ionic liquid is modified
Element is more easy to and acrylic amide graft copolymerization, and initiator manganese pyrophosphate-oxalic acid system can make reaction more complete, reduces former
The waste of material improves the conversion ratio of reaction, improves the economic benefit of reflection.
Test example two, flocculating effect test
Waste water of paper mill 600mL is taken, is averagely fitted into 6 beakers, measures its turbidity, COD（COD）, biochemical need
Oxygen amount（BOD）And suspension content（SS）, data are recorded, and think that embodiment 1-3 and comparative example 1-3 is added in 6 beakers respectively
Flocculant 1.5mg obtained stirs 10min, stands, and is measuring turbidity, COD, BOD and SS, calculates turbidity removal rate, COD is gone
Except rate, BOD removal rates and SS removal rates, 2 are the results are shown in Table.
2 flocculating effect of table
| Group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Turbidity removal rate/% | 98.2 | 99.7 | 96.5 | 97.2 | 92.7 | 94.9 |
| COD removal rates/% | 90.5 | 94.3 | 92.4 | 84.9 | 80.2 | 82.5 |
| BOD removal rates/% | 88.4 | 92.1 | 90.3 | 82.8 | 78.3 | 80.6 |
| SS removal rates/% | 91.6 | 93.5 | 89.7 | 84.1 | 79.5 | 81.8 |
As shown in Table 2, sewage treatment flocculating agent produced by the present invention has preferable flocculating effect.With comparative example 1-3 phases
Than sewage treatment flocculating agent turbidity made from 1-3 of the embodiment of the present invention, the removal effect of COD, BOD and SS are preferable, illustrate this hair
It is bright effectively to improve the performance of flocculant under the action of alkali ionic liquid, modified konjac glucomannan agent initiator,
Reach preferable flocculating effect.
Test example three, degradation rate test
Flocculant made from embodiment 1-3 and comparative example 1-3 is added separately in the soil extract of the same terms, in
37 DEG C are degraded 90 days, are sampled respectively to the 5th day, 10 days, 20 days, 30 days, 60 days, 90 days, are calculated degradation rate, the results are shown in Table 3.
3 degradation rate of table
As shown in Table 3, sewage treatment flocculating agent degradation rate produced by the present invention is higher, and the feature of environmental protection is preferable.With comparative example 1-3
It compares, sewage treatment flocculating agent produced by the present invention is degradable, safety and environmental protection, illustrates the preparation of sewage treatment flocculating agent of the present invention
Method can effectively reduce environmental pollution, and improve graft copolymerization using alkali ionic liquid and modified konjac glucomannan
The degradability of object, to reach good degradability.Meanwhile it is best real for can be seen that the embodiment of the present invention 2 from table 1-3
Apply example.
Claims (6)
1. a kind of preparation method of sewage treatment flocculating agent, which is characterized in that include the following steps：
S1 washes 10-20g wheat bran pulp waters 4-5 times, is added into 200-250mL acid mixed liquors after natural air drying, and water-bath extracts 1-
2h, cooling and standings, filtering obtain filter residue；The filter residue is washed to neutrality, is added into 100-200mL alkali mixed liquors, 1- is extracted
2h is filtered, and is washed, dry, obtains cellulose；
Cellulose obtained by 5g steps S1 is added into 5-10mL alkali ionic liquids S2, and stirs and 15-25mL hydroxides are added
Sodium solution stirs evenly, and obtains cellulose solution；The cellulose solution is added into vacuum sealing Fu, 4-8g etherificates are added
1-2h is reacted in agent at 50-70 DEG C, recycles etherifying agent, hot water washing, and hydrochloric acid is adjusted to neutrality, washs, obtain hydroxypropyl methyl fiber
Plain ether；
S3 takes 1-2g konjaku glucomannans to be placed in 10-20mL water, and 1-5mL sodium hydroxide solutions are added in stirring, stirs 10-
After 20min, 2-3g sodium tripolyphosphates are added, 60-80 DEG C of water-bath 8-12h is washed, dry, obtains modified konjac glucomannan；
S4 is by hydroxypropyl methyl cellulose ether obtained by step S2 with modified taro Glucomannan obtained by step S3 by weight 5:1 is mixed
It closes, is uniformly mixed, obtains modified mixture；The modified mixture 1-2g is taken, is added into 20-30mL water, is passed through nitrogen and stirs
20-40min is mixed, initiator is added at 50-70 DEG C, stirs 10-20min, adds acrylamide, reacts 40-60min, it is cold
But, it washs, it is dry, obtain graft copolymer；
S5 such as is added at the formaldehyde and diethylamine of amount of substance into graft copolymer obtained by step S4, be stirred to react 1-2h to get.
2. the preparation method of sewage treatment flocculating agent as described in claim 1, which is characterized in that acid mixing in the step S1
Liquid is by acetic acid and dilute sulfuric acid by weight 1:2 compositions, alkali mixed liquor is by 0.5M sodium hydroxides and ammonium hydroxide by weight 3:2 compositions.
3. the preparation method of sewage treatment flocculating agent as described in claim 1, which is characterized in that the step S2 neutral and alkalis from
The preparation method of sub- liquid is：
（1）By N- methylimidazoles and allyl chloride in molar ratio 1:1.1 are added into three-necked flask, and 120 DEG C of magnetic stirring apparatus are cold
But flow back 1.5h, and ethyl acetate washing is evaporated under reduced pressure, crystallizes, dry, obtains -3 methylimidazole villaumite of 1- allyls；
（2）By equimolar step（1）- 3 methylimidazole villaumite of gained 1- allyls is mixed with the sodium hydroxide solution of 1M, and 100
Microwave reaction 25min at DEG C, cooling, rotary evaporation, it is dry to get.
4. the preparation method of sewage treatment flocculating agent as described in claim 1, which is characterized in that etherifying agent in the step S2
By chloromethanes and propylene oxide by weight 1:(3-4) is formed.
5. the preparation method of sewage treatment flocculating agent as described in claim 1, which is characterized in that initiator in the step S4
For manganese pyrophosphate-oxalic acid system, by manganese pyrophosphate and oxalic acid by weight 3:2 compositions.
6. the preparation method of sewage treatment flocculating agent as described in claim 1, which is characterized in that initiator in the step S4
Addition be 0.1-0.2 times of modified mixture weight, the addition of acrylamide is the 1.5-2.5 of modified mixture weight
Times.
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| WO1999015564A1 (en) * | 1997-09-19 | 1999-04-01 | Board Of Regents Of University Of Nebraska | Production of microcrystalline cellulose by reactive extrusion |
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