CN110078355A - A kind of flocculant and its synthetic method applied to sludge conditioning - Google Patents
A kind of flocculant and its synthetic method applied to sludge conditioning Download PDFInfo
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- CN110078355A CN110078355A CN201910466617.5A CN201910466617A CN110078355A CN 110078355 A CN110078355 A CN 110078355A CN 201910466617 A CN201910466617 A CN 201910466617A CN 110078355 A CN110078355 A CN 110078355A
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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
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
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Abstract
The invention discloses a kind of flocculants and its synthetic method applied to sludge conditioning.Flocculant is polymer represented by general formula (1)；The synthetic method of flocculant be by lignin and 2- bromine isobutyl acylbromide and organic ion solution under 4 DEG C of ice-water bath synthetic macromolecule initiator；Under 4 DEG C of ice-water baths and nitrogen protection, under copper bromide and reaction ligand catalysis, macromole evocating agent polymerize to obtain final flocculant with reaction monomers.The Novel wooden quality Flokal B that the present invention obtains has powerful adsorption function, can be widely applied to the flocculation of inorganic colloid and heavy metal cation in sludge；Its molecular structure for preparing synthesis is controllable, and reaction condition is mild, environmental-friendly, is suitble to widely apply.
Description
Technical field
The invention belongs to technical field of sludge treatment, in particular to a kind of flocculant and its synthesis applied to sludge conditioning
Method.
Background technique
Sludge is usually the by-product after municipal sewage treatment is good, still contains a large amount of moisture, contains in Solid content
A large amount of germ, helminth, organic toxicant, inorganic heavy metal and silt etc., often also with foul smell, if any heap
It puts, or deals with improperly, often result in secondary pollution.Since water content often reaches 90% or more in sludge, solids wadding therein
The conveying of body structure the problems such as causing freight height, take up a large area, and is directly over general dehydration and is also difficult to reach
Ideal effect.Common sludge dewatering treatment mode has sludge condensation, sludge dewatering, sludge temperature and sludge conditioning.Sludge
Often there is the problems such as power consumption is big, cocnentration factor is not high in concentration.Contained by the sludge after natural desiccation and mechanical dehydration processing mode
Water rate, but a disadvantage is that dewatering time is long, maintenance cost is high, and the power consumption of mechanical dehydration is high.Sludge is stable is usually by detesting
Oxygen digestion process can produce available biogas, but it is at high cost to inject capital into, and the production gas time is long, and operation management is at high cost,
And it is influenced vulnerable to environment.
The minimizing of sludge is realized by sludge treatment and resource recycling is the more excellent solution that sludge is rationally disposed
Scheme.Contain a large amount of microorganism EPS, organic nutrition and various microelements in sludge, treated by dehydration minimizing
Sludge passes through compost fermentation, may be used as vegetation soil, wherein such as humic acid can be directly used as fertilizer for further processing extraction
Material.But also contain a large amount of inorganic heavy metal and toxin in compost, without direct compost is handled, often result in heavy metal
Plant richness product, enter human body eventually by food chain, therefore, application compost is needed by innoxious and temperature processing.
Moreover, the sludge by dehydration is directly over compost fermentation, nutrients utilization is not high, and it is dewatered also result in it is a large amount of organic
Nutrients loss.
In order to carry out minimizing and harmless treatment to sludge, it is often necessary to carry out sludge conditioning.Common sludge conditioning
Method has chemical conditioning, material conditioning and microorganism conditioning.Physics conditioning has ultrasonic wave conditioning and microwave conditioning, ultrasonic wave conditioning
Sludge extracellular polymeric can be made to disintegrate, mud granule dispersion, specific surface area increases, but dewatering performance of sludge is caused to deteriorate；Microwave
Conditioning fast, easily operated control and saving energy with heating speed, but its depth for penetrating sludge is limited, and conditioning effect is paid no attention to
Think.Microorganism conditioning is to be used as flocculant by microbial cell, improves the dewatering of sludge, but often process cycle
Long, treatment effect is unobvious.
Common chemical conditioning is to use inorganic matter, organic polymer object or natural modified organic polymer as flocculation
Agent improves sludge.Often dosage is big for inorganic conditioner, it is larger to cause volume after sludge dewatering, and to pH and ionic strength
It is more demanding.Organic high polymer coagulant has gradually replaced inorganic conditioner, and dosage is few, by pH and ionic strength affect
It is small, and the sludge quantity after conditioning is small, but often synthesis technology is complicated, technique requires height to be difficult to control, at high cost.Natural modified height
It is honest and clean that molecular flocculant has starch, cellulose, chitin and lignin etc. to do modified and graft copolymerization, synthetic raw material mostly
Valence, conditioning effect are efficient.But common flocculation organic matter is generally by Mannich graft copolymerization, or with height
Potassium manganate does initiator graft copolymerization, and reaction adjusts harshness, and yield is not high.ATRP is Carnegie-Mellon University
A kind of atom transfer radical polymerization method that Matyjaszewski is developed, has been widely used in the modification of lignin
In grafting, have many advantages, such as that reaction condition is mild, synthetic polymer molecule is controllable, and it is applied to the wooden of sludge flocculant
The modified graft reaction of element has not been reported.
Summary of the invention
To solve the above-mentioned problems, the embodiment of the invention provides a kind of flocculant applied to sludge conditioning and its synthesis
Method.
The technical solution is as follows:
A kind of flocculant applied to sludge conditioning, flocculant are compound represented by general formula (1).
Specifically, " Lignin " in general formula (1) indicates poly- guaiacyl, poly- lilac base in lignin molecule structure
Or poly- oxybenzene based structures, in general formula (1)m,n,p,qRespectively indicate the repetition list in the respective general formula (1) in square brackets " [] "
First quantity；m,n,p,qIt is the positive integer more than or equal to 1.
Further, the R in general formula (1)1Independently selected from general formula (2), general formula (3), general formula (4), general formula (5), general formula
(6), general formula (7)One or more of.
Further, the R in general formula (2)2, R in general formula (3)3, R in general formula (4)3, R in general formula (5)5, general formula
(6) R in6, R in general formula (7)7It can be 7 ~ 10 independently selected from the alkyl or carbon atom number that carbon atom number is 1 ~ 6
Benzene alkyl.
A kind of synthetic method of the flocculant applied to sludge conditioning, comprising the following steps:
1. prepared by macromole evocating agent: 10 ~ 15 parts of lignin being dissolved in 200 ~ 500 parts of organic ion liquid, 95-105 DEG C adds
4.5 ~ 6h of heat, after lignin safely dissolution, the 2- bromine isobutyl acylbromide reaction of 70 ~ 80 parts of addition under 4 DEG C of ice-water baths forms anti-for 24 hours
Answer liquid；Reaction solution is added in 500 ~ 1000 parts of water with 0.01 ~ 0.1 part/min speed and obtains sediment, sediment with 500 ~
After 1000 parts of ether are washed and filtered 3 ~ 5 times, then vacuum freeze drying obtains macromole evocating agent；
2. lignin-base flocculant synthesize: the macromole evocating agent for taking 1 ~ 1.5 part of step (1) of precise to prepare be added to
In 200 ~ 500 parts of organic ion liquid, solion reaction system is formed；Then, under 4 DEG C of ice-water baths and nitrogen protection, point
0.01 ~ 0.02 part of copper bromide and 0.5 ~ 1.5 part of reaction ligand are added not into solion reaction system；By reaction monomers
The mixed solution mixed with methanol by 1:2 ~ 1:5 mass ratio is added with 0.01 ~ 0.1 part/min speed to above-mentioned solion
Reaction system reacts 4 h at 15~30 DEG C；Then, it with 500 ~ 1000 parts of distillation water washings and suction filtration 3 ~ 5 times, obtains reaction and produces
Object；Reaction product is placed in in acetone solvent, and 24 h are extracted at 120 DEG C, obtain white gum polymer；White gum is poly-
It closes 500 ~ 1000 parts of distillation water washings of object and filters 3 ~ 5 times, vacuum freeze drying obtains flocculant.
Specifically, step 1. in lignin be high-boiling alcohol lignin, acetic acid lignin or fiber enzymolysis xylogen in
It is a kind of.
Specifically, step 1. in organic ion liquid be fluorination one or more of heterocyclic compound.
Specifically, step 1. in reactant in can add in 24 ~ 60 parts of pyrroles, imidazoles, pyridine, pyridazine or pyrazines
It is one or more of.
Specifically, step 2. in reaction ligand be pentamethyl-diethylenetriamine, 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyls
Trien, N1- (2- (dimethylamino) ethyl)-N2 ((dimethylamino) methyl)-N1, N2 dimethyl ethane -1,2-
Diamines, N, N- (ethane -1,2- diyl) bis- (N, N', N'- trimethyl formamides), N, N- di-2-ethylhexylphosphine oxide (N, N', N'-
One of trimethyl formamide).
Specifically, step 2. in reaction monomers can use general formula (8)It indicates.
The technical solution adopted by the present invention at least has the advantages that the present invention passes through ATRP graft copolymerization,
It will be
In the monomer polymerization to lignin molecule that can produce anion in water phase, novel lignin Flokal B is obtained,
The flocculant has powerful adsorption function, can be widely applied to the flocculation of inorganic colloid and heavy metal cation in sludge.This hair
The preparation method product purity of the flocculant of bright synthesis is high, and the right structure-controllable of the polyphosphazene polymer of synthesis, reaction condition is mild, ring
Border is friendly, is suitble to widely apply.
Detailed description of the invention
Fig. 1 is the flocculant general formula structure figure provided in an embodiment of the present invention applied to sludge conditioning；
Fig. 2 is a kind of lignin provided in an embodiment of the present invention1H-NMR spectrum；
Fig. 3 is a kind of lignin macromole evocating agent provided in an embodiment of the present invention1H-NMR spectrum；
Fig. 4 is a kind of lignin graft polymers provided in an embodiment of the present invention1H-NMR spectrum；
Fig. 5 is that a kind of lignin provided in an embodiment of the present invention, a kind of lignin macromole evocating agent, a kind of grafting of lignin are poly-
Close the ATR-FTIR spectrogram of object；
Fig. 6 is the TGA thermal stability figure of a kind of lignin provided in an embodiment of the present invention and a kind of lignin graft polymers；
Fig. 7 is the sludge specific resistance figure that a kind of lignin graft polymers provided in an embodiment of the present invention is applied to after sludge flocculation；
Fig. 8 is the moisture content of the cake that a kind of lignin graft polymers provided in an embodiment of the present invention is applied to after sludge flocculation
Figure；
Fig. 9 is the filtrate turbidity figure that a kind of lignin graft polymers provided in an embodiment of the present invention is applied to after sludge flocculation；
Figure 10 is total TOC figure that a kind of lignin graft polymers provided in an embodiment of the present invention is applied to after sludge flocculation；
Figure 11 is the molecular linkage map of organic matter HPSEC in raw sewage after present invention method is extracted；
Figure 12 is the organic matter HPSEC after a kind of L-g-P10 conditioning raw sewage after present invention method is extracted
Molecular linkage map；
Figure 13 is the organic matter HPSEC after a kind of L-g-P15 conditioning raw sewage after present invention method is extracted
Molecular linkage map；
Figure 14 is the organic matter HPSEC after a kind of L-g-P20 conditioning raw sewage after present invention method is extracted
Molecular linkage map；
Figure 15 is the organic matter HPSEC after a kind of L-g-P30 conditioning raw sewage after present invention method is extracted
Molecular linkage map.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
A kind of flocculant applied to sludge conditioning, flocculant are compound represented by general formula (1).
Specifically, " Lignin " in general formula (1) indicates poly- guaiacyl, poly- lilac base in lignin molecule structure
Or poly- oxybenzene based structures, in general formula (1)m,n,p,qRespectively indicate the repetition list in the respective general formula (1) in square brackets " [] "
First quantity；m,n,p,qIt is the positive integer more than or equal to 1.
Further, the R in general formula (1)1Independently selected from general formula (2), general formula (3), general formula (4), general formula (5), general formula
(6), general formula (7)One or more of.
Further, the R in general formula (2)2, R in general formula (3)3, R in general formula (4)3, R in general formula (5)5, general formula
(6) R in6, R in general formula (7)7It can be 7 ~ 10 independently selected from the alkyl or carbon atom number that carbon atom number is 1 ~ 6
Benzene alkyl.
A kind of flocculant synthetic method applied to sludge conditioning, comprising the following steps:
Macromole evocating agent preparation: 10 ~ 15 parts of lignin are dissolved in 200 ~ 500 parts of organic ion liquid, 95-105 DEG C of heating
70 ~ 80 parts of 2- bromine isobutyl acylbromide reaction is added after lignin safely dissolution, under ice-water bath and forms reaction solution for 24 hours by 4.5 ~ 6h；
Reaction solution is added in 500 ~ 1000 parts of water with 0.01 ~ 0.1 part/min speed and obtains sediment, 500 ~ 1000 parts of second of sediment
After ether is washed and filtered 3 ~ 5 times, then vacuum freeze drying obtains macromole evocating agent.
The synthesis of lignin-base flocculant: 1 ~ 1.5 part of macromole evocating agent of precise is taken to be added to 200 ~ 500 parts
In organic ion liquid, solion reaction system is formed；Then, under ice-water bath and nitrogen protection, respectively to solion
0.01 ~ 0.02 part of copper bromide and 0.5 ~ 1.5 part of reaction ligand are added in reaction system；By reaction monomers and methanol by 1:2 ~
The mixed solution of 1:5 mass ratio mixing, is added with 0.01 ~ 0.1 part/min speed to above-mentioned solion reaction system, 15~
4h is reacted at 30 DEG C；Then, with 500 ~ 1000 parts of distillation water washings and suction filtration 3 ~ 5 times, reaction product is obtained；The reaction produces
Object is placed in in acetone solvent, and 24 h are extracted at 120 DEG C, obtain white gum polymer；White gum polymer with 500 ~
It 1000 parts of distillation water washings and filters 3 ~ 5 times, vacuum freeze drying obtains flocculant.
Wherein, lignin is one of high-boiling alcohol lignin, acetic acid lignin or fiber enzymolysis xylogen.
Wherein, organic ion liquid is one or more of fluorination heterocyclic compound.
Wherein, reaction ligand is pentamethyl-diethylenetriamine, 1, Isosorbide-5-Nitrae, 7,10,10- hexamethyl triethylenes four
Amine, N1- (2- (dimethylamino) ethyl)-N2 ((dimethylamino) methyl)-N1, N2 dimethyl ethane -1,2- diamines, N, N-
(ethane -1,2- diyl) bis- (N, N', N'- trimethyl formamides), N, N- di-2-ethylhexylphosphine oxide (N, N', N'- trimethyl formyl
One or more of amine).
Wherein, reaction monomers are 3- methacryloxy -2- oxopropan sodium sulfonate, 3- methacryloxy propylamine
One or more of ylmethyl sodium sulfonate, O- ((methacryloxy) methyl) carbonyl sodium bisulfate.
One R of embodiment2\R3\R4\R5\R6\R7
R in general formula (2) of the present invention2, R in general formula (3)3, R in general formula (4)3, R in general formula (5)5, in general formula (6)
R6, R in general formula (7)7, optionally, citing: methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, amyl, neopentyl, just base, 1- methyl amyl, 2- methyl amyl, 3- methyl amyl, 2- dimethyl
Butyl, 3- dimethylbutyl, 2,3- methyl butyl, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, ethylbenzene, 1- methyl-ethyl benzene base,
2- methyl-ethyl benzene base, propyl phenyl, butyl phenyl, 1- first propyl phenyl, 2- first propyl phenyl, 3- first propyl phenyl, 1- diformazan
Ethylphenyl, 2- dimethylethyl phenyl.
Two lignin of embodiment
Lignin used in the present invention is one of high-boiling alcohol lignin, acetic acid lignin or fiber enzymolysis xylogen.
High-boiling alcohol lignin, be using high boiling solvent (hbs), such as Isosorbide-5-Nitrae butanediol, ethylene glycol, benzene alcohol, ethyl acetate,
The product that boiling is extracted is carried out to lignin raw material.Lignin raw material can using larch, wheat straw, Chinese alpine rush or
Needle grass etc., by drying, smashing, sifting and drying step obtains.
Three organic ion liquid of embodiment
Organic ion liquid is one or more of fluorination heterocyclic compound.Specifically, nitrogen heterocyclic compounds, citing are fluorinated
Are as follows: 1- allyl-3- methylimidazole fluoride, 3- methyl-1-vinyl-2,5- dihydro-1HImidazoles -3- fluoride, 2- first
Simultaneously [1,2-a] pyrazine fluoride, 1- methylpyrazine fluoride, the fluorination of 4,4- thebaine of base -6,7,8,8a- nafoxidine
Object, 4- methyl morpholine fluoride, 4- allyl -1- methyl -3,4- dihydro pyrazine fluoride, 5- allyl -1- methylpyrimidine fluorine
Compound, 3- allyl -1- methyl -2,3- dihydro-pyrimidin fluoride, 4- methyl -3,4- dihydro -2H- 1,4- oxazines fluoride, 4-
Methyl -4H- 1,4- oxazines fluoride, 2- allyl -4- methyl -4H- 1,4- oxazines fluoride.Preferred fluorination nitrogen heterocyclic compounds
Are as follows: 1- allyl-3- methylimidazole fluoride, 3- methyl-1-vinyl-2,5- dihydro-1HImidazoles -3- fluoride, 2- allyl
Base -4- methyl -4H- 1,4- oxazines fluoride, 4- allyl -1- methyl -3,4- dihydro pyrazine fluoride, 5- allyl -1- first
Yl pyrimidines fluoride and 3- allyl -1- methyl -2,3- dihydro-pyrimidin fluoride.
Example IV lignin graft polymers synthesis characterization
Using1H-NMR and FTIR characterizes the lignin graft polymers (L-g-P) of synthesis.
1H-NMR characterization is measured using 500 MHz DRX-500 type Nuclear Magnetic Resonance (German Bruker company).Point
5mg lignin (Lignin), 5mg macromole evocating agent (Lignin-Br) and 5mg lignin graft polymers (L-g- are not taken
P (Lignin DMSO-d, Lignin-Br and Ligning-P CDCl) is dissolved in the corresponding deuterated reagent of 0.6 mL3- d is molten
Agent), Lignin, Lignin-Br, Lignin-g-P are measured respectively1H-NMR spectrum.FTIR characterization uses Vector333 type Fu
In leaf transformation infrared spectrometer (German Bruker company) be measured, a little sample is added using KBr pressed disc method and is placed in KBr powder
In end, tabletting is tested after sample is ground to uniformly.
GPC test uses Water1515 type gel permeation chromatograph (Waters, US), with THF is stream when test
Dynamic phase, 3ng sample is dissolved in 1mL THF, with 2.5 μm of organic membrane filter, then carries out the measurement of molecular weight.
Fig. 2, Fig. 3 and Fig. 4 be respectively a kind of lignin mentioned in the present invention, a kind of lignin macromole evocating agent,
A kind of lignin graft polymers1H-NMR spectrum.Relative to Fig. 2, occur multiple peaks at δ=1.8 ~ 2.2 in Fig. 3,
Wherein main peak is δ=2.07 a() and δ=2.1 b(), others are Interference Peaks, are shown in the lignin molecule in this embodiment
Phenolic hydroxyl group and alcoholic extract hydroxyl group replaced respectively by 2- bromo isobutyl acylbromide, and then produce chemical shift, it was demonstrated that lignin divides greatly
The synthesis of sub- initiator.
Relative to Fig. 2, occur multiple proton peaks in Fig. 4, the proton peak at chemical shift δ=6.48 and δ=6.40 point
Do not belong to the proton peak at the c in Fig. 4 and d on carbon atom, respectively represents e and f in Fig. 4 in chemical shift δ=4.43 and δ=6.48
The CH at place2On proton peak, the proton peak at chemical shift δ=8.18 represents proton on the NH in Fig. 4 at g, in chemical potential
Move the CH represented in Fig. 4 at h at δ=4.942Proton peak, it is seen that this map major embodiment be graft side chain polymer spy
Levy peak.
Fig. 5 is a kind of lignin mentioned in the present invention, a kind of lignin macromole evocating agent, a kind of grafting of lignin
The ATR-FTIR spectrogram of polymer, it is known that, after lignin is acylated, in 1741.81cm-1And 1257.3cm-1Place has more a carbonyl
The stretching vibration peak of (C=O) and ehter bond C-O-C show that acylbromide group has been grafted on lignin, macromole evocating agent
Lingin-Br synthesis is completed.It is found by graft copolymer spectrogram, 2850cm-1And 2950cm-1There is methylene (- CH in place2) on C-
H stretching vibration absworption peak；1140cm-1The characteristic peak at place is that C-O-C stretching vibration occurs in open chain aliphatic anhydride in graft side chain
Peak, due to the introducing of monomer, hence it is evident that be better than the peak Lignin-Br, these characteristic peaks confirm the polymer of synthesis.
Five thermodynamics of embodiment characterization
TGA test uses 4000 thermogravimetric analyzer of PerKin Elmer TGA (PerKinElmer company, the U.S.).Take 5mg sample
It is placed in crucible；In nitrogen atmosphere, tested with the heating rate of 10 K/min to 900 DEG C.
A kind of lignin and a kind of thermal stability of lignin graft polymers that the present invention synthesizes are by TGA in nitrogen atmosphere
In measure, test results are shown in figure 6, and L-g-P10, L-g-P15, L-g-P20 and L-g-P30 are illustrated respectively in grafting in figure
The molecular number of lignin and monomer ratio is 1:10,1:15,1:20 and 1:30 in copolymer.Unmodified lignin is in warm in Fig. 6
When decomposition amount reaches 2.5%, thermal decomposition temperature is 189.9 DEG C, and the aromatic rings chemical structure coke residual volume of lignin is at 900 DEG C
When be 31.4%.For lignin modified when thermal decomposition amount reaches 2.5%, thermal decomposition temperature is compared to unmodified lignin
Thermal decomposition temperature significantly improves, the thermal decomposition temperature of L-g-P10, L-g-P15, L-g-P20 and L-g-P30 is respectively 318.5 DEG C,
334.2 DEG C, 354.2 DEG C and 384.4 DEG C, and the thermal decomposition temperature of the lignin of graft modification rises as grafted chain length increases
Height, liquid crystal phase transition temperature are also increased slightly.In addition, the thermal decomposition residual volume of lignin-base liquid crystal polymer is also more unmodified
Lignin it is low.Generally speaking, the thermal stability of the lignin-base liquid crystal polymer by graft modification increases, and heat point
Solution temperature also increases with the increase of polymer molecular weight.
Six sludge conditioning dewatering of embodiment
Under room temperature, the L-g-P of a certain amount of lignin and different polymerization degree is rapidly added into sludge, dosage exists
Between 0.01%~0.5%, start magnetic stirring apparatus, be first quickly stirred to react 2 min, then stir reaction 8min slowly, extracts supernatant
Liquid and EPS are measured.
The measurement of dehydration property: sludge specific resistance (SRF) indicate the sludge of Unit Weight when filtering under a certain pressure
Resistance in unit filter area.Sludge dewatering is same as above, and is carried out decompression and is filtered to obtain filter cake, natural air drying.Pinpoint metal spraying, shooting
SEM wadding body picture.Using Sand box box counting method, corresponding fractal dimension D is obtained by Graphical Methodf.The public affairs of sludge specific resistance
Formula can be expressed as:
r = 2pA2b/μω
In formula, p is filter pressure (kgm-2)；A is filter area (m2), μ is the dynamic viscosity (kgsm of filtrate-2)；ω
To filter the dry solids wt (kgm that the filtrate of unit volume retains on filter medium-3)；B is equation of filtration t/V=bV
The slope of straight line representated by+a, t are filtration time (s)；V is filtrate volume (m3)。
The measurement of supernatant fluid turbidity: after flocculant conditioning is added in sludge, filtering resulting filtrate has certain impurity, filtrate
Muddiness, can reflect flocculant to the removal ability of colloidal solid, fine particles and some color compositions in sludge, and it is straight
The reversed physical quantity for reflecting sludge conditioning effect quality.Its turbidity is directly surveyed with nephelometer.
The effect that the flocculant of synthesis of the invention is applied to sludge dewatering is as shown in Figure 7 and Figure 8.It is learnt from Fig. 7,
It being flocculated after solidifying agent conditioning, sludge specific resistance SRF is gradually reduced, when dosage is with the percentages referring now to sludge weight,
Within the scope of the dosage of 0.0005~0.001 g/g, sludge specific resistance SRF value is reduced sharply with the increase of this dosage, is greater than
0.001 g/g later SRF value then increases unobvious as dosage increases.As can be seen from Figure 8 conditioned rear mud
Cake water cut changing law is substantially consistent with sludge specific resistance SRF variation.By analyzing above it is found that with flocculant poly degree
Increasing dewatering performance of sludge constantly enhances, and the coagulation effect of L-g-P30 is best, and dehydration property is best, with traditional flocculant phase
Than the reasonable dosage of flocculant of the invention is 0.001 g/g or so, far below 0.01~0.03g/g of traditional flocculant
Dosage.Fig. 9 is that different flocculant dosages improve the filtrate turbidity after sludge, it can be seen that the filter after flocculant improves
Liquid turbidity all significantly reduces, and whole with reducing after the increase of flocculant dosage, trend is identical with sludge specific resistance SRF, L-g-P30
The turbidity of filtrate is finally down to 12.84NTU by the sludge after conditioning.
Influence of seven flocculation of embodiment to sludge TOC
Total organic carbon (TOC) measurement uses TOC-L CPN type analyzer (Shimadzu), using 680 DEG C of combustion catalysis oxidizing process,
Combustion catalysis oxidizing process makes it not only can effectively aoxidize labile low molecular weight organic compound, but also can aoxidize
It is difficult to the insoluble and macromolecular organic compound decomposed.
From in Figure 10, as can be seen that comparing former mud, (DOC passes through dissolved organic carbon in sludge after flocculant improves
TOC variation reflection) content has micro reduction (0.35~1.32 mg/L), tend to be steady when dosage reaches 0.001 g/g
Fixed, for DOC content it is found that DOC content is minimum after L-g-P30 conditioning, next is L-g- after comparing 4 kinds of coagulant conditionings
P20, L-g-P15 and L-g-P10, this is consistent with sludge SRF value changing rule, it is known that flocculant makees the removal of total organic carbon
With little.
Influence of eight flocculation of embodiment to EPS
Take 50mL sludge in centrifuge tube, in 3000 rmin-1Revolving speed under be centrifuged 10 min, collect sludge supernatant
1. adding 0.05% NaCl solution of 15mL in remaining precipitating, stirs evenly rapidly in vortex oscillation instrument, then shaking
Revolving speed is 150 rmin in bed-1Level shakes 10 min, later in 5000 rmin-1Revolving speed under be centrifuged 10min, collect
Sludge supernatant is 2.；0.05% NaCl solution of 15mL is added in precipitating after centrifugation, is stirred rapidly in vortex oscillation instrument
It is even, 30min is heated in 60 DEG C of water-baths, later in 5000 rmin-1Revolving speed under be centrifuged 20min, collect supernatant 3..It closes
And supernatant 1., supernatant 2. with supernatant 3., it is to be measured after 0.45 μm of membrane filtration.
Efficient numerical method (HPSEC) uses Waters liquid chromatographic system, by 2487 double wave of Waters
Long absorption detector, 1525 pump group of Waters at.Separating chromatographic column used is TSKgelG3000SWXL.Mobile phase is
5mol·L-1Phosphate buffer and 0.01 molL-1NaCl solution crosses 0.22 μm of filter membrane, then ultrasound later
15min, flow rate of mobile phase are 1.0 mLmin-1, measurement wavelength is 254 nm, and sampling volume is 200 μ L.Polystyrene sulphur
Standard substance of the sour sodium (PSS) as relative molecular mass, PSS relative molecular mass used in graticule is respectively 1.8 ×
103、4.2×103、6.5×103。
Figure 11, Figure 12, Figure 13, Figure 14 and Figure 15 are respectively that raw sewage, the L-g-P10 after the above method extracts are handled
The molecular linkage map of organic matter HPSEC in group, L-g-P15 processing group, L-g-P20 processing group and L-g-P30 processing group.Wherein, exist
The molecule peak of relative molecular weight > 5000 generally represents protein and polysaccharide；Molecular weight component 1000~5000 is mainly humic
Acid and low molecular weight group；Molecular weight < 1000 is small molecule scaffold substance.Have Figure 11-15 display, molecular weight 60000,
700000 and 1200000 molecule peak is mainly the mating type EPS of macromolecular, in flocculation and sludge silt and
Other inorganic matters are taken together, and the 1000 of intermediate molecular weight, 1200,2500,3500,4000,25000 and 40000 molecules
Small molecular protein, polysaccharide and the humic acid etc. that peak represents, which are not flocculated, to be taken away, in the supernatant after still keeping flocculation.
Further, BCA method, anthrone colorimetric is respectively adopted in the protein in the EPS solution of extraction, polysaccharide, humic acid
Method and ZBG21005-87 method determine, the results are shown in Table 1.Table 1 shows that the removal rate of protein, carbohydrate and humic acid is not
Height, between 3.53%~14.35%.
Table 1
| Group | Protein (g/kg) | Carbohydrate (g/kg) | Humic acid (g/kg) | Hg(mg/kg) | Cu(mg/kg) | Pb(mg/kg) | Cr(mg/kg) |
| Control group | 87.31±4.76 | 234.46±37.63 | 47.15±1.78 | 175.09±12.63 | 278.41±35.26 | 217.68±53.62 | 28.74±1.35 |
| L-g-P10 | 84.23±3.64 | 232.26±41.26 | 45.26±1.25 | 163.15±23.65 | 236.37±41.29 | 185.31±46.28 | 21.26±1.74 |
| L-g-P15 | 78.28±5.26 | 230.32±32.06 | 44.36±2.07 | 123.74±32.46 | 214.45±57.32 | 134.72±62.35 | 18.47±2.43 |
| L-g-P20 | 75.37±4.19 | 228.51±41.67 | 44.25±1.26 | 87.26±27.45 | 185.31±62.78 | 102.26±72.03 | 14.32±2.21 |
| L-g-P30 | 74.78±3.67 | 227.75±23.46 | 43.79±2.31 | 67.74±23.54 | 174.52±58.34 | 87.48±25.06 | 12.18±184 |
Removal of the embodiment nine to Heavy Metals in Sludge
ICP-AES method: weighing 0.1 g sample, be placed in micro-wave diminishing pot, and 6mL nitric acid, 2mL hydrochloric acid, 3mL hydrogen is added
Fluoric acid, 1mL hydrogen peroxide, is put into microwave dissolver and is cleared up.It takes out after cooling, is transferred to sample using a small amount of water
In polytetrafluoroethylene beaker, 3mL perchloric acid is added, smolders to close and does, remove cooling beaker, 5mL nitric acid dissolved residue is added,
It is settled in 100mL volumetric flask, shakes up after cooling.If there is insoluble matter, filtering is done.Using the full spectral pattern inductance of Plasma 2000
Coupled plasma spectrometer measures mercury, copper, lead, chromium content in sludge and after conditioning in filtrate.
By table 1, it can be seen that L-g-P30 is highest to the removal rate of mercury, copper, lead, chromium, respectively 61.31%,
37.32%、59.81%、57.62%。
By embodiment six, embodiment seven, embodiment eight and embodiment nine as can be seen that the one of which that the present invention synthesizes
Flocculant, which improves sludge, has good dewatering, the organic carbon content in filtrate, gross protein after its conditioning, total
Sugar and content of humic acid decline unobvious, the mating type EPS of only least a portion of macromolecular, in flocculation and sludge
Silt and other inorganic matters be taken together；And L-g-P30 is highest to the removal rate of mercury in filtrate, copper, lead, chromium, point
It Wei 61.31%, 37.32%, 59.81%, 57.62%；This illustrates the flocculant after improving sludge, and still there are a large amount of in filtrate
Organic matter, while the heavy metal in sludge can also be removed to a certain extent, be provided for the circular regeneration and waste utilization of filtrate
Completely new solution route.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of flocculant applied to sludge conditioning, which is characterized in that the flocculant is chemical combination represented by general formula (1)
Object；
" Lignin " in the general formula (1) indicates poly- guaiacyl, poly- lilac base or poly- hydroxyl in lignin molecule structure
Phenyl structure, in the general formula (1)m,n,p,qRespectively indicate the repetitive unit in the respective general formula (1) in square brackets " [] "
Quantity；It is describedm,n,p,qIt is the positive integer more than or equal to 1.
2. the flocculant synthetic method according to claim 1 applied to sludge conditioning, which is characterized in that the general formula
(1) R in1Independently selected from general formula (2), general formula (3), general formula (4), general formula (5), general formula (6), general formula (7)One or more of.
3. the general formula (1) according to claim 2, which is characterized in that the R in the general formula (2)2, the general formula (3)
In R3, R in the general formula (4)4, R in the general formula (5)5, R in the general formula (6)6, R in the general formula (7)7
The benzene alkyl that the alkyl or carbon atom number that can be 1 ~ 6 independently selected from carbon atom number be 7 ~ 10.
4. a kind of synthetic method of claim 1 ~ 3 applied to sludge conditioning flocculant, which is characterized in that including following
Step:
Macromole evocating agent preparation: 10 ~ 15 parts of lignin are dissolved in 200 ~ 500 parts of organic ion liquid, 95-105 DEG C of heating
70 ~ 80 parts of 2- bromine isobutyl acylbromide reaction is added after lignin safely dissolution, under 4 DEG C of ice-water baths and forms reaction for 24 hours by 4.5 ~ 6h
Liquid；The reaction solution is added in 500 ~ 1000 parts of water with 0.01 ~ 0.1 part/min speed and obtains sediment, the sediment is used
After 500 ~ 1000 parts of ether are washed and filtered 3 ~ 5 times, then vacuum freeze drying obtains macromole evocating agent；
The synthesis of lignin-base flocculant: the macromole evocating agent for taking 1 ~ 1.5 part of step of precise 1. to prepare is added
Into 200 ~ 500 parts of organic ion liquid, solion reaction system is formed；Then, it is protected in 4 DEG C of ice-water baths and nitrogen
Under shield, 0.01 ~ 0.02 part of copper bromide is added into the solion reaction system respectively and 0.5 ~ 1.5 part of reaction is matched
Body；The mixed solution that reaction monomers are mixed with methanol by 1:2 ~ 1:5 mass ratio, with 0.01 ~ 0.1 part/min speed be added to
Above-mentioned solion reaction system reacts 4 h at 15~30 DEG C；Then, with 500 ~ 1000 parts of distillation water washings and suction filtration 3 ~ 5
It is secondary, obtain reaction product；The reaction product is placed in in acetone solvent, and 24 h are extracted at 120 DEG C, obtain white gum
Polymer；500 ~ 1000 parts of distillation water washings of the white gum polymer and filter 3 ~ 5 times, vacuum freeze drying is wadded a quilt with cotton
Solidifying agent.
5. the synthetic method according to claim 4 applied to sludge conditioning flocculant, which is characterized in that the step is 1.
In the lignin be one of high-boiling alcohol lignin, acetic acid lignin or fiber enzymolysis xylogen.
6. the synthetic method according to claim 4 applied to sludge conditioning flocculant, which is characterized in that the step is 1.
In the organic ion liquid be fluorination one or more of heterocyclic compound.
7. the synthetic method according to claim 4 applied to sludge conditioning flocculant, which is characterized in that the step is 1.
In the reactant in can add one or more of 24 ~ 60 parts of pyrroles, imidazoles, pyridine, pyridazine or pyrazine.
8. the flocculant synthetic method according to claim 4 applied to sludge conditioning, which is characterized in that the step is 2.
In the reaction ligand be pentamethyl-diethylenetriamine, 1,1,4,7,10,10- hexamethyl trien, N1-
(2- (dimethylamino) ethyl)-N2 ((dimethylamino) methyl)-N1, N2 dimethyl ethane -1,2- diamines, N, N- (ethane -
1,2- diyl) bis- (N, N', N'- trimethyl formamides), N, in N- di-2-ethylhexylphosphine oxide (N, N', N'- trimethyl formamide)
One kind.
9. being applied to sludge conditioning flocculant and synthetic method described according to claim 1 ~ 4, which is characterized in that the step
2. the reaction monomers in can use general formula (8)It indicates.
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| CN114426655A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Novel lignin-based oil-in-water emulsion demulsifier, preparation method thereof and treatment method of crude oil-in-water emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110526328A (en) * | 2019-09-06 | 2019-12-03 | 苏州清溪环保科技有限公司 | A kind of preparation method for the processing material of heavy metal in sewage |
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| CN114426655A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Novel lignin-based oil-in-water emulsion demulsifier, preparation method thereof and treatment method of crude oil-in-water emulsion |
| CN114426655B (en) * | 2020-10-10 | 2023-11-14 | 中国石油化工股份有限公司 | Lignin-based water-in-oil emulsion demulsifier, preparation method thereof and treatment method of crude oil water-in-oil emulsion |
| CN112777918A (en) * | 2020-12-11 | 2021-05-11 | 北京林业大学 | Fractal dimension and granularity-based online control method for sludge oxidation conditioning |
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