A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water
Technical field
The present invention relates to the technical field of water process, more particularly to a kind of multiple-effect water treatment agent and its preparation method and application
The method for treating water of the multiple-effect water treatment agent.
Background technology
In water treatment field, flocculation sediment is a kind of conventional processing method, and it has, and simple to operate, cost is low, handle
The advantages of effect is good.The mechanism of action of flocculation is commonly considered as having compression double electric layer and charge neutralization, macromolecule water process
The adsorption bridging effect of agent, the volume of flco sweep precipitation etc..The process of flocculation is the process of colloidal solid loss of stability, glue
Body material and small suspension grain are gathered into larger particle, so as to be easy to precipitate from liquid.Adding water treatment agent can be with
Accelerate this mechanism, absorption of these aggregates to the various impurity of dissolving can be greatly enhanced, advantageously in water
The purification of matter.
Water treatment agent is widely used in raw water and sewage treatment area, can reduce the sense such as turbidity, colourity of raw water
See index.A variety of macromolecule organics, some heavy metals and radioactive substance are removed by water treatment agent, both can be certainly into independence
Processing system, can also be combined with other processing unit processes, be used as pretreatment, intermediate treatment and final process mistake
Journey, it may also be used for the concentration process before sludge dewatering, improves the dewatering of sludge.
The species of water treatment agent can generally be divided into inorganic water treatment agent, organic water treatment agent and microorganism water process
Agent, and in actual applications, be often combined them according to the difference of water treatment agent property.
Water after the harmless processing of water treatment agent can be with reuse.Current domestic annual industrial water, city water, sewage
Million tons of process demand water treatment agent, thus research water treatment agent tool have very important significance.
Inorganic water treatment agent is the water treatment agent of consumption maximum in water treatment agent, has been formd in recent years with aluminium salt, molysite
With a few major class products based on polysilicon acid etc..Inorganic water treatment agent can be divided into low-molecular inorganic water process by its molecular size range
Agent and inorganic polymer water treatment agent.
Low-molecular inorganic water treatment agent mainly has aluminum sulfate, aluminium chloride, ferrous sulfate, ferric sulfate, iron chloride etc..It is inorganic low
Molecule water treatment agent is although cheap, ample supply and prompt delivery, but due to reasons such as coagulation consumption is big, wadding many, the coagulation effect differences of the quantity of slag,
Oneself is progressively replaced by inorganic polymer water treatment agent in actual waste water processing.
Inorganic polymer water treatment agent as the inorganic water treatment agent of the second generation, with more traditional water treatment agent (such as aluminum sulfate,
Iron chloride etc.) efficiency of coagulation is more excellent, price relatively low, economically feasible cheap compared with organic polymer water treatment agent etc. again
Advantage, be successfully applied in the various handling processes of feedwater, industrial wastewater and municipal sewage (including pretreatment, middle
Reason and advanced treating), it is increasingly becoming main flow water treatment agent.But due to inorganic water treatment agent exist hydrolytic instability, relative point
The problems such as son amount and the poor more organic water treatment agent of adsorption bridging ability.
The more inorganic water treatment agent of organic polymer water treatment agent has is influenceed smaller, water treatment agent consumption by salt coexists
Small, sinking speed is fast, produce the quantity of slag it is few, it is disposable the advantages of.But it is due to organic polymer water treatment agent generally existing monomer
The defect such as residual toxicity, higher selectivity, expensive, limits its extensive use to a certain extent.
Satisfied treatment effect can not generally be obtained to complicated sewage system using single water treatment agent, thus it is compound
Water treatment agent turns into study hotspot in recent years.It was verified that composite water disposal agent can overcome being permitted using single water treatment agent
It is more not enough, the effect better than single water treatment agent is shown, is the main trend of water treatment agent development.
The content of the invention
It is contemplated that not enough being managed for the single, flocculating effect in processing raw water source of composite water disposal agent in the prior art
The technical problem such as think there is provided a kind of multiple-effect water treatment agent and preparation method thereof, and a kind of application multiple-effect water treatment agent is provided
Method for treating water, the efficient multiplexing of water treatment agent is realized by lower floor's water technique of backflow, production cost is reduced, improves at water
Manage efficiency.
Specifically, first, the invention provides a kind of multiple-effect water treatment agent, including in terms of parts by weight such as the following group
Point:2 ~ 10 parts of acrylamide oligomers grafted graphene oxide, 5 ~ 40 parts of polyacrylamide, 20 ~ 40 parts of poly aluminium iron silicate, poly- two
3 ~ 25 parts of the dilute propyl ammonium chloride of methyl two, 1 ~ 5 part of sodium acid carbonate.
In the multiple-effect water treatment agent of present disclosure, acrylamide oligomers grafted graphene oxide work is employed first
For important component, graphene oxide is of great interest in recent years, and most important of which is its high-ratio surface
Product and extensive and excellent adsorption property, in the present invention, employ acrylamide oligomers and it are modified, on the one hand carry
High flocculation ability, using graphene oxide as base material, the acrylamide oligomers of grafting are stretched out from surface of graphene oxide, are formed
Many dentalations, are conducive to the formation of colloid, improve the effect of flocculation;On the other hand, heavy metal ion, poisonous small molecule,
Especially benzene-like compounds pollutant has extremely strong Adsorption effect, to realize that the water body in complicated Pollution System source has
Efficient detergent power.
Specifically, acrylamide oligomers grafted graphene oxide includes 3 ~ 10wt% of graphene oxide and acrylamide is low
90 ~ 97wt% of polymers, the acrylamide oligomers molecular weight is 5000 ~ 20000.
To improve overall flocculating effect, it is easy to the formation of larger micelle, while the Molecular Weight for Polyacrylamide added is
200 ~ 10,000,000, ion degree is 10% ~ 80%.
To realize segmentation flocculation, the water treatment technology for adapt to multiple dosing, repeatedly flocculating, the polyacrylamide of use includes
Molecular weight is 200 ~ 4,000,000 10 ~ 30wt% of polyacrylamide, and molecular weight is 400 ~ 8,000,000 40% ~ 50wt% of polyacrylamide
With 20% ~ 40wt% of polyacrylamide that molecular weight is 800 ~ 10,000,000.
Secondly, the invention provides a kind of preparation method of multiple-effect water treatment agent, it is characterised in that comprises the following steps:
(1)The carboxylated of graphene oxide:
Addition sodium hydroxide and monoxone in 1 ~ 10mg/mL graphene oxide water solution, hybrid reaction 1 ~ 10 hour,
Separation, washing, obtain the graphene oxide of carboxylated;
(2)Acrylamide oligomers grafted graphene oxide:
Mixed oxidization graphene and acrylamide oligomers in DMSO, add back flow reaction at EDCI, 45 DEG C, separate,
Washing, obtains acrylamide oligomers grafted graphene oxide;
(3)The preparation of multiple-effect water treatment agent:
By acrylamide oligomers grafted graphene oxide, polyacrylamide, the dilute propyl group of poly dimethyl two more than 45 DEG C
Ammonium chloride mixes in proportion and is naturally cooling to room temperature, sequentially adds poly aluminium iron silicate, sodium acid carbonate, is well mixed i.e.
Can.
The parts by weight of each component are as follows:
Acrylamide oligomers grafted graphene oxide 2 ~ 10
Polyacrylamide 5 ~ 40
Poly aluminium iron silicate 20 ~ 40
The dilute propyl ammonium chloride 3 ~ 25 of poly dimethyl two
Sodium acid carbonate 1 ~ 5.
According to grafting needs, carboxylated degree can be controlled by adjusting carboxylation process, it is preferred that step(1)Middle oxidation
Graphene aqueous solution:Sodium hydroxide:Monoxone=1L:1~2g:1~2g.
Likewise, the control of grafting amount can also be by being controlled to the raw material dosage during grafting, it is preferred that step
Suddenly(2)Middle DMSO:Graphene oxide:Acrylamide oligomers:EDCI=1L:3~10g:90~97g:10~100g.
Finally, the invention provides a kind of method for applying above-mentioned water treatment agent to carry out water process, it is characterised in that at least
Comprise the following steps:
A. mix stages:Raw water is introduced into mixing pit, above-mentioned multiple-effect water treatment agent is added, is well mixed;
B. initial flocculation stage:Water after being well mixed in step A is introduced into the first flocculation basin and carries out initial flocculation;
C. flocculated stage again:Upper water after initial flocculation in step B is introduced into the second flocculation basin, in flow process
It is middle to add multiple-effect water treatment agent described above, flocculated again in the second flocculation basin;
D. filtration stage:The water flocculated again in step C is filtered by filter plant.
Further, it is the utilization ratio of raising water treatment agent, in addition to step C ' refluxing stages:Will be preliminary in step B
Lower floor's water after flocculation passes back into mixing pit.
According to the concrete condition of raw water, the amount that multiple-effect water treatment agent adds raw water in step A is 10 ~ 500mg/L;Step C
The amount that middle multiple-effect water treatment agent adds water is 1 ~ 100mg/L.
Compared to prior art, the beneficial effects of the present invention are it is following some.
(1)Flocculating setting efficiency high, turbidity removal, decoloring ability are strong.Using composite water disposal agent formula, organic high score is combined
Sub- water treatment agent, flocculation aid, the feature performance benefit of inorganic polymer water treatment agent, by verifying repeatedly, coordinate each water treatment agent
Charge effect, has accomplished the optimization of flocculating effect, compared to single water treatment agent and commercially available composite water disposal agent, just thinks
For water quality, processing time about 10% is reduced.
(2)It is widely used, it is oligomeric by adding acrylamide especially for the higher water quality of benzene class, heavy metal classes content
Thing grafted graphene oxide, realizes the specific adsorption removal ability that similar water treatment agent does not possess in the prior art, tests table
Bright, the clearance highest to benzene class impurity to 85%, can alleviate the pressure of follow-up process processing.
(3)Cost-effective reduction, by the way that levels water in flocculation process is drawn respectively, improves the effective of water treatment agent
Utilization rate, the extraction of upper water reduces the pressure of subsequent processes;The backflow of lower floor's water, adequately achieves water treatment agent
Multiplexing, through measuring and calculating, for drinking water treatment standard, every cube of cost of water treatment reduction about 5%;Trade effluent is tentatively located
Manage as middle water quality standard, every cube of cost of water treatment reduces about 7%.
(4)Water treatment agent secondary pollution is small, the presence of graphene oxide, effectively increases the cohesiveness of micelle, reduces
Secondary pollution in flocculation process sewerage disposing agent caused by the diffusion of relevant monomer.
(5)Applicable pH range is wide, generally, without extra adjustment raw water pH, it is to avoid inorganic water treatment agent is used
During pH adjust process, improve the application of product.
Embodiment
(One)The preparation of multiple-effect water treatment agent.
Embodiment 1-1
(1)The carboxylated of graphene oxide
Sodium hydroxide and monoxone, graphene oxide water solution are added in 5mg/mL graphene oxide water solution:Hydrogen
Sodium oxide molybdena:Monoxone=1L:2g:2g, hybrid reaction 4 hours, separation, washing obtain the graphene oxide of carboxylated;
(2)Acrylamide oligomers grafted graphene oxide
Mixed oxidization graphene and acrylamide oligomers in DMSO, add EDCI, wherein, DMSO:Graphene oxide:
Acrylamide oligomers:EDCI=1L:8g:90g:50g.Back flow reaction at 45 DEG C, separation, washing, obtains acrylamide oligomers
Grafted graphene oxide;
(3)The preparation of multiple-effect water treatment agent
By acrylamide oligomers grafted graphene oxide, polyacrylamide, the dilute propyl group of poly dimethyl two more than 45 DEG C
Ammonium chloride mixes in proportion and is naturally cooling to room temperature, sequentially adds poly aluminium iron silicate, sodium acid carbonate, is well mixed i.e.
Can.
The parts by weight of each component are as follows:
Acrylamide oligomers grafted graphene oxide 10, polyacrylamide 30, poly aluminium iron silicate 40, poly dimethyl two
Dilute propyl ammonium chloride 25, sodium acid carbonate 5.
Embodiment 1-2:In the present embodiment, the preparation process such as embodiment 1-1 of multiple-effect water treatment agent, only in each component
Adjusted in proportioning.
The parts by weight of each component are as follows:Acrylamide oligomers grafted graphene oxide 8, polyacrylamide 35 gathers
Aluminium iron silicate 35, the dilute propyl ammonium chloride 20 of poly dimethyl two, sodium acid carbonate 5.
In embodiment 1-3, the present embodiment, the preparation process such as embodiment 1-1 of multiple-effect water treatment agent, only in each component
Adjusted in proportioning.
The parts by weight of each component are as follows:Acrylamide oligomers grafted graphene oxide 6, polyacrylamide 40 gathers
Aluminium iron silicate 30, the dilute propyl ammonium chloride 25 of poly dimethyl two, sodium acid carbonate 5.
In embodiment 1-4, the present embodiment, the preparation process such as embodiment 1-1 of multiple-effect water treatment agent, only in each component
Adjusted in proportioning.
The parts by weight of each component are as follows:Acrylamide oligomers grafted graphene oxide 4, polyacrylamide 20 gathers
Aluminium iron silicate 40, the dilute propyl ammonium chloride 25 of poly dimethyl two, sodium acid carbonate 5.
In embodiment 1-5, the present embodiment, the preparation process such as embodiment 1-1 of multiple-effect water treatment agent, only in each component
Adjusted in proportioning.
The parts by weight of each component are as follows:Acrylamide oligomers grafted graphene oxide 2, polyacrylamide 10 gathers
Aluminium iron silicate 40, the dilute propyl ammonium chloride 14 of poly dimethyl two, sodium acid carbonate 2.
(Two)Multiple-effect water treatment agent handles raw water.
1. raw water parameter:pH:7.51, turbidity(NTU):75.6;COD(mg/L):58.05;Colourity:240 times;Temperature:Room
Temperature.
2. experiment condition:5 beakers are taken to contain respectively into raw water 1L, 200rpm quickly stirs 30s, 5 burnings after 30s terminates
The water treatment agent 200mg that embodiment 1-1 is configured into 1-5 is separately added into cup, changes rotating speed 40rpm, 15min is stirred, slowly
After speed stirring terminates, stop stirring, liquid is stood, and after flocculation terminates, takes under liquid level that water quality is detected at 2cm.
3. experimental result:Corresponding to the water sample of the embodiment 1-1 water treatment agent processing configured into 1-5, labeled as knot
Fruit 2-1 to 2-5, design parameter list is referring to table 1.
Table 1
By above-mentioned experimental data, it can realize that turbidity, COD and colourity are whole using the multiple-effect water treatment agent of the present invention
The removal efficiency of body is improved, wherein, the clearance that turbidity removal rate is up to 92.86%, COD is up to 96.38%, chroma removal rate
Up to 93.75%.
(Three)The influence of original sub-block technique.
In following experiment, the flocculation tankage of use is 100 cubes of standard analog ponds, the overall water intake velocity 20 of control
Cubic meter/hour, integrally go out 20 cubic meters/hour of water speed.
Embodiment 3-1.
A. mix stages:Raw water is introduced into mixing pit, the multiple-effect water treatment agent added in embodiment 1-1 is well mixed;
B. initial flocculation stage:Water after being well mixed in step A is introduced into the first flocculation basin and carries out initial flocculation;
C. flocculated stage again:Upper water after initial flocculation in step B is introduced into the second flocculation basin, in flow process
It is middle to add multiple-effect water treatment agent described above, flocculated again in the second flocculation basin;
C ' refluxing stages:Lower floor's water after initial flocculation in step B is passed back into mixing pit.
D. filtration stage:The water flocculated again in step C is filtered by filter plant.
The amount that multiple-effect water treatment agent adds raw water in step A is 200mg/L;Multiple-effect water treatment agent adds water in step c
Measure as 100mg/L.
Embodiment 3-2.
A. mix stages:Raw water is introduced into mixing pit, the multiple-effect water treatment agent added in embodiment 1-1 is well mixed;
B. initial flocculation stage:Water after being well mixed in step A is introduced into the first flocculation basin and carries out initial flocculation;
C. flocculated stage again:Upper water after initial flocculation in step B is introduced into the second flocculation basin, in flow process
It is middle to add multiple-effect water treatment agent described above, flocculated again in the second flocculation basin;
D. filtration stage:The water flocculated again in step C is filtered by filter plant.
The amount that multiple-effect water treatment agent adds raw water in step A is 200mg/L;Multiple-effect water treatment agent adds water in step c
Measure as 100mg/L.
Embodiment 3-3.
A. mix stages:Raw water is introduced into mixing pit, the multiple-effect water treatment agent added in embodiment 1-1 is well mixed;
B. initial flocculation stage:Water after being well mixed in step A is introduced into the first flocculation basin and carries out initial flocculation;
C. flocculated stage again:Upper water after initial flocculation in step B is introduced into the second flocculation basin, in flow process
It is middle to add multiple-effect water treatment agent described above, flocculated again in the second flocculation basin;
C ' refluxing stages:Lower floor's water after initial flocculation in step B is passed back into mixing pit.
D. filtration stage:The water flocculated again in step C is filtered by filter plant.
The amount that multiple-effect water treatment agent adds raw water in step A is 150mg/L;Multiple-effect water treatment agent adds water in step c
Measure as 150mg/L.
Embodiment 3-4.
A. mix stages:Raw water is introduced into mixing pit, the multiple-effect water treatment agent added in embodiment 1-1 is well mixed;
B. initial flocculation stage:Water after being well mixed in step A is introduced into the first flocculation basin and carries out initial flocculation;
C. flocculated stage again:Upper water after initial flocculation in step B is introduced into the second flocculation basin, in flow process
It is middle to add multiple-effect water treatment agent described above, flocculated again in the second flocculation basin;
C ' refluxing stages:Lower floor's water after initial flocculation in step B is passed back into mixing pit.
D. filtration stage:The water flocculated again in step C is filtered by filter plant.
The amount that multiple-effect water treatment agent adds raw water in step A is 250mg/L;Multiple-effect water treatment agent adds water in step c
Measure as 50mg/L.
Comparative example 3-5.
A. mix stages:Raw water is introduced into mixing pit, the multiple-effect water treatment agent added in embodiment 1-1 is well mixed;
B. flocculated stage:Water after being well mixed in step A is introduced into the first flocculation basin to be flocculated;
C. filtration stage:The water flocculated in step B is filtered by filter plant.
The amount that multiple-effect water treatment agent adds raw water in step A is 300mg/L.
Experimental result:Corresponding to embodiment 3-1 to 3-4, comparative example 3-5 water treatment technology, water is specific before and after the processing
Parameter list is referring to table 2.
Table 2:
By above-mentioned experimental data,(1)Compared to one time flocculating setting technique, using secondary flocculating setting technique energy
Enough effective raising water treatment capacities, suitably adjust initial flocculation and the water treatment agent addition in flocculation process can be real again
Now to the adjustment of water treatment efficiency, in the case where raw water situation is complicated, technique adjustment is conducive to realize that efficiency is improved;(2)
Under same process step, the clearance of the turbidity, COD, colourity of raw water is significantly improved using lower floor's water technique of backflow.