CN108178259A - A kind of preparation method and application of polyaluminium magnalium titanium - Google Patents
A kind of preparation method and application of polyaluminium magnalium titanium Download PDFInfo
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- CN108178259A CN108178259A CN201711318705.8A CN201711318705A CN108178259A CN 108178259 A CN108178259 A CN 108178259A CN 201711318705 A CN201711318705 A CN 201711318705A CN 108178259 A CN108178259 A CN 108178259A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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Abstract
The present invention relates to a kind of preparation method and applications of polyaluminium magnalium titanium.Liquor alumini chloridi and magnesium chloride solution are prepared, the molar ratio according to Mg/Al is 0.1~0.6：1, aluminium chloride and magnesium chloride solution are mixed, obtain aluminium chloride magnesium solution, is taken out after placing 20~30min in refrigerator, the molar ratio according to Ti/Al is 0.1~0.6：1, by 0.11~0.66mL of titanium tetrachloride liquid liquid relief in aluminium chloride magnesium solution, it is thoroughly mixed uniformly, chlorination magnalium titanium solution is obtained, the sodium hydroxide solution of a concentration of 2mol/L is added dropwise into chlorination magnalium titanium solution, is stirred and evenly mixed when being added dropwise, after being added dropwise, water bath with thermostatic control is persistently stirred, and is protected from light curing at room temperature to get to polyaluminium magnalium titanium.Present invention process is simple, at low cost, and obtained composite macromolecule coagulant has pollutant better charge neutrality, adsorption bridging effect, and coagulation effect is more preferably.
Description
Technical field
The present invention relates to a kind of preparation method and applications of polyaluminium magnalium titanium, belong to water-treatment technology field.
Background technology
The rapid development of industrial or agricultural, population increase, water resource for the survival of mankind is increasingly poor, and water resources crisis is increasingly
Aggravation.At present, water pollution and water shortage problem increasingly become an important factor for restricting economic development.In order to save water resource,
The utilization rate of water is improved, mitigates and eliminates water pollution and endangered caused by the mankind and environment, it is necessary to strengthen water process work.In water
In contamination control, water supply purification processing, dirty (useless) water depth treatment for reuse and sludge dehydration treatment technology technology, coagulation technology
It is using most common treatment technology unit.The behavior of coagulation process and effect decide the fortune of follow-up water and wastewater treatment flow
Row operating mode, effluent quality and cost.The medicament added in coagulation process is known as coagulant or flocculant, and coagulating treatment
Effect is critically depend on the quality of coagulant, thus research and development are novel, efficient coagulant is to realize that water treatment procedure is excellent
The core of change.
Traditional coagulant typically refers to aluminium salt and molysite, such as aluminum sulfate, alchlor, ferric trichloride and ferric sulfate；
Inorganic polymer flocculant is typically the hydroxyl polynuclear complex or hydroxy polymer of Al (III), Fe (III), Si (IV), such as poly-
Close aluminium, polymeric iron, polymeric silicicacid etc.；Tend to the centre of hydroxide precipitation when they are all Al (III), Fe (III) saline hydrolysis
Product.But its structure of inorganic polymer flocculant is easier to be arranged in regular micro-crystal type, is self-assembled into as chain and branch
Shape can also play adsorption bridging effect more stronger than traditional inorganic coagulant.
The advantages of inorganic polymer flocculant, is that it is more excellent than traditional flocculant efficiency, compares organic polymer coargulator
It is cheap, but compared with organic polymer coargulator, the molecular weight of inorganic polymer flocculant and flocculation bridge formation ability phase
Difference is very big, and being used alone has the shortcomings that dosage is more with the sludge quantity of generation greatly.At present in coagulation technology field, develop
New and effective, nontoxic, inexpensive coagulant, flocculant become a urgent task.
If a large amount of engineering practice shows coagulant more than two kinds (classes) or two kinds (class) or flocculant to pass through difference
It adds and is used in compounding or to form a kind of composite flocculation agent product use by mixing or reacting under certain condition, then
It can be achieved to have complementary advantages, the coagulating treatment effect of water and waste water can be improved, widen application range and reduce processing cost.At present,
In water and wastewater treatment, two or more coagulant or flocculant be used in compounding existing a large amount of engineering practice and
Application example, and achieved good application effect.Since compound coagulant can overcome many of the single flocculant of use not
Foot, flocculating property can be improved while cost of water treatment is reduced, so, the research and development and application of composite flocculation agent just become current
The main direction of development of one of the hot issue in water and wastewater treatment field and novel, efficient and economic flocculant.
Composite coagulant flocculant excellent effect in terms of water process, more single inorganic flocculating agent have preferably wadding
Solidifying effect and wide application prospect.
In order to further improve the coagulation effect of inorganic coagulant and reduce product dosage, research and development prepare a kind of new and effective
Inorganic Composite Polymeric Coagulants be necessary.It is found by numerous studies and application practice：If aluminium salt and magnesium salts are being added
Enter and be copolymerized under conditions of titanium tetrachloride, by formation there is synergistic function can prepare with more preferable coagulation effect
The inorganic polymer coagulant product of fruit.
Invention content
When the present invention is directed to existing Al-based coagulant as sewage treatment drug, added amount of chemical is big, sewage disposal
Effect unobvious, the flco of generation is more fragile, is easily broken when water body is disturbed, and sinking speed is smaller, residual Al is to people
Body health there are the problems such as larger threat, provide a kind of polyaluminium magnalium titanium (PCAMT) Inorganic Composite Polymeric Coagulants and
Its preparation and application obtains the Inorganic Composite Polymeric Coagulants with good coagulation effect.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of preparation method of polyaluminium magnalium titanium, is following steps：
(1) it takes Aluminium chloride hexahydrate that deionized water is added to be sufficiently stirred dissolving and obtains colourless transparent solution, be configured to a concentration of
The liquor alumini chloridi of 0.1~0.3mol/L, taking Magnesium dichloride hexahydrate that deionized water is added to be sufficiently stirred dissolving, to obtain water white transparency molten
Liquid is configured to the magnesium chloride solution of a concentration of 0.05~0.2mol/L；
(2) it is 0.1~0.6 according to the molar ratio of Mg/Al：1, aluminium chloride obtained by step (1) and magnesium chloride solution are mixed,
Aluminium chloride magnesium solution is obtained, is placed in refrigerator, is taken out after placing 20-30min in being -20~5 DEG C in temperature, according to Ti/Al's
Molar ratio is 0.1~0.6：1, by 0.11~0.66mL of titanium tetrachloride liquid liquid relief in aluminium chloride magnesium solution, it is sufficiently stirred mixed
It closes uniformly, obtains chlorination magnalium titanium solution；
(3) it is 0.2~1.2 according to the molar ratio of n (OH)/n (Al+Mg+Ti)：1, add dropwise into chlorination magnalium titanium solution
Enter the sodium hydroxide solution of a concentration of 2mol/L, stirred and evenly mixed when being added dropwise, after being added dropwise, water bath with thermostatic control persistently stirs 1.5
~2h, bath temperature are 30~80 DEG C, then place and are protected from light curing 12~for 24 hours at room temperature to get to polyaluminium magnalium titanium.
Purity >=97% of the aluminium chloride, purity >=98% of magnesium chloride, content >=99% of titanium tetrachloride liquid.
In the step (2) in aluminium chloride magnesium solution preparation process, mixing speed when aluminium chloride and magnesium chloride solution mix
For 200~400r/min, titanium tetrachloride liquid and aluminium chloride magnesium solution mixed process, mixing speed are 100~300r/min.
In the step (3), it is 30~80min that sodium hydroxide solution, which adds in the time, be added dropwise terminal pH for 5.5~
6.5。
Polyaluminium magnalium titanium is Inorganic Composite Polymeric Coagulants, applied to feedwater, municipal sewage, paper waste and spinning
Knit dyeing waste water field, water supply, municipal sewage water treatment agent when, polyaluminium magnalium Ti-inorganic composite high-molecular mixes
Solidifying agent dosage is 4~20mg/L, and applicable pH value is 6~9；For paper waste and the water treatment agent of textile printing and dyeing wastewater
When, polyaluminium magnalium Ti-inorganic composite macromolecule coagulant dosage is 4~25mg/L, and applicable pH value is 5~9.
In processing feedwater or municipal sewage, the pH of water body is adjusted to 6~9 with soda acid in advance, by polyaluminium magnalium
Titanium is uniformly added into water body and stirs, and mixing speed is 50~300r/min, and it is 40~65 DEG C to maintain temperature, and the residence time 20~
45min；When handling paper waste or textile printing and dyeing wastewater, water body pH is adjusted to 5~9 with soda acid in advance, by polyaluminium
Magnalium titanium is uniformly added into water body and stirs, and mixing speed is 50~400r/min, and it is 40~65 DEG C to maintain temperature, the residence time
20~45min.
Polyaluminium magnalium titanium (PCAMT) Inorganic Composite Polymeric Coagulants of the present invention have compared with prior art
Following excellent results：
(1) polyaluminium magnalium titanium (PCAMT) Inorganic Composite Polymeric Coagulants of the invention, are with aluminium chloride, chlorination
Magnesium and titanium tetrachloride are raw material, are mixed using sodium hydroxide (NaOH) solution is added drop-wise to aluminium chloride, magnesium chloride and titanium tetrachloride
Aqueous solution in method prepare polyaluminium magnalium titanium (PCAMT).The composite macromolecule coagulant product has stability
It is good, it is strong to colloidal solid adsorption bridging ability, coagulation effect is good, applied widely, water outlet pH is close to neutrality, facilitate subsequent processing
The advantages that.
(2) polyaluminium magnalium titanium (PCAMT) Inorganic Composite Polymeric Coagulants of the invention and aluminium polychloride (chlorination
Aluminium) coagulant compares, introduce magnesium chloride and titanium tetrachloride, magnesium salts as water treatment agent, have flco formed fast, particle it is big and
Closely knit, floc settling velocity is fast, turbidity removal and the advantages that good decolorizing effect.Tetravalence complex compound [the TiO that titanium ion hydrolysis generates4]n
In contained Ti-O-Ti keys so that form more chain reticular structures, so as to which the volume improved in coagulation process is beaten the effect of catching,
So that composite macromolecule coagulant has pollutant better charge neutrality, adsorption bridging effect, coagulation effect is more preferably.
(3) polyaluminium magnalium titanium (PCAMT) Inorganic Composite Polymeric Coagulants of the invention, due in aluminium chloride, chlorine
Change in the mixed solution of magnesium and titanium tetrachloride and add sodium hydroxide (NaOH) solution, alkalized to titanium tetrachloride, make four
Titanium chloride prehydrolysis so as to alleviate its strong hydrolysis to a certain extent, has weight to the subsequent processing of coagulation water outlet
Want meaning.
(4) preparation method of the present invention is simple, and technological process is short, and obtained products application is in feedwater, municipal sewage, papermaking
Waste water and textile printing and dyeing wastewater field, application field is wide, adding less, and at low cost and effect is good.
Specific embodiment
Presently in connection with embodiment, specifically the present invention is described in further detail.
A kind of preparation method of polyaluminium magnalium titanium, is following steps：
(1) it takes Aluminium chloride hexahydrate that deionized water is added to be sufficiently stirred dissolving and obtains colourless transparent solution, be configured to a concentration of
The liquor alumini chloridi of 0.1~0.3mol/L, taking Magnesium dichloride hexahydrate that deionized water is added to be sufficiently stirred dissolving, to obtain water white transparency molten
Liquid is configured to the magnesium chloride solution of a concentration of 0.05~0.2mol/L；
(2) it is 0.1~0.6 according to the molar ratio of Mg/Al：1, aluminium chloride obtained by step (1) and magnesium chloride solution are mixed,
Aluminium chloride magnesium solution is obtained, is placed in refrigerator, is taken out after placing 20~30min in being -20~5 DEG C in temperature, according to Ti/Al's
Molar ratio is 0.1~0.6：1, by 0.11~0.66mL of titanium tetrachloride liquid liquid relief in aluminium chloride magnesium solution, it is sufficiently stirred mixed
It closes uniformly, obtains chlorination magnalium titanium solution；
(3) it is 0.2~1.2 according to the molar ratio of n (OH)/n (Al+Mg+Ti)：1, add dropwise into chlorination magnalium titanium solution
Enter the sodium hydroxide solution of a concentration of 2mol/L, stirred and evenly mixed when being added dropwise, after being added dropwise, water bath with thermostatic control persistently stirs 1.5
~2h, bath temperature are 30~80 DEG C, then place and are protected from light curing 12~for 24 hours at room temperature to get to polyaluminium magnalium titanium.
Purity >=97% of the aluminium chloride, purity >=98% of magnesium chloride, content >=99% of titanium tetrachloride liquid.
In the step (2) in aluminium chloride magnesium solution preparation process, mixing speed when aluminium chloride and magnesium chloride solution mix
For 200~400r/min, titanium tetrachloride liquid and aluminium chloride magnesium solution mixed process, mixing speed are 100~300r/min.
In the step (3), it is 30~80min that sodium hydroxide solution, which adds in the time, be added dropwise terminal pH for 5.5~
6.5。
Polyaluminium magnalium titanium is Inorganic Composite Polymeric Coagulants, applied to feedwater, municipal sewage, paper waste and spinning
Knit dyeing waste water field, water supply, municipal sewage water treatment agent when, polyaluminium magnalium Ti-inorganic composite high-molecular mixes
Solidifying agent dosage is 4~20mg/L, and applicable pH value is 6~9；For paper waste and the water treatment agent of textile printing and dyeing wastewater
When, polyaluminium magnalium Ti-inorganic composite macromolecule coagulant dosage is 4~25mg/L, and applicable pH value is 5~9.
In processing feedwater or municipal sewage, the pH of water body is adjusted to 6~9 with soda acid in advance, by polyaluminium magnalium
Titanium is uniformly added into water body and stirs, and mixing speed is 50~300r/min, and it is 40~65 DEG C to maintain temperature, and the residence time 20~
45min；When handling paper waste or textile printing and dyeing wastewater, water body pH is adjusted to 5~9 with soda acid in advance, by polyaluminium
Magnalium titanium is uniformly added into water body and stirs, and mixing speed is 50~400r/min, and it is 40~65 DEG C to maintain temperature, the residence time
20~45min.
Embodiment 1
(1) it weighs 2.4163g Aluminium chloride hexahydrates white crystal and 0.6099g Magnesium dichloride hexahydrate white crystals is dissolved in
In the deionized water of 60mL, being sufficiently stirred makes its dissolving obtain the aluminium chloride magnesium solution of water white transparency；
(2) it is taken out after the aluminium chloride magnesium solution for obtaining water white transparency being positioned over to -10 DEG C of refrigerator preservation 20min；
(3) it is 0.3 according to the molar ratio of Ti/Al, pipettes the titanium tetrachloride liquid of 0.33mL in the chlorination obtained by step (2)
To get chlorination magnalium titanium solution in magnalium solution.
(4) it is 0.4 according to the molar ratio of n (OH)/n (Al+Mg+Ti), the mixed solution in (3) adds in a concentration of dropwise
Sodium hydroxide (NaOH) solution of 2mol/L, after being added dropwise, 2h is persistently stirred in 60 DEG C of waters bath with thermostatic control.
(5) chlorination magnalium titanium solution obtained by step (4) is positioned in the environment of room temperature is protected from light, curing is for 24 hours to get to poly-
Close chlorination magnalium titanium (PCAMT) Inorganic Composite Polymeric Coagulants.
Purity >=97% of the aluminium chloride, purity >=98% of magnesium chloride, content >=99% of titanium tetrachloride liquid.
In the step (1), the molar ratio according to Mg/Al is 0.3.
In the step (1) in aluminium chloride magnesium solution preparation process, mixing speed when aluminium chloride and magnesium chloride solution mix
For 250r/min, titanium tetrachloride liquid and aluminium chloride magnesium solution mixed process, mixing speed 200r/min.
In the step (4), sodium hydroxide solution adds in the time as 45min, and it is 5.6 that terminal pH, which is added dropwise,.
Embodiment 2
(1) 2.4163g Aluminium chloride hexahydrates white crystal and 1.0165g Magnesium dichloride hexahydrates are weighed
White crystal is dissolved in the deionized water of 60mL, and being sufficiently stirred makes its dissolving obtain the chlorination magnalium of water white transparency
Solution；
(2) it is taken out after the aluminium chloride magnesium solution for obtaining water white transparency being positioned over to -15 DEG C of refrigerator preservation 25min；
(3) it is 0.5 according to the molar ratio of Ti/Al, pipettes the titanium tetrachloride liquid of 0.55mL in the chlorination obtained by step (2)
To get chlorination magnalium titanium solution in magnalium solution.
(4) it is 0.6 according to the molar ratio of n (OH)/n (Al+Mg+Ti), the mixed solution in (3) adds in a concentration of dropwise
Sodium hydroxide (NaOH) solution of 2mol/L, after being added dropwise, 2h is persistently stirred in 60 DEG C of waters bath with thermostatic control.
(5) chlorination magnalium titanium solution obtained by step (4) is positioned in the environment of room temperature is protected from light, curing is for 24 hours to get to poly-
Close chlorination magnalium titanium (PCAMT) Inorganic Composite Polymeric Coagulants.
Purity >=97% of the aluminium chloride, purity >=98% of magnesium chloride, content >=99% of titanium tetrachloride liquid.
In the step (1), the molar ratio according to Mg/Al is 0.5.
In the step (1) in aluminium chloride magnesium solution preparation process, mixing speed when aluminium chloride and magnesium chloride solution mix
For 300r/min, titanium tetrachloride liquid and aluminium chloride magnesium solution mixed process, mixing speed 250r/min.
In the step (4), sodium hydroxide solution adds in the time as 60min, and it is 5.8 that terminal pH, which is added dropwise,.
Embodiment 3
(1) it takes Aluminium chloride hexahydrate that deionized water is added to be sufficiently stirred dissolving and obtains colourless transparent solution, after fully dissolving
It is configured to the liquor alumini chloridi of a concentration of 0.2mol/L；
(2) it takes Magnesium dichloride hexahydrate that deionized water is added to be sufficiently stirred dissolving and obtains colourless transparent solution, after fully dissolving
It is configured to the magnesium chloride solution of a concentration of 0.1mol/L；
(3) it is 0.5 according to the molar ratio of Mg/Al, the solution that (1) and (2) obtains is mixed, it is molten to obtain chlorination magnalium
Liquid takes out after solution to be positioned over to -5 DEG C of refrigerator preservation 30min；
(4) it is 0.4 according to the molar ratio of Ti/Al, the titanium tetrachloride liquid for pipetting 0.44mL is added to obtained by step (3)
In aluminium chloride magnesium solution, chlorination magnalium titanium solution is obtained；
(5) it is 0.8 according to the molar ratio of n (OH)/n (Al+Mg+Ti), is added dropwise to chlorination magnalium titanium solution a concentration of
Sodium hydroxide (NaOH) solution of 2mol/L, after being added dropwise, 1.5h is persistently stirred in water bath with thermostatic control, and thermostat temperature is 60 DEG C；
(6) chlorination magnalium titanium solution obtained by step (5) is positioned in the environment of room temperature is protected from light, curing 20h is to get to poly-
Close chlorination magnalium titanium solution.
Purity >=97% of the aluminium chloride, purity >=98% of magnesium chloride, content >=99% of titanium tetrachloride liquid.
In the step (3) in aluminium chloride magnesium solution preparation process, mixing speed when aluminium chloride and magnesium chloride solution mix
For 350r/min, titanium tetrachloride liquid and aluminium chloride magnesium solution mixed process, mixing speed 300r/min.
In the step (5), sodium hydroxide solution adds in the time as 70min, and it is 6.2 that terminal pH, which is added dropwise,.
Embodiment 4
A kind of preparation method of polyaluminium magnalium titanium, is following steps：
(1) it takes Aluminium chloride hexahydrate that deionized water is added to be sufficiently stirred dissolving and obtains colourless transparent solution, be configured to a concentration of
The liquor alumini chloridi of 0.2mol/L takes Magnesium dichloride hexahydrate that deionized water is added to be sufficiently stirred dissolving and obtains colourless transparent solution, matches
The magnesium chloride solution of a concentration of 0.08mol/L is made；
(2) it is 0.4 according to the molar ratio of Mg/Al, aluminium chloride obtained by step (1) and magnesium chloride solution is mixed, obtain chlorine
To change magnalium solution, be placed in refrigerator, taken out after placing 25min in being -15 DEG C in temperature, the molar ratio according to Ti/Al is 0.5,
By titanium tetrachloride liquid liquid relief 0.55mL in aluminium chloride magnesium solution, it is thoroughly mixed uniformly, obtains chlorination magnalium titanium solution；
(3) it is 1.0 according to the molar ratio of n (OH)/n (Al+Mg+Ti), concentration is added dropwise into chlorination magnalium titanium solution
For the sodium hydroxide solution of 2mol/L, stirred and evenly mixed when being added dropwise, after being added dropwise, 2.0h, water-bath are persistently stirred in water bath with thermostatic control
Temperature is 50 DEG C, is then placed within and is protected from light curing 18h at room temperature to get to polyaluminium magnalium titanium.
Purity >=97% of the aluminium chloride, purity >=98% of magnesium chloride, content >=99% of titanium tetrachloride liquid.
In the step (2) in aluminium chloride magnesium solution preparation process, mixing speed when aluminium chloride and magnesium chloride solution mix
For 300r/min, titanium tetrachloride liquid and aluminium chloride magnesium solution mixed process, mixing speed 200r/min.
In the step (3), sodium hydroxide solution adds in the time as 75min, and it is 6.4 that terminal pH, which is added dropwise,.
The water treatment applications embodiment of product of the present invention
Application Example 1
By experiments of single factor, the preparation of polyaluminium magnalium titanium (PCAMT) Inorganic Composite Polymeric Coagulants has been investigated
Stirring in water bath temperature in the process；Mg/Al molar ratios；Ti/Al molar ratios；N (OH)/n (Al+Mg+Ti) molar ratio is to coagulation efficiency
Influence.The inspection target of coagulation efficiency is mainly influence of the different parameters to Kaolin water sample turbidity.
Prepared polyaluminium magnalium Ti-inorganic composite macromolecule coagulant dosage is 4.32mg/L.
The water quality index of simulated water sample is：126.0~136.0NTU of raw water turbidity, pH value is 7.25~7.85.Coagulation is gone
Turbid effect is as shown in table 1-4：
Table 1
Table 2
Table 3
Table 4
The treatment effect for handling Kaolin water sample under four kinds of different conditions by obtaining above is analyzed：
(1) residual turbidity of water outlet increases afterwards as the increase of water-bath steady temperature first reduces, and is in water-bath steady temperature
Reach minimum when 60 DEG C.It can be seen that water-bath steady temperature has great influence to coagulation effect, certain water-bath is constant
Temperature can optimised coagulation effect.It is best to turbidity removal effect when bath temperature is 60 DEG C.This is because Al3+And Ti4+'s
Hydrolysis rate is exceedingly fast, and is the endothermic reaction, so Al can be accelerated by properly increasing reaction bath temperature3+And Ti4+The speed of hydrolysis,
Make Al3+And Ti4+The hydroxyl formed in complex increases, and improves basicity, and can promote Al3+And Ti4+It is hydrolyzed towards deep layer
Direction is smoothed out, and forms the hydroxyl compound of high polymerization degree.When temperature is higher than 60 DEG C, since constant temperature water bath is excessively high, Al3+With
Ti4+The high polymerization degree complex relative stability of formation reduces, and complex decomposition rate is accelerated, the hydroxyl combined on hydroxyl compound
Radix amount is reduced, and basicity is reduced, so as to reduce product property.
(2) residual turbidity of water outlet increases afterwards as the increase of the molar ratio of Mg/Al first reduces, in the molar ratio of Mg/Al
Reach minimum when being 0.5.It can be seen that the molar ratio of Mg/Al has great influence, certain Mg/Al to coagulation effect
Molar ratio can optimised coagulation effect.It is remaining turbid to be reduced to by 1.32NTU when Mg/Al molar ratios become 0.5 from 0.1
0.51NTU, magnesium salts is as water treatment agent, and there is flco to be formed, and fast, particle is big and closely knit, floc settling velocity is fast, turbidity removal and de-
The advantages that color effect is good.When continue to increase Mg/Al molar ratios become 0.6 when, it is remaining turbid to be increased to 0.62NTU.This is because with
The increase of Mg/Al molar ratios, the easily absorption of a large amount of Mg ions make its positively charged, make micelle and polychloride magnalium titanium on micelle surface
Flocculant is mutually exclusive, hinders flocculant and the adsorption bridging of micelle is acted on, turbidity removal effect is caused to decline.
(3) residual turbidity of water outlet increases afterwards as the increase of the molar ratio of Ti/Al first reduces, in the molar ratio of Ti/Al
Reach minimum when being 0.5.It can be seen that the molar ratio of Ti/Al has great influence, certain Ti/Al to coagulation effect
Molar ratio can optimised coagulation effect.It is remaining turbid to be reduced to by 1.75NTU when Ti/Al molar ratios become 0.5 from 0.1
0.45NTU.When continue to increase Ti/Al molar ratios become 0.6 when, it is remaining turbid to be increased to 0.49NTU.This is because as Ti/Al rubs
The increase of your ratio, the Ti entrained by product4+Increase and can form more chain reticular structures, so as to improve the net in coagulation process
The volume effect of sweeping is caught, but when Ti/Al molar ratios are excessively high, due to Ti4+It is water-disintegrable relatively strong, the Ti of too high amount4+It can make under water body pH
Drop, so as to be unfavorable for the progress of coagulation process, causes turbidity removal effect to reduce.Application example the result shows that, in Ti/Al molar ratios
When being 0.5, Ti in polyaluminium magnalium titanium solution (PCAMT)4+And Al3+Coagulation synergistic effect it is best, the removal of turbidity is imitated
Fruit is optimal.
(4) residual turbidity of water outlet increases afterwards as the increase of the molar ratio of n (OH)/n (Al+Mg+Ti) first reduces, in n
(OH) molar ratio of/n (Al+Mg+Ti) reaches minimum when being 0.6.It can be seen that mole of n (OH)/n (Al+Mg+Ti)
Comparing coagulation effect has great influence, and the molar ratio of certain n (OH)/n (Al+Mg+Ti) can optimised coagulation effect.With n
(OH) increase of the molar ratio of/n (Al+Mg+Ti), Al3+Hydrolysate is based on moderate polymer, and the constituents are not only
Remain higher positive charge, single particle positive charge is high, has a good absorption charge neutrality ability, and with opposite steady
It is qualitative, it ensure that effective performance of coagulation.When the molar ratio of n (OH)/n (Al+Mg+Ti) constantly increases, in coagulant
Ti4+Hydrolyzation morphology is gradually converted from monomer to polymeric form, when the molar ratio of n (OH)/n (Al+Mg+Ti) further increases, Ti4+
Hydrolyzation morphology then further converted from polymeric form to high polymer, but the titanium complex of part high polymerization degree is unstable, can go out
Existing a degree of decomposition.Therefore, with the increase of the molar ratio of n (OH)/n (Al+Mg+Ti), Ti4+Hydrolysis be one and first gather
The process decomposed after conjunction.In conclusion the molar ratio of n (OH)/n (Al+Mg+Ti)=0.6 when, it is best to turbidity removal effect.
Application Example 2
Polyaluminium magnalium titanium prepared by embodiment 1 is applied to municipal sewage treatment, and polyaluminium magnalium Ti-inorganic is answered
It is 15mg/L to close high-molecular coagulant adopting dosage, and it is 7.0 that waste water is adjusted pH with soda acid in advance, and polyaluminium magnalium titanium is uniform
It adds in waste water and stirs, mixing speed is 60~300r/min, and it is 40 DEG C, residence time 25min to maintain temperature, original city
The turbidity of sewage is 230NTU, and the turbidity of the water after final process is 0.48NTU.
Application Example 3
Polyaluminium magnalium titanium prepared by embodiment 2 is applied to the water treatment agent of paper waste, polyaluminium magnalium
Ti-inorganic composite macromolecule coagulant dosage is 20mg/L, and it is 5.5 that waste water is adjusted pH with soda acid in advance, by aluminium polychloride
Magnesium titanium is uniformly added into waste water and stirs, and mixing speed is 60~400r/min, and it is 50 DEG C, residence time 40min to maintain temperature,
The turbidity of raw sewage is 245NTU, and the turbidity of the water after final process is 0.40NTU.
Application Example 4
Polyaluminium magnalium titanium prepared by embodiment 3 is handled using Mr. Yu school lake water, for the water process of earth's surface lake water
Medicament, polyaluminium magnalium Ti-inorganic composite macromolecule coagulant dosage are 10mg/L, and polyaluminium magnalium titanium is uniformly added
Enter in lake water water sample and stir, mixing speed is 50~200r/min, maintains the original temperature of lake water water sample, the residence time is
30min.The initial water quality index of lake water is：54.0 ± 1.00NTU of raw water turbidity, the absorbance in the case where wavelength is 254nm are
0.043~0.056, COD (COD) is 27.0 ± 3.00mg/L or so, and pH value is after 7.50 ± 0.3, final process
The turbidity of water is 0.50NTU, and COD (COD) removal rate reaches 96%~99%.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail in good embodiment, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (6)
1. a kind of preparation method of polyaluminium magnalium titanium, which is characterized in that be following steps：
(1) it takes Aluminium chloride hexahydrate that deionized water is added to be sufficiently stirred dissolving and obtains colourless transparent solution, it is configured to a concentration of 0.1~
The liquor alumini chloridi of 0.3mol/L takes Magnesium dichloride hexahydrate that deionized water is added to be sufficiently stirred dissolving and obtains colourless transparent solution, matches
The magnesium chloride solution of a concentration of 0.05~0.2mol/L is made；
(2) it is 0.1~0.6 according to the molar ratio of Mg/Al：1, aluminium chloride obtained by step (1) and magnesium chloride solution are mixed, obtained
Aluminium chloride magnesium solution, is placed in refrigerator, is taken out after placing 20~30min in being -20~5 DEG C in temperature, according to mole of Ti/Al
Than being 0.1~0.6：1, by 0.11~0.66mL of titanium tetrachloride liquid liquid relief in aluminium chloride magnesium solution, it is thoroughly mixed
It is even, obtain chlorination magnalium titanium solution；
(3) it is 0.2~1.2 according to the molar ratio of n (OH)/n (Al+Mg+Ti)：1, it is added dropwise into chlorination magnalium titanium solution dense
The sodium hydroxide solution for 2mol/L is spent, is stirred and evenly mixed when being added dropwise, after being added dropwise, 1.5~2h is persistently stirred in water bath with thermostatic control,
Bath temperature is 30~80 DEG C, is then placed within and is protected from light curing 12~for 24 hours at room temperature to get to polyaluminium magnalium titanium.
2. a kind of preparation method of polyaluminium magnalium titanium as described in claim 1, which is characterized in that the aluminium chloride it is pure
Degree >=97%, purity >=98% of magnesium chloride, content >=99% of titanium tetrachloride liquid.
3. a kind of preparation method of polyaluminium magnalium titanium as described in claim 1, which is characterized in that in the step (2)
In aluminium chloride magnesium solution preparation process, mixing speed is 200~400r/min when aluminium chloride and magnesium chloride solution mix, four chlorinations
Titanium liquid and aluminium chloride magnesium solution mixed process, mixing speed are 100~300r/min.
4. a kind of preparation method of polyaluminium magnalium titanium as described in claim 1, which is characterized in that in the step (3),
Sodium hydroxide solution adds in the time as 30~80min, and it is 5.5~6.5 that terminal pH, which is added dropwise,.
5. a kind of application of polyaluminium magnalium titanium, which is characterized in that polyaluminium magnalium titanium is composite coagulant coagulation
Agent, applied to feedwater, municipal sewage, paper waste and textile printing and dyeing wastewater field, water supply, municipal sewage water process medicine
During agent, polyaluminium magnalium Ti-inorganic composite macromolecule coagulant dosage is 4~20mg/L, and applicable pH value is 6~9；With
When the water treatment agent of paper waste and textile printing and dyeing wastewater, polyaluminium magnalium Ti-inorganic composite macromolecule coagulant adds
It measures as 4~25mg/L, applicable pH value is 5~9.
6. a kind of application of polyaluminium magnalium titanium as claimed in claim 4, it is characterised in that：It is dirty in processing feedwater or city
During water, the pH of water body is adjusted to 6~9 with soda acid in advance, polyaluminium magnalium titanium is uniformly added into water body and stirred, is stirred
Speed is 50~300r/min, and it is 40~65 DEG C to maintain temperature, 20~45min of residence time；In processing paper waste or weaving
During dyeing waste water, water body pH is adjusted to 5~9 with soda acid in advance, polyaluminium magnalium titanium is uniformly added into water body and stirred,
Mixing speed is 50~400r/min, and it is 40~65 DEG C to maintain temperature, 20~45min of residence time.
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