Background technology
Polysilicate aluminum ferric chloride is a kind of composite type inorganic polymer flocculation agent that grows up on silicic acid and aluminium salt, the molysite flocculation agent basis gathering.The electronegative silicic acid that gathers has higher relative molecular mass, and the colloidal solid in the water body is had very strong adsorptive power; And the polymeric aluminum molysite can hydrolysis in water forms the hydrolysis hydroxyl ion of the lotus of serial positively charged, has stronger charge neutrality ability.The two is combined into a kind of product, makes it become the inorganic polymer coagulant that has charge neutrality effect and adsorption bridging ability simultaneously.Because it is good to have a coagulation effect, handle low temperature, low-cloudy water has special efficacy, low price, characteristics such as the kish ion in water is low cause the very big concern of field of water treatment.
The aluminium foil spent pickle liquor refers to mainly that electric aluminum foil factory etching process produces contains the aluminic acid wastewater.One tame large-scale electric aluminum foil factory produces this waste liquid daily more than 1000 tons, the whole nation tens of families of existing the type enterprise.At present, to the processing of this spent acid be with in the alkali with after emit, so not only to consume a large amount of alkali, and can produce a large amount of white lake solid residues, bring new environmental problem.
Iron and steel pickling waste liquid is typical metal pickling waste liquid, all contains a large amount of acidic substance and ferrous ion, if directly discharging will cause severe contamination to receiving water body and edatope.Existing treatment process is to adopt that air distillation---condensation method reclaims hydrochloric acid, but the residual HCl of this method is too high, and higher to temperature requirement in the production, energy consumption is big, and equipment corrosion is serious, and more serious to the DR of environment.
Electric aluminum foil factory etching process produces contains the aluminic acid wastewater, before being discharged into sewage network, needs through WWT.An important step is carried out the acid-base neutralisation processing to these acid waste waters exactly in this treatment process; Raising along with the pH value of waste water; Aluminium salt generation hydrolysis in the waste water forms aluminum hydroxide precipitation; In follow-up pulp water separating device, be retained down, after drying, become solid aluminum hydroxide material (being commonly called as the aluminium slag).This unbodied white lake solid has higher activity, can under relatively mild condition, be dissolved by acid.
Have the polysilicate aluminum ferric chloride polymeric flocculant of good shelf-stability and flocculating property for aluminium foil acid, steel acid lotion and the aluminium slag of utilizing of the present invention for feedstock production, do not see bibliographical information at present as yet.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing aluminium foil acid, ferrous acid to prepare aluminum chlorate of polymerized silicic acid iron, is to utilize the aluminium foil acid (AlCl that produces behind the electronic aluminum foil corrosion
3Content is at 7-15%, HCl content 2.0-4.0%), (Fe content is 5-10% to iron and steel ferrous acid washing lotion, H
2SO
4Content 3-5%), water glass and aluminium slag production waste are handled the method with the efficient flocculant polysilicate aluminum ferric chloride.The present invention is in order to utilize industrial produced wastes, to promote green production process, a kind of turbidity to sewage, the preparation method of chroma removal rate PASFC high, that stability in storage is good and the method for application and WWT thereof being provided.
In order to address the above problem, the technical scheme that the present invention adopts is:
A kind of method for preparing aluminum chlorate of polymerized silicic acid iron, comprise the steps: (1) with 100 parts of steel acid lotions with after the acid of 200 parts aluminium foil mixes, reacted 0.5-2 hour with 1.5-3 part oxygenant chloric acid sodium then, control reaction temperature 50-80 ℃; (2) the aluminium foil acid of 800-1300 part is added in continuation, and control mixing solutions temperature is 40-60 ℃, according to Si/ (Al+Fe) ratio dropping metasilicate pentahydrate sodium solution 100-300 part of 0.05-0.2, reacts 1-4 hour; (3) add the Al (OH) of 65-120 part then
3The aluminium slag makes mixing solutions alkalization polymerization, ageing, and control pH value was reacted 1-3 hour between 2.0-3.5, finally made inorganic macromolecule flocculant poly silicic acid aluminium chloride ferrum product.
A kind of aluminum chlorate of polymerized silicic acid ferrous solution that adopts method for preparing, it is a kind of aluminum chlorate of polymerized silicic acid iron inorganic polymer copolymer solution.Its application method is:
Use distilled water diluting: with polysilicate aluminum ferric chloride solution dilution to concentration is 30-50%; With hydrochloric acid with the pH regulator of waste water to 7.0-8.0; Then respectively according to the aluminum chlorate of polymerized silicic acid ferric flocculant: the volume ratio of sewage is that the ratio of 0.5-5:1000 under agitation slowly adds in the waste water; Stirred 2-5 minute, said sewage is printing and dyeing, life or industrial sewage.
The present invention utilizes the staple FeSO in the acid liquid of iron and steel
4And H
2SO
4, aluminium foil acid staple AlCl
3And the staple Al (OH) of HCl, aluminium slag
3Deng trade waste is raw material, and auxiliary metasilicate pentahydrate sodium makes Fe through oxidation
2+Ion is converted into Fe
3+Technologies such as ion, acid are dissolved, polymerization utilize active aluminium hydroxide composition in the aluminium slag to regulate the pH value and the basicity of mixing solutions under comparatively gentle reaction conditions, form stable multipolymer polysilicate aluminum ferric chloride inorganic polymer.Key of the present invention be make full use of the industrial waste raw material, with the aluminium slag as the consumption acid starting material, promote aluminium, silicon, iron to form stable multipolymer, polymerization Control strong operability, the good stability of product, be convenient to suitability for industrialized production.Not only solve these discharging wastes problems, and can be enterprise's considerable economic benefit, product again can reuse and sewage treatment process, the green production that promotes enterprise with develop a circular economy.
The invention has the beneficial effects as follows: the aluminum chlorate of polymerized silicic acid iron that adopts this method to prepare can be widely used in the processing of dyeing waste water, sewage, trade effluent etc.; Have the very strong COD of removing, decolouring, turbidity removal ability, and form that alumen ustum is big and closely knit, the alumen ustum settling time short.
Embodiment
Embodiment 1
A kind of method of utilizing aluminium foil acid, ferrous acid to prepare aluminum chlorate of polymerized silicic acid iron comprises the steps:
(1) with 100 parts of steel acid lotions with after the acid of 200 parts aluminium foil mixes, react 50 ℃ of controlled temperature, 0.5 hour reaction times with 1.5 parts of oxygenant chloric acid sodium;
(2) continue to add 800 parts aluminium foil acid, control mixing solutions temperature is 40 ℃, and the Si/ according to 0.05 (Al+Fe) ratio drips 100 parts of metasilicate pentahydrate sodium solution, reacts 1 hour;
(3) add 70 parts Al (OH) then
3The aluminium slag makes mixing solutions alkalization polymerization, ageing, and control pH value was reacted 1 hour 2.0, finally made inorganic macromolecule flocculant poly silicic acid aluminium chloride ferrum solution.
Embodiment 2
A kind of method of utilizing aluminium foil acid, ferrous acid to prepare aluminum chlorate of polymerized silicic acid iron comprises the steps:
(1) with 100 parts of steel acid lotions with after the acid of 200 parts aluminium foil mixes, react 60 ℃ of controlled temperature, 1 hour reaction times with 2.0 parts of oxygenant chloric acid sodium;
(2) continue to add 1000 parts aluminium foil acid, control mixing solutions temperature is 50 ℃, and the Si/ according to 0.1 (Al+Fe) ratio drips 200 parts of metasilicate pentahydrate sodium solution, reacts 2 hours;
(3) add 86 parts Al (OH) then
3The aluminium slag makes mixing solutions alkalization polymerization, ageing, and control pH value was reacted 2 hours 2.5, finally made inorganic macromolecule flocculant poly silicic acid aluminium chloride ferrum solution.
Embodiment 3
A kind of method of utilizing aluminium foil acid, ferrous acid to prepare aluminum chlorate of polymerized silicic acid iron comprises the steps:
(1) with 100 parts of steel acid lotions with after the acid of 200 parts aluminium foil mixes, react 80 ℃ of controlled temperature, 2 hours reaction times with 3 parts of oxygenant chloric acid sodium;
(2) continue to add 1300 parts aluminium foil acid, control mixing solutions temperature is 60 ℃, and the Si/ according to 0.2 (Al+Fe) ratio drips 300 parts of metasilicate pentahydrate sodium solution, reacts 4 hours;
(3) add 112 parts Al (OH) then
3The aluminium slag makes mixing solutions alkalization polymerization, ageing, and control pH value was reacted 3 hours 3.5, finally made inorganic macromolecule flocculant poly silicic acid aluminium chloride ferrum solution.
Embodiment 4
A kind of aluminum chlorate of polymerized silicic acid iron product preparing method's practical implementation instance:
(1) oxidation
With the steel acid lotion of Zhaoqing Bi Jiang Environmental Protection Technology Co., Ltd, the aluminium foil acid and the commercially available technical grade NaClO of Zhaoqing Huafeng Electronic Aluminum Foil Co., Ltd.
3Be raw material, wherein steel acid lotion (ferrous acid) staple: FeSO
4, 23.5%; H
2SO
4, 6.5%; All the other are water; Aluminium foil acid main chemical compositions: AlCl
3, 10.2%; HCl, 3.6%; All the other are water; VAL-DROP is technical grade, NaClO3%>=98%.
After the acid of 20-40g ferrous acid and 40-80g aluminium foil mixed, add 0.62-1.28g VAL-DROP after being warmed up to 70 ℃, also stirring 1-2 hour of insulation is with Fe
2+All be converted into Fe
3+
(2) silicic acid activation
Contain Fe to what step (1) made
3+Add the acid of 160-320g aluminium foil in the aluminium foil acid, controlled temperature is 40-60 ℃ and stirs, with 12-25g Na
2SiO
35H
2The O wiring solution-forming slowly adds in the mixing solutions, and insulation is also stirred 1-3h, obtains the oligomeric composite solution of aluminium-iron-silicon.
(3) aluminum chlorate of polymerized silicic acid iron is produced in alkalization, polymerization
The oligomer solution that step (2) is made is warmed up to 80 ℃, keeps and stirs and the slow 14.5-30g of adding aluminium slag (Al (OH)
3%>=82%), stirring reaction, copolymer-1-3h obtain copolymerized macromolecule flocculant poly silicic acid aluminium chloride ferrum.
The polysilicate aluminum ferric chloride flocculant that the present invention is made is used for dyeing waste water, and compares with the treatment effect of Poly aluminum Chloride (PAC) (PAC) and aluminium iron polychloride (PAFC), and used dyeing waste water is taken from Zhaoqing, Guangdong Province dyeing and finishing factory, and sewage quality is following:
pH |
COD
Cr/(mg/L)
|
Colourity/degree |
Turbidity/NTU |
9.2 |
355.6 |
1018 |
35.2 |
Get a certain amount of aluminum chlorate of polymerized silicic acid ferrous solution, Poly aluminum Chloride (PAC) and aluminium iron polychloride solid phase prod; Will be with distilled water diluting according to the 30-50% of silicic acid aluminium chloride ferrum solution dilution to concentration; And solid Poly aluminum Chloride (PAC) and aluminium iron polychloride be diluted to same concentrations; With hydrochloric acid with the pH regulator of waste water to 7.0-8.0, then respectively according to flocculation agent: the volume ratio of dyeing waste water is that the ratio of 1000:0.5-5 under agitation slowly adds in the waste water, stirs after 2-5 minute behind the static certain hour; Get supernatant liquid and analyze water quality, the result is following:
Flocculation agent |
COD
CrClearance/%
|
Chroma removal rate/% |
Turbidity removal rate/% |
Alumen ustum settling time/min |
PASFC |
81.5 |
90.3 |
97.6 |
4-8 |
PAFC |
72.3 |
72.9 |
85.5 |
7-12 |
PAC |
68.6 |
65.6 |
74.9 |
12-18 |
Compare with PAC, PAFC, among the PASFC because the performances such as adsorptive power, charge neutrality ability of compound gathering silicic acid, gathering aluminium and gathering several kinds of flocculation agents of iron, the hydrolysis complexing product that the aggressiveness of generation is bigger, because of
Can bring into play charge neutrality effect and the effect of intensive adsorption bridging after this is added in the water simultaneously, thereby show better turbidity removal, decolour and fall COD usefulness.