CN102774889A - Method for producing poly aluminum ferric chloride (PAFC) by utilizing caustic sludge - Google Patents

Method for producing poly aluminum ferric chloride (PAFC) by utilizing caustic sludge Download PDF

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Publication number
CN102774889A
CN102774889A CN2012102206118A CN201210220611A CN102774889A CN 102774889 A CN102774889 A CN 102774889A CN 2012102206118 A CN2012102206118 A CN 2012102206118A CN 201210220611 A CN201210220611 A CN 201210220611A CN 102774889 A CN102774889 A CN 102774889A
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China
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alkaline residue
water
hydrochloric acid
aluminium iron
iron polychloride
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CN2012102206118A
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刘进龙
张立果
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Abstract

The invention discloses a method for producing PAFC by utilizing caustic sludge. The method includes the steps of mixing the caustic sludge, hydrochloric acid and water for full reaction at a room temperature; adding iron into an aluminum chloride solution obtained in the first step to displace heavy metal; and adding hydrochloric acid into the aluminum chloride solution in which the heavy metal is precipitated so as to adjust acidity, adding calcium aluminate to adjust basicity, adding water, molysite and an oxidation assistant for 4-6 hours of reaction, and performing filter press to obtain a filtrate which is the PAFC. According to the method, the caustic sludge produced in aluminum profile plants is recycled, so that the landfill cost is saved, reproduced products can be used for purifying water plants, and the national sustainable development strategy is accorded with; and the PAFC water purifier produced through the method is good in quality and can be directly used by water purification plants, secondary pollution is avoided in the production process, comprehensive recycling of resources is achieved, a positive significance for environmental protection is provided.

Description

A kind of method of utilizing alkaline residue to produce aluminium iron polychloride
Technical field
The present invention relates to a kind of method of utilizing alkaline residue to produce aluminium iron polychloride.
Background technology
China has become the big producing country of world aluminum section bar through the great development of two more than ten years.Aluminium section bar output was sure to occupy the No. 1 in the world in continuous 5 years.Guangdong is the whole nation and even the most concentrated zone of global aluminium enterprise, and industry size is big, and yearly capacity is above more than 200 ten thousand tons.Architectural aluminum section need carry out surface treatment, needs to use great amount of water resources.The aluminium section bar enterprise that YO is 100,000 tons is used for aluminium material surface and handles the year water consumption that each operation cleans and be about 2,000,000 m 3, the water after cleaning is the main source of aluminium section bar plant trade effluent.The major pollution thing comprises fluorion, ammonia nitrogen, COD, sexavalent chrome, organism, sulfate radical, phosphate radical etc. in the aluminium factory effluent; Even secondary discharge standard discharging by requirement at present; Still can cause certain pollution to water body, failing qualified discharge then endangers bigger.The aluminium section bar trade effluent generally adopts in the alkali and adjusting and coagulant sedimentation art breading, produces a large amount of mud.Except containing a large amount of aluminum compound and calcium cpd, also contain compounds such as a spot of zinc, nickel, copper in the composition of these mud, the composition more complicated, present most of factories adopt the method for landfill to handle these mud.This not only takies limited land resources, and the waste resource, contaminate environment.Along with the development of Chinese industrial, consequent environmental problem is also more and more outstanding.The reasonable use of water resources, problems such as industrial residue reasonable resource utilization obtain people's attention day by day.Alkaline residue through aluminium section bar plant is produced carries out analysis of components, and combines the raw-material demand of water purification agent industry, and the alkaline residue that proposes recycling aluminium shape surface treatment plant is produced the water purification agent aluminium iron polychloride, and is used for the processing of sewage and trade effluent.
Aluminium section bar enterprise process of surface treatment is different, and the waste residue that causes producing after the wastewater treatment is also different.Different waste water treatment process reaches different operation waste water separate treatment, and the kind of the waste residue that obtains is different.Section aluminum waste water is handled the waste residue that obtains and is broadly divided into two types: the one, and chromium residue; The 2nd, alkaline residue.The processing mode of different waste residues is also different.But the waste residue combination treatment of at present many aluminium section bar manufacturing enterprises is stacked, and this is unfavorable for waste reside comprehensive utilization, should produce different classes of waste residue to aluminium section bar according to its characteristics classification, and then comprehensive utilization.
The waste water of painting workshop is owing to contain deleterious sexavalent chrome, and it is handled general elder generation and becomes trivalent chromium to hexavalent chrome reduction, adds alkali again and makes it deposition.Deposition is through press filtration, and obtaining water cut is the wet mud about 70 %, and its staple is a white lake, and wherein part is a crystal, and part is an amorphous body, also has a spot of Cr (OH) 3, Fe 3O 4And Na 2Impurity such as O.According to " national Hazardous wastes register " classification, chromate waste water is handled waste residue and is belonged to Hazardous wastes, must be according to the requirement of " Hazardous wastes shifts the receipts or other documents in duplicate management method ", and entrusting has the professional Hazardous wastes of qualification to handle company's collection and treatment.Except stringent regulations, innoxious, the comprehensive utilization of resources that also should develop chromium residue energetically by way of.
The aluminium section bar manufacturing enterprise that has is in order to obtain better surface treatment effect, and process of surface treatment adopts fluorine-containing technology.Contain a certain amount of aluminum ion, fluorion, organism etc. in the fluoride waste, common treating method is to add lime to generate white lake, Calcium Fluoride (Fluorspan), adds white lake, Calcium Fluoride (Fluorspan) deposition that flocculation agent such as SEPIGEL 305 makes generation again; In order to make the fluorion deposition more thorough, often to add excessive lime, these excessive lime also can be stayed in the throw out, and account for the significant proportion of waste sludge discharge amount.The staple of waste residue is white lake, CaF 2And calcium hydroxide, compounds such as a spot of zinc, nickel, copper.Precipitating sludge is through filter press, and obtaining water ratio is the wet mud about 70 %, about 5000 tons of the annual discharging of the aluminium section bar enterprise that its year output is 200,000 tons.This waste residue quantity is big, and composition is complicated.Present most of factory does not all also find a kind of proper method to handle this waste residue, and most way is to adopt the method for landfill to handle.This not only wastes resource, and contaminate environment, has increased the waste water and the sludge treatment cost of enterprise.
There is the process of surface treatment of some aluminium section bar manufacturing enterprises to adopt not fluorine-containing technology.Its waste water adopts sodium hydroxide to reconcile the pH value, produces aluminum hydroxide precipitation, introduces flocculation agent again, destroys the stability of waste liquid, makes the sludge coagulating deposition.Deposition is through press filtration, and obtaining water cut is the wet mud about 80 %, and its staple is a white lake, and wherein part is a crystal, and part is an amorphous body, also has impurity such as a spot of nickel compound and tin compound.To the not comprehensive utilization of the alkaline residue aluminium section bar industrial residue of fluorinated calcium, some researchs have been carried out both at home and abroad.
Waste water circulation and waste reside comprehensive utilization all have very significant meaning for aluminium section bar production sustainable economic development and environment protection in the aluminium production process.The key of dealing with problems is to seek a technical and all feasible economically scheme, with wastewater treatment recycle and the integrated consideration of waste reside comprehensive utilization.Therefore the developing direction of aluminium section bar enterprise surface treatment wastewater treatment is: middle water reuse, and reduce enterprise water use amount and quantity discharged, and waste residue is given resource utilization utilize again, reduce the discharging of waste residue.The research of aluminium section bar factory effluent should not be limited to how to handle making its emission standard that reaches regulation, and should pay attention to cycling utilization of wastewater research.To wastewater treatment recycle and the suitable integrated consideration of waste reside comprehensive utilization, the waste residue combination treatment of at present many aluminium section bar manufacturing enterprises is stacked and is unfavorable for waste reside comprehensive utilization, and aluminium section bar produces different classes of waste residue should be according to its characteristics classification comprehensive utilization.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing alkaline residue to produce aluminium iron polychloride, method of the present invention be directed against to as if the alkaline residue of fluorinated calcium not.
The technical scheme that the present invention taked is:
A kind of method of utilizing alkaline residue to produce aluminium iron polychloride may further comprise the steps:
1) under the room temperature, alkaline residue, hydrochloric acid, water three mixing are fully reacted;
2) add iron to displace heavy metal in the aluminum chloride liquid that upwards step makes;
3) upwards go on foot adding hydrochloric acid adjusting acidity in the aluminum chloride liquid that is settled out heavy metal, add calcium aluminate again, add entry, molysite and oxidation promoter again, react after 4-6 hour to regulate basicity, press filtration, gained filtrating is aluminium iron polychloride.
In the step 1), described alkaline residue, hydrochloric acid, water three's mass ratio is 1: (0.5-0.7): (5-7).
In step 1) and the step 3), the mass concentration of described hydrochloric acid is 30-37%.
Step 2) in, the molar weight of the iron of adding attach most importance to the metal molar amount 2-3 doubly.
Step 2) in, the time of reaction is 24-48 hour.
In the step 3), described molysite is an iron(ic)chloride.
In the step 3), described oxidation promoter is a kind of in nitric acid, hydrogen peroxide, VAL-DROP, Peracetic Acid, the ammonium persulphate.
In the step 3), the mass ratio of the aluminum chloride in the product, calcium aluminate, oxidation promoter, hydrochloric acid is 10: (1.2-1.4): (0.1-0.2): (0.005-0.007).
The invention has the beneficial effects as follows: the present invention carries out recycling with the alkaline residue that aluminium section bar plant produced, thereby has practiced thrift the landfill expense, and born again product can be used for purifying water factory again, meets the national sustainable development strategy; The water purification agent Poly aluminum Chloride (PAC) weight of iron that the present invention produced is good, can directly be cleaned water factory and utilize, and simultaneously in process of production, does not produce secondary pollution, has realized the resource comprehensive recycling, the positive meaning that environment protection is had.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explanation:
Embodiment 1:
A kind of method of utilizing alkaline residue to produce aluminium iron polychloride may further comprise the steps:
1) under the room temperature, be that the hydrochloric acid, water three of 36wt% mixes and fully reacts 5-10h with alkaline residue, concentration; Wherein, described alkaline residue, hydrochloric acid, water three's mass ratio is 1:0.5:5;
2) add iron to displace heavy metal in the aluminum chloride liquid that upwards step makes; Wherein, the molar weight of the iron of adding is 2 times of heavy metal molar weight in the alkaline residue;
3) upwards go on foot the hydrochloric acid that adds 36wt% in the aluminum chloride liquid that is settled out heavy metal and regulate acidity, add calcium aluminate again, add entry, molysite and VAL-DROP again, react after 4-6 hour to regulate basicity, press filtration, gained filtrating is aluminium iron polychloride; Wherein, the mass ratio of contained aluminum chloride, calcium aluminate, VAL-DROP, hydrochloric acid is 10:1.2:0.1:0.005 in the product, and the add-on of water is for confirming according to the solid content of last products therefrom.
Embodiment 2:
A kind of method of utilizing alkaline residue to produce aluminium iron polychloride may further comprise the steps:
1) under the room temperature, be that the hydrochloric acid, water three of 36wt% mixes and fully reacts 5-10h with alkaline residue, concentration; Wherein, described alkaline residue, hydrochloric acid, water three's mass ratio is 1:0.7:7;
2) add iron to displace heavy metal in the aluminum chloride liquid that upwards step makes; Wherein, the molar weight of the iron of adding is 3 times of heavy metal molar weight in the alkaline residue;
3) upwards go on foot the hydrochloric acid that adds 36wt% in the aluminum chloride liquid that is settled out heavy metal and regulate acidity, add calcium aluminate again, add entry, molysite and ammonium persulphate again, react after 4-6 hour to regulate basicity, press filtration, gained filtrating is aluminium iron polychloride; Wherein, the mass ratio of contained aluminum chloride, calcium aluminate, ammonium persulphate, hydrochloric acid is 10:1.4:0.2:0.007 in the product, and the add-on of water is for confirming according to the solid content of last products therefrom.
Embodiment 3:
A kind of method of utilizing alkaline residue to produce aluminium iron polychloride may further comprise the steps:
1) under the room temperature, be that the hydrochloric acid, water three of 36wt% mixes and fully reacts 5-10h with alkaline residue, concentration; Wherein, described alkaline residue, hydrochloric acid, water three's mass ratio is 1:0.6:6;
2) add iron to displace heavy metal in the aluminum chloride liquid that upwards step makes; Wherein, the amount of the iron of adding is 2.5 times of heavy metal molar weight in the alkaline residue;
3) upwards go on foot the hydrochloric acid that adds 36wt% in the aluminum chloride liquid that is settled out heavy metal and regulate acidity, add calcium aluminate again, add entry, molysite and ammonium persulphate again, react after 4-6 hour to regulate basicity, press filtration, gained filtrating is aluminium iron polychloride; Wherein, the mass ratio of contained aluminum chloride, calcium aluminate, ammonium persulphate, hydrochloric acid is 10:1.35:0.15:0.006 in the product, and the add-on of water is for confirming according to the solid content of last products therefrom.
Through detecting, the product basicity of embodiment 1-3: 70-90, solid content: 10-20wt%, pH (aqueous solution of processing concentration and be 1wt% is tested): 4-5, water-insoluble :≤0.05 mg/L, heavy metal content :≤0.0001mg/L.
Among the present invention; Described raw material alkaline residue is the alkaline residue of fluorinated calcium not; The source is aluminium section bar plant, and commercially available, it is the mud of water cut 80-85wt%; Staple is the white lake (content of white lake in the solid matter in the alkaline residue >=85wt%), also contain nickel compound and tin compound impurity.

Claims (8)

1. method of utilizing alkaline residue to produce aluminium iron polychloride is characterized in that: may further comprise the steps:
1) under the room temperature, alkaline residue, hydrochloric acid, water three mixing are fully reacted;
2) add iron to displace heavy metal in the aluminum chloride liquid that upwards step makes;
3) upwards go on foot adding hydrochloric acid adjusting acidity in the aluminum chloride liquid that is settled out heavy metal, add calcium aluminate again, add entry, molysite and oxidation promoter again, react after 4-6 hour to regulate basicity, press filtration, gained filtrating is aluminium iron polychloride.
2. a kind of method of utilizing alkaline residue to produce aluminium iron polychloride according to claim 1, it is characterized in that: in the step 1), described alkaline residue, hydrochloric acid, water three's mass ratio is 1: (0.5-0.7): (5-7).
3. a kind of method of utilizing alkaline residue to produce aluminium iron polychloride according to claim 1, it is characterized in that: in step 1) and the step 3), the mass concentration of described hydrochloric acid is 30-37%.
4. a kind of method of utilizing alkaline residue to produce aluminium iron polychloride according to claim 1 is characterized in that: step 2) in, the molar weight of the iron of adding attach most importance to the metal molar amount 2-3 doubly.
5. a kind of method of utilizing alkaline residue to produce aluminium iron polychloride according to claim 1 is characterized in that: step 2) in, the time of reaction is 24-48 hour.
6. a kind of method of utilizing alkaline residue to produce aluminium iron polychloride according to claim 1, it is characterized in that: in the step 3), described molysite is an iron(ic)chloride.
7. a kind of method of utilizing alkaline residue to produce aluminium iron polychloride according to claim 1 is characterized in that: in the step 3), described oxidation promoter is a kind of in nitric acid, hydrogen peroxide, VAL-DROP, Peracetic Acid, the ammonium persulphate.
8. a kind of method of utilizing alkaline residue to produce aluminium iron polychloride according to claim 1; It is characterized in that: in the step 3), the mass ratio of the aluminum chloride in the product, calcium aluminate, oxidation promoter, hydrochloric acid is 10: (1.2-1.4): (0.1-0.2): (0.005-0.007).
CN2012102206118A 2012-06-29 2012-06-29 Method for producing poly aluminum ferric chloride (PAFC) by utilizing caustic sludge Pending CN102774889A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103818967A (en) * 2013-12-30 2014-05-28 中国神华能源股份有限公司 Treatment method of acid waste liquid in aluminum oxide production process with coal ash acid process
CN106277085A (en) * 2016-08-09 2017-01-04 广州博芳环保科技股份有限公司 A kind of method utilizing aluminium section bar plant sludge to prepare aluminium polychlorid
CN108946841A (en) * 2018-08-03 2018-12-07 河北泽世康环保科技有限公司 The method and water quality cleansing agent of water quality cleansing agent are prepared using waste catalyst after Friedel-Crafts reaction

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Publication number Priority date Publication date Assignee Title
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CN102229443A (en) * 2011-05-30 2011-11-02 江门市慧信净水材料有限公司 Method for preparing polyaluminium chloride ferric flocculant by using municipal sewage sludge
CN102260029A (en) * 2011-05-25 2011-11-30 童益 Method for preparing multi-copolymerization diacid water purifying agent from aluminum alloy sludge

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1182637A (en) * 1996-11-18 1998-05-27 吴敦虎 Making method for boron mud composite coagulant and usage thereof
CN102260029A (en) * 2011-05-25 2011-11-30 童益 Method for preparing multi-copolymerization diacid water purifying agent from aluminum alloy sludge
CN102229443A (en) * 2011-05-30 2011-11-02 江门市慧信净水材料有限公司 Method for preparing polyaluminium chloride ferric flocculant by using municipal sewage sludge

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Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103818967A (en) * 2013-12-30 2014-05-28 中国神华能源股份有限公司 Treatment method of acid waste liquid in aluminum oxide production process with coal ash acid process
CN103818967B (en) * 2013-12-30 2016-03-30 中国神华能源股份有限公司 Flyash acid system produces the treatment process of acid waste liquid in alumina process
CN106277085A (en) * 2016-08-09 2017-01-04 广州博芳环保科技股份有限公司 A kind of method utilizing aluminium section bar plant sludge to prepare aluminium polychlorid
CN108946841A (en) * 2018-08-03 2018-12-07 河北泽世康环保科技有限公司 The method and water quality cleansing agent of water quality cleansing agent are prepared using waste catalyst after Friedel-Crafts reaction

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Inventor after: Zhang Liguo

Inventor after: Liu Jinlong

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Application publication date: 20121114