CN102557213A - High-zinc composite ferroaluminum denitrified coagulant and preparation process thereof - Google Patents
High-zinc composite ferroaluminum denitrified coagulant and preparation process thereof Download PDFInfo
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Abstract
The invention provides a high-zinc composite ferroaluminum denitrified coagulant and a preparation process thereof. The liquid product of the coagulant is light khaki or red brown and the solid product of the coagulant is light yellow or khaki. The coagulant is a multifunctional inorganic composite water treatment agent with strong flocculating ability and capable of removing nitrogen from zinc salt, removing colloidal substance from aluminum salt and removing pollutants such as organic matters, heavy metal and the like from iron salt, wherein the denitrification effect is improved by 30 to 65 percent compared with that of the traditional coagulant. The main raw material is aluminized zinc slag; the additive is industrial zinc chloride solid or zinc sulfate solid; and the adding amount of the additive is 0 to 5 percent. The preparation process is a mixed acid leaching and alkali copolymerization method; the temperature of a reaction kettle is 25 to 100 DEG C; the pressure is normal pressure; and the equipment is simple. The high-zinc composite ferroaluminum denitrified coagulant can be applied in the technical fields of treatment on water such as urban sewage, industrial waste water, lake water with serious eutrophication and the like.
Description
Technical field
The invention belongs to water-treatment technology field, relate to a kind of high zinc compound ferro-aluminum denitrogenation coagulating agent and preparation technology thereof.
Background technology
In the last thirty years; Industrial or agricultural causes China's water environment pollution problem serious day by day with economic fast development; Wherein the nitrogen and phosphorus content in the water body sharply increases; Cause wawter bloom, the red tide phenomenon of surface water body frequently to break out, the health of hydrobiological normal growth and human body is arrived in serious threat, so denitrogenation dephosphorizing becomes one of focus of water-treatment technology field.Conventional denitrification dephosphorization technique generally adopts biological process, but has bottleneck problems such as the high flow rate of oxygen and energy, unstable operation, also denitrogenation up to standard generally need adopt tertiary treatment, cost obviously increases.Therefore simple, the lower-cost denitride technology of technology becomes scientific research and development field important in the water treatment, is of great immediate significance.
At present, noxious waste pollution has become the significant problem in the whole world, and the existing solid refuse of China surpasses 6,000,000,000 tons, and annual growth by 10%.Therefore, low-cost, the efficient disposal becomes the key point of being badly in need of solving noxious waste pollution, and wherein recycling treatment becomes the important means of economy, environmental protection, and utilizes waste to prepare the research focus that coagulating agent is a water treatment field always.The expert adopts solid waste such as coal gangue, flyash, iron ore, kaolin mine tailing, iron and steel pickling waste liquid, rare earth compound, black liquid, power station waste, waste plastic, organic waste materials to prepare various inorganic and organic coagulating agent both at home and abroad.This aspect report " utilizes flyash to produce the method for inorganic Al-Fe polymerized coagulant " referring to the national inventing patent of Yao Gang and Zhou Shufang, and application number is 01128398.X; The national inventing patent of Cheng Hongde, Liang Ning etc. " cleaning agent of aqueous aluminium iron polysilicate waste water and working method thereof ", application number is 00113030.7; The national inventing patent of Liu Qiwang, Chen Jiang equality " utilizes industrial residue one-step synthesis inorganic polymer flocculant--PAFS ", and application number is 200410046302.9.
In general, traditional coagulation process can dephosphorization, but nitric efficiency is very low.The national inventing patent that State Intellectual Property Office of the People's Republic of China is authorized " utilization aluminize cadmia prepare the method (ZL200910014566.9) of inorganic macromolecular composite ferro-aluminum zinc coagulant " provides a kind of utilization cadmia of aluminizing to prepare that package stability is better, coagulation effect is excellent and the method for lower-cost inorganic macromolecular composite ferro-aluminum zinc coagulant, but does not relate to denitrification functions.In the domestic and foreign literature DB, not seeing at present has the pertinent literature of efficient denitrification function coagulating agent preparation report.
Summary of the invention
The present invention is directed to the lower present situation of coagulating agent nitric efficiency, the high zinc compound ferro-aluminum denitrogenation coagulating agent and the preparation technology thereof that provide a kind of employing to aluminize the cadmia preparation.
The technical scheme that the present invention adopts is:
The component and the content of the compound ferro-aluminum denitrogenation of high zinc coagulating agent are:
Used Hydrogen chloride is technical grade, liquid.
Used dilute sulphuric acid is a technical grade, liquid.
Used sodium hydroxide is technical grade, solid, and sodium hydrate content is greater than 95%.
Used additive is zinc chloride or zinc sulfate, technical grade, and solid, zinc chloride content is greater than 90%, and zinc sulfate content is greater than 95%.
The preparation technology who above-mentioned each component is processed the compound ferro-aluminum denitrogenation of the high zinc of the present invention coagulating agent is:
A, employing wet method are broken for thin piece slag specimen article with 4%～6% the cadmia of aluminizing;
B, be that 85 ℃～100 ℃ and stirring velocity are under 200 rev/mins～600 rev/mins the condition in temperature; Massfraction with 40%～60% is that the massfraction of 10%～20% dilute hydrochloric acid solution and 10%～30% is that 20%～80% dilution heat of sulfuric acid joins in the above-mentioned bulk sample and leaches; The control leaching time is 3 hours～7 hours; Under temperature is 25 ℃～40 ℃ condition, filter then, obtain the I that filtrates, subsequent use;
C, be that 25 ℃～40 ℃ and stirring velocity are that zinc chloride solid with 0%～5% or zinc sulfate solid join among the above-mentioned filtrating I, obtain filtrate II, and be subsequent use under 200 rev/mins～400 rev/mins the condition in temperature;
D, low whipping speed are that the sodium hydrate solid with 0.1%～0.3% mixes with 6%～22% water, obtains sodium hydroxide solution, and is subsequent use under 400 rev/mins～800 rev/mins the condition;
E, be that 40 ℃～70 ℃ and stirring velocity are under 400 rev/mins～800 rev/mins the condition in temperature; Above-mentioned sodium hydroxide solution is joined in the above-mentioned filtrate II; Control pH value is 2～3, and polymerization 5 hours～30 hours makes light khaki color or liquid product russet;
F, application turning barrel formula furnace drying method are prepared into liquid product faint yellow or the solid shape product of khaki color, and the hot-air inlets temperature is 100 ℃～130 ℃.
Advantage of the present invention is:
1, the present invention is a main raw material with the solid waste cadmia of aluminizing; With industrial zinc chloride solid or zinc sulfate solid is additive; Adopt mixing acid to leach and add the method for alkali copolymerization, prepare the compound ferro-aluminum denitrogenation of the high zinc coagulating agent that package stability is better and denitrification effect is excellent.
2, the compound ferro-aluminum denitrogenation of high zinc of the present invention coagulating agent, production process is a normal pressure, it is 25 ℃～100 ℃ that temperature of reaction kettle requires.
3, the compound ferro-aluminum denitrogenation of high zinc of the present invention coagulating agent is the novel inorganic polymer compound coagulant that on conventional aluminum salt, iron salt coagulant basis, grows up, and can be applicable to the serious fields such as lake water of municipal effluent, trade effluent and eutrophication.
4, the compound ferro-aluminum denitrogenation of high zinc of the present invention coagulating agent is to have zinc salt denitrogenation and strong flocculation ability, aluminium salt concurrently to remove the multifunctional inorganic composite water treatment medicament that colloidalmaterial, molysite remove pollutents such as organic substance and heavy metal, and denitrification effect improves 30%～65% than traditional coagulating agent.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
Adopt wet method that the cadmia of aluminizing of 6kg is broken for thin piece slag specimen article.In temperature is that 85 ℃～100 ℃ and stirring velocity are under 200 rev/mins～600 rev/mins the condition; With the massfraction of 61L is that the massfraction of 12% dilute hydrochloric acid solution and 10L is that 50% dilution heat of sulfuric acid joins in the above-mentioned bulk sample and leaches; The control leaching time is 3 hours; Under temperature is 25 ℃～40 ℃ condition, filter then, obtain the I that filtrates, subsequent use.Low whipping speed is under 400 rev/mins～800 rev/mins the condition, and the sodium hydrate solid of 0.25kg is mixed with the water of 19L, obtains sodium hydroxide solution, and is subsequent use.In temperature is that 40 ℃～70 ℃ and stirring velocity are under 400 rev/mins～800 rev/mins the condition, and above-mentioned sodium hydroxide solution is joined among the above-mentioned filtrating I, and control pH value is 2.8, and polyase 13 0 hour makes liquid product russet.
Embodiment 2
Adopt wet method that the cadmia of aluminizing of 5kg is broken for thin piece slag specimen article.In temperature is that 85 ℃～100 ℃ and stirring velocity are under 200 rev/mins～600 rev/mins the condition; With the massfraction of 46L is that the massfraction of 17% dilute hydrochloric acid solution and 9L is that 35% dilution heat of sulfuric acid joins in the above-mentioned bulk sample and leaches; The control leaching time is 5 hours; Under temperature is 25 ℃～40 ℃ condition, filter then, obtain the I that filtrates, subsequent use.In temperature is that 25 ℃～40 ℃ and stirring velocity are under 200 rev/mins～400 rev/mins the condition, and zinc chloride solid or the zinc sulfate solid of 3kg joined among the above-mentioned filtrating I, obtains filtrate II, subsequent use.Low whipping speed is under 400 rev/mins～800 rev/mins the condition, and the sodium hydrate solid of 0.18kg is mixed with the water of 15L, obtains sodium hydroxide solution, and is subsequent use.In temperature is that 40 ℃～70 ℃ and stirring velocity are under 400 rev/mins～800 rev/mins the condition, and above-mentioned sodium hydroxide solution is joined in the above-mentioned filtrate II, and control pH value is 2, and polymerization 5 hours makes light khaki liquid product.
Embodiment 3
Adopt wet method that the cadmia of aluminizing of 4.5kg is broken for thin piece slag specimen article.In temperature is that 85 ℃～100 ℃ and stirring velocity are under 200 rev/mins～600 rev/mins the condition; With the massfraction of 40L is that the massfraction of 18% dilute hydrochloric acid solution and 20L is that 60% dilution heat of sulfuric acid joins in the above-mentioned bulk sample and leaches; The control leaching time is 7 hours; Under temperature is 25 ℃～40 ℃ condition, filter then, obtain the I that filtrates, subsequent use.In temperature is that 25 ℃～40 ℃ and stirring velocity are under 200 rev/mins～400 rev/mins the condition, and zinc chloride solid or the zinc sulfate solid of 5kg joined among the above-mentioned filtrating I, obtains filtrate II, subsequent use.Low whipping speed is under 400 rev/mins～800 rev/mins the condition, and the sodium hydrate solid of 0.3kg is mixed with the water of 23L, obtains sodium hydroxide solution, and is subsequent use.In temperature is that 40 ℃～70 ℃ and stirring velocity are under 400 rev/mins～800 rev/mins the condition, and above-mentioned sodium hydroxide solution is joined in the above-mentioned filtrate II, and control pH value is 3, and polymerization 15 hours makes liquid product russet.
Embodiment 4
Adopt wet method that the cadmia of aluminizing of 4.5kg is broken for thin piece slag specimen article.In temperature is that 85 ℃～100 ℃ and stirring velocity are under 200 rev/mins～600 rev/mins the condition; With the massfraction of 40L is that the massfraction of 15% dilute hydrochloric acid solution and 12L is that 40% dilution heat of sulfuric acid joins in the above-mentioned bulk sample and leaches; The control leaching time is 3 hours; Under temperature is 25 ℃～40 ℃ condition, filter then, obtain the I that filtrates, subsequent use.In temperature is that 25 ℃～40 ℃ and stirring velocity are under 200 rev/mins～400 rev/mins the condition, and zinc chloride solid or the zinc sulfate solid of 0.5kg joined among the above-mentioned filtrating I, obtains filtrate II, subsequent use.Low whipping speed is under 400 rev/mins～800 rev/mins the condition, and the sodium hydrate solid of 0.15kg is mixed with the water of 10L, obtains sodium hydroxide solution, and is subsequent use.In temperature is that 40 ℃～70 ℃ and stirring velocity are under 400 rev/mins～800 rev/mins the condition, and above-mentioned sodium hydroxide solution is joined in the above-mentioned filtrate II, and control pH value is 2.5, and polymerization 8 hours makes light khaki liquid product.
Embodiment 5
Adopt wet method that the cadmia of aluminizing of 6kg is broken for thin piece slag specimen article.In temperature is that 85 ℃～100 ℃ and stirring velocity are under 200 rev/mins～600 rev/mins the condition; With the massfraction of 61L is that the massfraction of 12% dilute hydrochloric acid solution and 10L is that 50% dilution heat of sulfuric acid joins in the above-mentioned bulk sample and leaches; The control leaching time is 3 hours; Under temperature is 25 ℃～40 ℃ condition, filter then, obtain the I that filtrates, subsequent use.Low whipping speed is under 400 rev/mins～800 rev/mins the condition, and the sodium hydrate solid of 0.25kg is mixed with the water of 19L, obtains sodium hydroxide solution, and is subsequent use.In temperature is that 40 ℃～70 ℃ and stirring velocity are under 400 rev/mins～800 rev/mins the condition, and above-mentioned sodium hydroxide solution is joined among the above-mentioned filtrating I, and control pH value is 2.8, and polyase 13 0 hour makes liquid product russet.Use turning barrel formula furnace drying method liquid product is prepared into the solid shape product of khaki color, the hot-air inlets temperature is 120 ℃.
Embodiment 6
Adopt wet method that the cadmia of aluminizing of 5kg is broken for thin piece slag specimen article.In temperature is that 85 ℃～100 ℃ and stirring velocity are under 200 rev/mins～600 rev/mins the condition; With the massfraction of 46L is that the massfraction of 17% dilute hydrochloric acid solution and 9L is that 35% dilution heat of sulfuric acid joins in the above-mentioned bulk sample and leaches; The control leaching time is 5 hours; Under temperature is 25 ℃～40 ℃ condition, filter then, obtain the I that filtrates, subsequent use.In temperature is that 25 ℃～40 ℃ and stirring velocity are under 200 rev/mins～400 rev/mins the condition, and zinc chloride solid or the zinc sulfate solid of 3kg joined among the above-mentioned filtrating I, obtains filtrate II, subsequent use.Low whipping speed is under 400 rev/mins～800 rev/mins the condition, and the sodium hydrate solid of 0.18kg is mixed with the water of 15L, obtains sodium hydroxide solution, and is subsequent use.In temperature is that 40 ℃～70 ℃ and stirring velocity are under 400 rev/mins～800 rev/mins the condition, and above-mentioned sodium hydroxide solution is joined in the above-mentioned filtrate II, and control pH value is 2, and polymerization 5 hours makes light khaki liquid product.Use turning barrel formula furnace drying method liquid product is prepared into pale yellow colored solid shape product, the hot-air inlets temperature is 100 ℃.
Application example
With the No.1,2,3 of above embodiment 1,2,3,4 preparations, the coagulation denitrogenation processing that the compound ferro-aluminum denitrogenation of 4 high zinc coagulating agent product is used to simulate landscape water, contrast with Poly aluminum Chloride (PAC) simultaneously.Raw water turbidity is 101～124NTU, pH value 7.89～8.12, COD
Cr129～143mg/L, ammonia nitrogen 7.45～7.82mg/L, 16 ℃ of water temperatures.Dispensing concentration is mg aluminium/L water sample.Result is listed in table 1.
The coagulation denitrification effect of the compound ferro-aluminum denitrogenation of the high zinc of table 1 coagulating agent
Visible from above result, the coagulation denitrification effect of the compound ferro-aluminum denitrogenation of high zinc coagulating agent obviously is superior to the Poly aluminum Chloride (PAC) coagulating agent.
Claims (5)
1. the compound ferro-aluminum denitrogenation of high zinc coagulating agent, its component and content are:
The preparation technology who above-mentioned each component is processed the compound ferro-aluminum denitrogenation of the high zinc of the present invention coagulating agent is:
A, employing wet method are broken for thin piece slag specimen article with 4%～6% the cadmia of aluminizing;
B, be that 85 ℃～100 ℃ and stirring velocity are under 200 rev/mins～600 rev/mins the condition in temperature; Massfraction with 40%～60% is that the massfraction of 10%～20% dilute hydrochloric acid solution and 10%～30% is that 20%～80% dilution heat of sulfuric acid joins in the above-mentioned bulk sample and leaches; The control leaching time is 3 hours～7 hours; Under temperature is 25 ℃～40 ℃ condition, filter then, obtain the I that filtrates, subsequent use;
C, be that 25 ℃～40 ℃ and stirring velocity are that zinc chloride solid with 0%～5% or zinc sulfate solid join among the above-mentioned filtrating I, obtain filtrate II, and be subsequent use under 200 rev/mins～400 rev/mins the condition in temperature;
D, low whipping speed are that the sodium hydrate solid with 0.1%～0.3% mixes with 6%～22% water, obtains sodium hydroxide solution, and is subsequent use under 400 rev/mins～800 rev/mins the condition;
E, be that 40 ℃～70 ℃ and stirring velocity are under 400 rev/mins～800 rev/mins the condition in temperature; Above-mentioned sodium hydroxide solution is joined in the above-mentioned filtrate II; Control pH value is 2～3, and polymerization 5 hours～30 hours makes light khaki color or liquid product russet;
F, application turning barrel formula furnace drying method are prepared into liquid product faint yellow or the solid shape product of khaki color, and the hot-air inlets temperature is 100 ℃～130 ℃.
2. the compound ferro-aluminum denitrogenation of high zinc according to claim 1 coagulating agent is characterized in that used Hydrogen chloride is technical grade, liquid.
3. the compound ferro-aluminum denitrogenation of high zinc according to claim 1 coagulating agent is characterized in that used dilute sulphuric acid is a technical grade, liquid.
4. the compound ferro-aluminum denitrogenation of high zinc according to claim 1 coagulating agent is characterized in that used sodium hydroxide is technical grade, solid, and sodium hydrate content is greater than 95%.
5. the compound ferro-aluminum denitrogenation of high zinc according to claim 1 coagulating agent is characterized in that used additive is zinc chloride or zinc sulfate, technical grade, and solid, zinc chloride content is greater than 90%, and zinc sulfate content is greater than 95%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183406A (en) * | 2013-03-14 | 2013-07-03 | 济南大学 | Preparation method of high-concentration PAM-aluminum, zinc iron composite water treatment agent |
| CN107416955A (en) * | 2017-05-31 | 2017-12-01 | 成都原端新材料科技有限公司 | A kind of denitrifier and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08206410A (en) * | 1995-02-06 | 1996-08-13 | Okinawa Sanrotsukusu Kk | Coagulant for water treatment |
| CN101497469A (en) * | 2009-03-11 | 2009-08-05 | 济南大学 | Method for preparing inorganic polymer composite aluminum iron zinc coagulant from aluminum plating zincilate |
| CN101734772A (en) * | 2008-11-14 | 2010-06-16 | 北京石油化工学院 | Composite flocculant for treating industrial waste water and preparation method |
-
2012
- 2012-03-01 CN CN 201210049731 patent/CN102557213B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08206410A (en) * | 1995-02-06 | 1996-08-13 | Okinawa Sanrotsukusu Kk | Coagulant for water treatment |
| CN101734772A (en) * | 2008-11-14 | 2010-06-16 | 北京石油化工学院 | Composite flocculant for treating industrial waste water and preparation method |
| CN101497469A (en) * | 2009-03-11 | 2009-08-05 | 济南大学 | Method for preparing inorganic polymer composite aluminum iron zinc coagulant from aluminum plating zincilate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183406A (en) * | 2013-03-14 | 2013-07-03 | 济南大学 | Preparation method of high-concentration PAM-aluminum, zinc iron composite water treatment agent |
| CN107416955A (en) * | 2017-05-31 | 2017-12-01 | 成都原端新材料科技有限公司 | A kind of denitrifier and preparation method thereof |
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