CN102115234A - Preparation method of flocculant capable of removing phosphate from red mud - Google Patents
Preparation method of flocculant capable of removing phosphate from red mud Download PDFInfo
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- CN102115234A CN102115234A CN2009102441686A CN200910244168A CN102115234A CN 102115234 A CN102115234 A CN 102115234A CN 2009102441686 A CN2009102441686 A CN 2009102441686A CN 200910244168 A CN200910244168 A CN 200910244168A CN 102115234 A CN102115234 A CN 102115234A
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Abstract
The invention provides a preparation method of a flocculant capable of removing phosphate from red mud, belonging to a preparation process of a flocculant for feed water and waste water treatment and relating to the field of sewage treatment in environment conservation. The preparation method comprises the following steps: adding alumyte and red mud particles in industrial hydrochloric acid, and performing the steps of mixing, reacting, aging and the like, so as to obtain the flocculant capable of removing phosphate. The flocculant produced by the preparation method is good in stability, and is suitable for the purification treatment of feed water and waste water; the effect of the flocculant is superior to that of the common polyaluminium chloride; and the preparation method is simple, is easy to achieve industrial production and has a wide open application prospect.
Description
Technical field
The invention belongs to technical field of sewage, particularly the dephosphorization technique in the sewage disposal.
Technical background
P contained compound is one of reason that causes rivers and creeks, water body in lake eutrophication.The wide material sources of P contained compound, the phosphorus loss in city domestic sewage, trade effluent and the soil all are its sources.Therefore, adopt an effective measure and control the content of phosphorus in city domestic sewage and the trade effluent, can avoid the eutrophication of water body to a great extent.
Current, the removal of phosphorus mainly contains two kinds of biological process and chemical methods in the waste water.Wherein biological phosphate-eliminating is based on the principle of biting the picked-up of phosphorus bacterium and discharging phosphorus, realizes the removal of phosphorus by aerobic-anaerobism alternate run.Biological phosphate-eliminating is a kind of method of relatively economical has simultaneously the valency pollutent in the removal water a advantage, but this method technology operation stability is poor, and the operation strictness is influenced greatly by wastewater temperature and potential of hydrogen, and is strong to organic concentration dependency in the water.Lower when organic concentration in the water, when phosphorus content is higher, the clearance of phosphorus is lower, has only 30%～40% usually, therefore single biological phosphate-eliminating technology is difficult to reach the national secondary discharge standard that is lower than 1mg/L.Chemical process is by adding one or more materials, by generating the sedimentary method of difficultly-soluble phosphates with phosphate radical, make phosphor in sewage become suspended particle, post precipitation separates to be removed, and physico-chemical processes can drop to the content of phosphorus the national secondary discharge standard of 1mg/L.The medicament commonly used of chemical dephosphorization is that flocculation agent generally is inorganic aluminate and inorganic molysite, as aluminum chloride and iron trichloride etc.This method is reliable, can obtain higher dephosphorizing rate, but this process is a precipitation-dissolution equilibrium reaction process, when phosphorus content is low in the water supply source, needs to add a large amount of medicaments usually and comes the precipitate phosphoric acid root, causes medicament expense to increase substantially thus.Simultaneously because metal ion content raising in the water outlet causes colourity to increase.In addition, the sludge moisture content that produces in treating processes is big, is difficult for handling, and easily causes secondary pollution.
The absorption method dephosphorization is a kind of emerging phosphorus removing method.The bigger serface that this method utilizes sorbent material to provide, by phosphorus adsorbent surface adhere to absorption, ion-exchange or surface precipitation process, phosphorus is separated from water.In addition, utilize the absorption-desorption method, realizing eliminating the purpose that can also reach the recovery phosphor resource, turn waste into wealth when phosphorus pollutes in the waste water.Therefore, adsorption and dephosphorization is greatly developed in field of waste water treatment, polytype sorbent material occurred, and is wherein the most representative with activated alumina.Yet this sorbent material but exists loading capacity big inadequately, the shortcoming that the cycle of operation is short.
Therefore; can not satisfy under the situation of more and more high-level water treatment market demand at traditional flocculant at aspects such as economy, securities; consider based on the market requirement and environmental protection industry characteristics; development, development of new economy, nontoxic, flocculating property is high, non-secondary pollution, environmentally friendly, cheap composite flocculant become the task of top priority; it all is extremely important to protection water surrounding, raising water supply security for the research and development that promotes the dephosphorization medicament.
Summary of the invention
The objective of the invention is provides a kind of Phosphorus flocculating agent and its preparation method at the weak point of dephosphorization technique and the high shortcoming of production cost of used flocculation agent in existing municipal effluent and the trade effluent.That the present invention has is with low cost, production technique simple, dephosphorization usefulness height, non-secondary pollution, environmentally friendly, to characteristics such as HUMAN HEALTH are harmless, flocculation agent of the present invention can also be handled the phosphorus-containing wastewater of lower concentration simultaneously, effect is obvious.
The invention provides a kind of preparation method of efficient liquid phosphate eliminating flocculant, step is as follows:
1) preparation aluminum chloride acid solution
Under the normal pressure, being 1: 3～1: 5 mixed with bauxitic clay and technical hydrochloric acid according to mass ratio, is to mix under 60 ℃～100 ℃ in temperature.React after 3～5 hours, it is 15～20 that dope is diluted to degree Beaume;
2) the pH value of adjustment aluminum chloride acid solution
With masher red mud is ground to particle and crosses 60～100 mesh sieves, under agitation slowly join in the aluminum chloride acid solution.Add-on is the mixed of 10: 5～10: 9 (ml/g) according to the liquid-solid ratio of acid solution and red mud, and the pH value of acid adjustment liquid is 0.5～1.5;
3) slaking of flocculation agent
With 2) acid solution adjusted after the pH value of step is 60 ℃～100 ℃ stirrings 3～5 hours down in temperature, promptly can make the phosphate eliminating flocculant that contains aluminium 6～10mg/L;
Innovation part of the present invention and characteristics
1) production cost is low for industrial sewage or domestic sewage treating, answers emphasis to consider the economic benefit of water conditioner, and the flocculation agent raw materials cost accounts for the major portion of its total cost.The raw material that prescription of the present invention adopts is bauxite, technical hydrochloric acid and red mud, and cost of material cheaply is easy to get, the cost performance height of cost.
2) city domestic sewage or trade effluent that the flocculation agent that dephosphorization usefulness height makes through the present invention was handled, its phosphorus content not only can reach the national secondary discharge standard of 1mg/L, can also concentration of treatment be the low-concentration phosphorus-containing wastewater of 1mg/L and 0.2mg/L.
3) good social benefit red mud is the solid slag that produces in the aluminium metallurgy process.Do raw material with it, both avoided the pollution of red mud, the new approach that has been again the disposal of solid waste and recycle demand environment.
4) be easy to realize that industrialization the present invention is not high to equipment requirements, the reaction conditions gentleness, operating process is simple, and different according to process object and sewage character can suitably be adjusted prescription in described scope, handle target contaminant with maximum efficiency ground.
Specific implementation method
The phosphate eliminating flocculant production craft step is as follows:
1) preparation aluminum chloride acid solution
Under the normal pressure, being 1: 4 mixed with bauxitic clay and technical hydrochloric acid according to mass ratio, is to mix under 80 ℃ in temperature.React after 4 hours, it is 17 that dope is diluted to degree Beaume;
2) the pH value of adjustment aluminum chloride acid solution
With masher red mud is ground to particle and crosses 80 mesh sieves, under agitation slowly join in the aluminum chloride acid solution.Add-on is the mixed of 10: 7 (ml/g) according to the liquid-solid ratio of acid solution and red mud, and the pH value of acid adjustment liquid is 1;
3) slaking of flocculation agent
With 2) acid solution adjusted after the pH value of step is 80 ℃ of stirrings 4 hours down in temperature, promptly can make the phosphate eliminating flocculant that contains aluminium 8mg/L;
The major ingredient and the concentration (in metal oxide) of the flocculation agent of producing according to above-mentioned processing step are as follows:
Al
2O
3 15.2mg/L
Fe
2O
3 2.683mg/L
SiO
2 3.451mg/L
CaO 7.393mg/L
Embodiment
Citing an actual example below, the present invention is described further, and be that the experiment waste water of 1mg/L and 0.2mg/L is handled to containing phosphorus concentration respectively with phosphate eliminating flocculant that the present invention was developed.Found that in the treating processes, the flco of generation is big, settling velocity is fast, and effect is remarkable.After treatment, waste water contains phosphorus concentration and can reduce to below the 0.02mg/L.
Embodiment 1
100kg hydrochloric acid is dropped in the reactor, and logical steam to 80 ℃ adds the 25kg bauxitic clay, and stirring reaction 4h is diluted to baume density 17 (proportion about 1.13～1.14) then; Logical again steam to 80 ℃ adds red mud particle 70kg simultaneously, and stirring reaction keeps boiling 4h.Reaction is left standstill and can be made brown efficient dephosphorization flocculation agent in 24 hours after finishing.
Get the phosphate eliminating flocculant that the present invention makes, being added to and containing in the experiment waste water that phosphorus concentration is 1mg/L and 0.2mg/L, is earlier that 300rpm stirs 2min with the rotating speed, stirs 30min with rotating speed 100rpm again, go supernatant liquor to carry out the phosphorus concentration analysis behind the sedimentation 30min, the results are shown in following table.
Claims (5)
1. the present invention relates to a kind of red mud phosphate eliminating flocculant preparation method of novel economizer, it is characterized in that: after at first industrial aluminium hydroxide (or bauxitic clay) and hydrochloric acid being mixed by a certain percentage and reacting for some time at a certain temperature, preparation acid hydroxy group liquor alumini chloridi; Then the red mud through being crushed to certain particle diameter is progressively joined in the acid hydroxy group liquor alumini chloridi liquid by a certain percentage, to improve the pH value of mixed solution; With the mixed solution regular hour of slaking at a certain temperature of adjusting, promptly make efficient red mud phosphate eliminating flocculant at last.
2. red mud according to claim 1 is meant red mud from sintering process, and powder particle diameter is 60～100 orders.
3. it is to adopt industrial aluminium hydroxide (or Al that acid hydroxy group aluminum chloride according to claim 1 prepares raw material
2O
3The quality percentage composition be the bauxite ore of 30-40%) and the quality percentage composition be the technical hydrochloric acid of 28-30%.
4. the mass ratio that is industrial aluminium hydroxide or bauxite ore and technical hydrochloric acid according to acid hydroxy group aluminum chloride preparation method according to claim 1 is 1: 3～1: 6.Mixing whipping temp is 60 ℃～100 ℃, and the reaction times is 3～5 hours, and whipping temp is 80 ℃, and the reaction times is 4 hours.Degree Beaume is 15～20, and best degree Beaume is 17.
5. red mud phosphate eliminating flocculant preparation method according to claim 1, a certain proportion of red mud from sintering process adds in the acid chlorization aluminum solutions, and liquid-solid ratio is 10: 5～10: 9 (ml/g), and the pH of mixed value is adjusted into 0.5～1.5, and optimal ph is 1.Curing temperature is 60 ℃～100 ℃, and the time is 3～5 hours, and the optimum cure temperature is 80 ℃, and the curing time is 4 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102441686A CN102115234A (en) | 2009-12-30 | 2009-12-30 | Preparation method of flocculant capable of removing phosphate from red mud |
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| CN2009102441686A CN102115234A (en) | 2009-12-30 | 2009-12-30 | Preparation method of flocculant capable of removing phosphate from red mud |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833118A (en) * | 2014-03-19 | 2014-06-04 | 重庆大学 | Preparation method of polyaluminium chloride coagulant |
| CN104105532A (en) * | 2011-08-30 | 2014-10-15 | 约瑟夫·扬尼切利 | Methods for treating waste waters using sulfidized red mud sorbents |
| CN104250036A (en) * | 2013-06-27 | 2014-12-31 | 沈阳铝镁设计研究院有限公司 | Phosphorus removal compound flocculating agent prepared from red mud and preparation method and use method |
| CN104326619A (en) * | 2014-10-08 | 2015-02-04 | 环境保护部南京环境科学研究所 | A<2>/O process based simultaneous nitrogen and phosphorus removal and algae reduction treatment system and method |
| CN104549173A (en) * | 2015-02-06 | 2015-04-29 | 中国环境科学研究院 | Preparation method and application of phosphorus-adsorbing material used in sewage |
| CN105152194A (en) * | 2015-07-16 | 2015-12-16 | 中国铝业股份有限公司 | Red mud separation and settlement method in alumina production |
| CN107043157A (en) * | 2017-05-31 | 2017-08-15 | 成都原端新材料科技有限公司 | Mineral dephosphorization agent and preparation method thereof |
| CN109879387A (en) * | 2019-03-22 | 2019-06-14 | 长沙如洋环保科技有限公司 | A kind of slaughter technics treatment process |
| CN110436552A (en) * | 2019-08-23 | 2019-11-12 | 河南亿群环保科技有限公司 | A kind of sewage treatment precipitating reagent |
| CN110694585A (en) * | 2019-09-23 | 2020-01-17 | 北京工业大学 | Preparation method of zirconium modified red mud phosphorus removal adsorbent |
| CN113800616A (en) * | 2021-09-30 | 2021-12-17 | 西安吉利电子化工有限公司 | Phosphorus removing agent for wastewater treatment |
-
2009
- 2009-12-30 CN CN2009102441686A patent/CN102115234A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104105532A (en) * | 2011-08-30 | 2014-10-15 | 约瑟夫·扬尼切利 | Methods for treating waste waters using sulfidized red mud sorbents |
| CN104250036A (en) * | 2013-06-27 | 2014-12-31 | 沈阳铝镁设计研究院有限公司 | Phosphorus removal compound flocculating agent prepared from red mud and preparation method and use method |
| CN104250036B (en) * | 2013-06-27 | 2016-08-10 | 沈阳铝镁设计研究院有限公司 | Utilize dephosphorization composite flocculation agent and preparation method and using method that red mud makes |
| CN103833118B (en) * | 2014-03-19 | 2015-03-25 | 重庆大学 | Preparation method of polyaluminium chloride coagulant |
| CN103833118A (en) * | 2014-03-19 | 2014-06-04 | 重庆大学 | Preparation method of polyaluminium chloride coagulant |
| CN104326619B (en) * | 2014-10-08 | 2017-05-24 | 环境保护部南京环境科学研究所 | A2/O process based simultaneous nitrogen and phosphorus removal and algae reduction treatment system and method |
| CN104326619A (en) * | 2014-10-08 | 2015-02-04 | 环境保护部南京环境科学研究所 | A<2>/O process based simultaneous nitrogen and phosphorus removal and algae reduction treatment system and method |
| CN104549173A (en) * | 2015-02-06 | 2015-04-29 | 中国环境科学研究院 | Preparation method and application of phosphorus-adsorbing material used in sewage |
| CN105152194A (en) * | 2015-07-16 | 2015-12-16 | 中国铝业股份有限公司 | Red mud separation and settlement method in alumina production |
| CN107043157A (en) * | 2017-05-31 | 2017-08-15 | 成都原端新材料科技有限公司 | Mineral dephosphorization agent and preparation method thereof |
| CN109879387A (en) * | 2019-03-22 | 2019-06-14 | 长沙如洋环保科技有限公司 | A kind of slaughter technics treatment process |
| CN110436552A (en) * | 2019-08-23 | 2019-11-12 | 河南亿群环保科技有限公司 | A kind of sewage treatment precipitating reagent |
| CN110694585A (en) * | 2019-09-23 | 2020-01-17 | 北京工业大学 | Preparation method of zirconium modified red mud phosphorus removal adsorbent |
| CN113800616A (en) * | 2021-09-30 | 2021-12-17 | 西安吉利电子化工有限公司 | Phosphorus removing agent for wastewater treatment |
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Application publication date: 20110706 |