CN103043759B - Method for preparing polyaluminium ferric chloride flocculating agent by pickling waste liquid and waste aluminium material - Google Patents
Method for preparing polyaluminium ferric chloride flocculating agent by pickling waste liquid and waste aluminium material Download PDFInfo
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- CN103043759B CN103043759B CN201210539665.0A CN201210539665A CN103043759B CN 103043759 B CN103043759 B CN 103043759B CN 201210539665 A CN201210539665 A CN 201210539665A CN 103043759 B CN103043759 B CN 103043759B
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Abstract
The invention discloses a method for preparing a polyaluminium ferric chloride flocculating agent by pickling waste liquids and waste aluminium materials. The method for preparing a polyaluminium ferric chloride flocculating agent, comprises: mixing waste aluminium materials after acid dissolution and pickling waste liquids, regulating a pH value by sodium hydroxide, and oxidizing and polymerizing the mixture by a strong oxide to obtain the polyaluminium ferric chloride flocculating agent. Compared with the prior art, the method uses the raw materials which are cheap and wide in source, and has advantages of simple process and easy operation. The addition of waste aluminium materials is controlled to regulate the pH valve, thereby effectively reducing the cost. The proportion of aluminium to iron in the raw materials is flexibly controlled, and the application range is winder.
Description
Technical field
The present invention relates to a kind of method and application thereof that utilizes spent pickle liquor and aluminium scrap material to prepare aluminium iron polychloride floculant, belong to the technical fields such as environmental chemical engineering, wastewater treatment.
Background technology
For improving steel surface structure or effects on surface, carry out processing treatment, often utilize the corrosive nature of strong acid to clean steel surface, and when cleaning proceeds to a certain degree, in washing lotion, acid concentration reduces, need to change eo-acid to maintain suitable pickling speed, residual liquor discharge forms the waste liquid of high-concentration metallic ions and residual acid, and its main component is solution of ferrous chloride.According to incompletely statistics, the spent pickle liquor that discharge in the whole nation is greater than 1 * 10
6m
3/ a.Spent pickle liquor is acid by force, concentration is high, waste liquid amount greatly, easily forms acid mist, if directly discharge can cause serious environmental pollution, also causes Fe in waste liquid simultaneously
2+, the useful resources such as spent acid waste.How to realize the resource utilization of spent pickle liquor, become the focus of domestic and international research, the technology of various comprehensive utilizations comprises neutralization bases wastewater, cyclic regeneration technique etc., and wherein preparing inorganic polymer flocculant is a main direction.
The output of China's aluminium section bar is every year with 40% speed increment, and the aluminium section bar output of China in 2007 reaches more than 600 ten thousand tons.In producing the process of aluminium section bar, have aluminium waste, as the generation of aluminium slag, aluminium bits, aluminium scrap stock.The recovery of aluminium waste, recycling, no matter resource, cost-saving from saving the earth, or environment protection, improves the each side such as human ecological environment and has very huge meaning.
20 century 70s, the development that the success of polymerize aluminum chloride is developed as inorganic polymer flocculant provides wide prospect, after first European patent publication of the eighties about aluminium iron polychloride, people then research aluminium iron polychloride.Aluminium iron polychloride is a kind of inorganic polymer flocculant of excellent property, it gets up the two advantages of polymerize aluminum chloride and poly-ferric chloride, both there is the good charge neutrality of aluminum salt flocculant, absorption, bridge formation and sweep coagulation effect, turbidity removal effect is good, to advantages such as equipment corrosion of piping are little; Have again that Ferric Salt Flocculants sedimentation is fast, subzero treatment performance is good, adapt to pH value scope wide, be easy to the advantages such as separation.
The patent and the document that utilize at present spent pickle liquor to prepare poly-ferric chloride have a lot, as Chinese patent application publication No., are wherein the patent of CN1266819A, CN1789147A, CN101780986A, CN102502747A, CN102603015A.But utilize aluminum feedstock and spent pickle liquor for starting material, regulate suitable pH environment, be aided with oxygenant, the report of preparing aluminium iron polychloride by the method for oxypolymerization seldom.The polymerized ferric-aluminum chloride coagulating agent product basicity that patent CN101074128A produces with calcium aluminate powder and spent pickle liquor is too low, and need to add stablizer.Patent CN102372308A adopts aluminum feedstock (bauxitic clay or aluminium hydrate powder) and spent pickle liquor to prepare aluminium iron polychloride, and its mother liquor preparation process is strict to the requirement of pressure.Huang Yongqiang (electroplates spent acid and prepares flocculant poly aluminium chloride ferrum and applied research thereof, water technology, 2010,36(12), 113 ~ 116) with calcium aluminate powder and plating spent acid, be raw material, with the method for catalyzed oxidation, prepare polymerize aluminum chloride, although technique is simple, but the oxygenant of its use is Sodium Nitrite, and oxidation efficiency is not high, in preparation process, introducing nitrite ion all has side effect to environment and HUMAN HEALTH.
Summary of the invention
The object of the invention is to provide a kind of method and application thereof that utilizes spent pickle liquor and aluminium scrap material to prepare aluminium iron polychloride floculant, solves the pollution problem of spent pickle liquor, refuse is made full use of simultaneously, turns waste into wealth.
The invention provides a kind of method of utilizing spent pickle liquor and aluminium scrap material to prepare aluminium iron polychloride floculant and there are following steps:
(1) with aluminium scrap material and technical hydrochloric acid under atmospheric pressure state, put into acid-resistant container reaction, when pH rises to 0.8 ~ 1.3, filter, generate containing aluminum solutions;
(2) after adding aluminium scrap material that it is dissolved completely in spent pickle liquor, the pH of its solution rises to 1.6 ~ 2.0, generates iron-containing liquor;
(3) iron-containing liquor containing in aluminum solutions and step (2) in step (1) is dropped in anticorrosive reaction vessel in proportion, the pH value that adds alkali adjusting mixed solution is 1.9 ~ 3.0;
(4) temperature of reaction vessel mixed solution is controlled to 65 ~ 85 ℃, low rate mixing, adds oxygenant, reacts 30 ~ 60 minutes, stops heating, and ageing 2 ~ 3 hours, makes aluminium iron polychloride floculant.
In above-mentioned steps (1), aluminium scrap material is aluminium scrap stock, aluminium bits and the aluminium slag that aluminium produces in the course of processing; Wherein aluminium content is 70 ~ 80%.
In above-mentioned steps (1), containing Al(III in aluminum solutions) concentration is 70 ~ 100g/L.
In above-mentioned steps (2), spent pickle liquor is iron and steel pickling waste liquid, and contained free acid is hydrochloric acid, and wherein Fe (II) concentration is 160 ~ 175g/L, and Fe (III) concentration is 15 ~ 20g/L.
In above-mentioned steps (3), the mol ratio of aluminium and iron is 6 ~ 9:4～1.
In above-mentioned steps (4), oxygenant is sodium chlorate, with solid form or solution form, adds.
The present invention also provides the turbidity removal of a kind of above-mentioned aluminium iron polychloride floculant for wastewater treatment process, decolouring, oil removing and other solid-liquid separation process.
Compared with prior art, the present invention has following beneficial effect:
1. utilize iron and steel pickling waste liquid and aluminium scrap material as the raw material of preparation, both are the waste material producing in industrial production, reduce the cost of preparing aluminium iron polychloride, also realized the comprehensive utilization of spent pickle liquor and aluminium scrap material simultaneously, alleviated the pollution of spent pickle liquor to environment.
2. the sodium chlorate that employing oxidisability is very strong is as oxygenant, and oxidation rate is fast, and efficiency is high, can be by the Fe in spent pickle liquor
2+all be oxidized to Fe
3+, the aluminium iron polychloride floculant stability of preparation is strong.
3. adopt the method first adjust the polymerization of basicity rear oxidation, in the process of dissolving aluminium scrap material, control pH, make the pH value of solution spontaneously increase, thereby can only add a small amount of alkali and make pH rising, the cost of aluminium iron polychloride is prepared in reduction.
4. whole preparation process is all carried out under normal pressure, to equipment require lowly, a whole set of technological operation is simple, can control flexibly the ratio of ferro-aluminum in raw materials, makes the range of application of flocculation agent more extensive.
Embodiment
The present invention is further described below in conjunction with case study on implementation, but does not limit the present invention.
Embodiment 1
(1) getting aluminium content is 70% aluminium scrap material 50g, and technical hydrochloric acid (HCl is 23%) 740g, puts in acid tolerance response container.When pH value of solution=1.0, to filter, filtrate is containing aluminum solutions;
(2) get iron and steel pickling waste liquid 55g, aluminium scrap material 0.22g, puts in acid tolerance response container, treats to dissolve completely the iron-containing liquor that solution is pH=1.8;
(3) iron-containing liquor containing in aluminum solutions and step (2) in step (1) is dropped in anticorrosive reaction vessel, drip while stirring the sodium hydroxide solution of 2mol/L, when pH=1.91, heating, is controlled at 75 ℃ by temperature, low rate mixing, add sodium chlorate 2.4g, react 40 minutes, stop heating, ageing is Al for 3 hours
2o
3content 10.2%, Fe
2o
3content 1.8%, the aluminium iron polychloride finished product that basicity is 40.6%.
Embodiment 2
(1) getting aluminium content is 75% aluminium scrap material 43g, and technical hydrochloric acid (HCl is 25%) 620g, puts in acid tolerance response container.When pH value of solution=1.1, to filter, filtrate is containing aluminum solutions;
(2) get iron and steel pickling waste liquid 105g, aluminium scrap material 0.45g, puts in acid tolerance response container, treats to dissolve completely the iron-containing liquor that solution is pH=1.9;
(3) iron-containing liquor containing in aluminum solutions and step (2) in step (1) is dropped in anticorrosive reaction vessel, drip while stirring the sodium hydroxide solution of 2mol/L, when pH=1.98, heating, is controlled at 70 ℃ by temperature, low rate mixing, add sodium chlorate 4.5g, react 50 minutes, stop heating, ageing is Al for 2 hours
2o
3content 8.6%, Fe
2o
3content 3.4%, the aluminium iron polychloride finished product that basicity is 39.8%.
Embodiment 3
(1) getting aluminium content is 80% aluminium scrap material 35g, and technical hydrochloric acid (HCl is 26%) 520g, puts in acid tolerance response container.When pH value of solution=0.9, to filter, filtrate is containing aluminum solutions;
(2) get iron and steel pickling waste liquid 150g, aluminium scrap material 0.6g, puts in acid tolerance response container, treats to dissolve completely the iron-containing liquor that solution is pH=1.7;
(3) iron-containing liquor containing in aluminum solutions and step (2) in step (1) is dropped in anticorrosive reaction vessel, drip while stirring the sodium hydroxide solution of 2mol/L, when pH=2.35, heating, is controlled at 75 ℃ by temperature, low rate mixing, add sodium chlorate 6.5g, react 40 minutes, stop heating, ageing is Al for 3 hours
2o
3content 7.1%, Fe
2o
3content 4.8%, the aluminium iron polychloride finished product that basicity is 47.1%.
Embodiment 4
(1) getting aluminium content is 78% aluminium scrap material 30g, and technical hydrochloric acid (HCl is 25%) 440g, puts in acid tolerance response container.When pH value of solution=1.1, to filter, filtrate is containing aluminum solutions;
(2) get iron and steel pickling waste liquid 190g, aluminium scrap material 0.82g, puts in acid tolerance response container, treats to dissolve completely the iron-containing liquor that solution is pH=1.9;
(3) iron-containing liquor containing in aluminum solutions and step (2) in step (1) is dropped in anticorrosive reaction vessel, drip while stirring the sodium hydroxide solution of 2mol/L, when pH=2.97, heating, is controlled at 70 ℃ by temperature, low rate mixing, add sodium chlorate 8.2g, react 40 minutes, stop heating, ageing is Al for 3 hours
2o
3content 5.8%, Fe
2o
3content 6.1%, the aluminium iron polychloride finished product that basicity is 54.6%.
Claims (4)
1. utilize spent pickle liquor and aluminium scrap material to prepare a method for aluminium iron polychloride floculant, it is characterized in that thering are following steps:
(1) with aluminium scrap material and technical hydrochloric acid under atmospheric pressure state, put into acid-resistant container reaction, when pH rises to 0.8 ~ 1.3, filter, generate containing aluminum solutions; Described aluminium scrap material is aluminium scrap stock, aluminium bits and the aluminium slag that aluminium produces in the course of processing;
(2) after adding aluminium scrap material that it is dissolved completely in spent pickle liquor, the pH of its solution rises to 1.6 ~ 2.0, generates iron-containing liquor; Described spent pickle liquor is iron and steel pickling waste liquid, and contained free acid is hydrochloric acid, and wherein Fe (II) concentration is 160 ~ 175g/L, and Fe (III) concentration is 15 ~ 20g/L;
(3) iron-containing liquor containing in aluminum solutions and step (2) in step (1) is dropped in anticorrosive reaction vessel in proportion, the pH value that adds alkali adjusting mixed solution is 1.9 ~ 3.0; Described aluminium and the mol ratio of iron are 6 ~ 9:4～1;
(4) temperature of reaction vessel mixed solution is controlled to 65 ~ 85 ℃, low rate mixing, adds oxygenant, reacts 30 ~ 60 minutes, stops heating, and ageing 2 ~ 3 hours, makes aluminium iron polychloride floculant.
2. the method for preparing aluminium iron polychloride floculant according to claim 1, is characterized in that: in above-mentioned steps (1), in aluminium scrap material, aluminium content is 70 ~ 80%.
3. the method for preparing aluminium iron polychloride floculant according to claim 1, is characterized in that: in above-mentioned steps (1), containing Al(III in aluminum solutions) concentration is 70 ~ 100g/L.
4. the method for preparing aluminium iron polychloride floculant according to claim 1, is characterized in that: in above-mentioned steps (4), oxygenant is sodium chlorate, with solid form or solution form, adds.
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| CN103420430B (en) * | 2013-08-16 | 2015-03-25 | 江门市中达环保科技有限公司 | Polyaluminum ferrous chloride purifier and production method thereof |
| CN104649385A (en) * | 2013-11-20 | 2015-05-27 | 重庆市宇洁化工有限公司 | Method for preparing poly-aluminum ferric chloride composite water purifying agent with waste hydrochloric acid |
| 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 |
| CN108275725A (en) * | 2018-02-09 | 2018-07-13 | 无锡日月水处理有限公司 | The method that polyaluminum ferric chloride is prepared using waste |
| CN109851014A (en) * | 2019-02-27 | 2019-06-07 | 临沂长荣环保科技有限公司 | Efficient water-purifying agent and its production technology |
| CN111847613B (en) * | 2020-08-03 | 2022-09-06 | 南京谱瑞环境科技有限公司 | Method for preparing polyaluminum ferric chloride coagulant by using steel pickling waste liquid and aluminum-containing waste material |
| CN112158932B (en) * | 2020-10-13 | 2022-01-18 | 北京化工大学 | Magnetic zero-valent iron polyaluminum chloride composite flocculant and preparation method and application thereof |
| CN113955806B (en) * | 2021-03-12 | 2023-08-01 | 衡阳市建衡实业有限公司 | Production method of polyaluminum ferric chloride |
| GR1010633B (en) * | 2022-12-15 | 2024-02-12 | Νταϊλιανης, Κωνσταντινος Νικολαου | Production of polyaluminum reffic chloride flocculants (pafc) with varying iron, aluminum and chlorine ratios and varying alkalinity by recycling of acidic waste from galvanizing plants and low-value aluminum scrap |
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| CN1463929A (en) * | 2002-06-06 | 2003-12-31 | 曹万印 | Process for producing composite coagulant polymeric aluminium chloride ferrum |
| CN100554177C (en) * | 2007-06-26 | 2009-10-28 | 上海大学 | A kind of preparation method of polymerized ferric-aluminum chloride composite coagulating agent |
| CN102372308B (en) * | 2010-08-12 | 2012-09-19 | 北京万水净水剂有限公司 | Process for producing polymeric aluminum ferric chloride coagulating agent by using pickling waste water containing iron |
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