CN103880143A - Process for preparing composite materials for removing arsenic from red mud - Google Patents
Process for preparing composite materials for removing arsenic from red mud Download PDFInfo
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- CN103880143A CN103880143A CN201410140102.3A CN201410140102A CN103880143A CN 103880143 A CN103880143 A CN 103880143A CN 201410140102 A CN201410140102 A CN 201410140102A CN 103880143 A CN103880143 A CN 103880143A
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Abstract
The invention discloses a process for preparing composite materials for removing arsenic from red mud. The process is characterized by comprising the steps of (1) adding the red mud slurry as raw materials to a diluted hydrochloric acid solution, heating to 80 DEG C-90 DEG C, and stirring; (2) after stirring, then cooling the mixture, filtering pickled red mud solids and filtrate, and then washing red mud solids with water; and (3) adding a reducing agent into red mud solids washed with water in step (2), carrying out a reduction reaction, and filtering after the reduction reaction is completed to obtain the obtained composite material for removing arsenic. Since the industrial red mud waste is used as the raw materials, the process disclosed by the method is environment friendly; the convenient preparation process is convenient and rapid and is conducive to large-scale production, and the obtained composite material has an excellent arsenic removal effect.
Description
Technical field
The present invention relates to material engineering field, particularly a kind of technique of utilizing industrial red mud waste residue to prepare arsenic removal matrix material.
Background technology
Arsenic and compound thereof are one of principal pollutant in trade effluent, the reveal any symptoms of arsenic acute poisoning is nauseating for having, vomiting, mouthful in Metallic Flavour, abdomen severe pain, etc., can produce dizziness, sural spasm, cyanosis so that shock compared with severe one, there is nervus centralis paralysis symptom in severe patient, limbs pain spasm, consciousness disappearance etc.
The contaminative waste residue of discharging when red mud is Aluminium industry extraction aluminum oxide, 1 ton of aluminum oxide of the every production of average, 1.0～2.0 tons of red muds of subsidiary generation.China is as large alumina producing state of the world the 4th, and the red mud of annual discharge is up to millions of tons.A large amount of red muds can not fully effectively utilize, and can only rely on large-area stockyard to stack, and has taken a large amount of soils, also environment has been caused to serious pollution.The a large amount of red mud of safe storage has very large challenge.The red mud leakage accident of 10 people's death that causes of Hungary's generation in 2010 has embodied the difficulty of safe handling red mud.It is existing that to utilize red mud to remove the technology of arsenic be to adopt ferric oxide/silicon-dioxide in red mud as matrix material, its working mechanism is mainly that the surface realization of activation red mud is adsorbed arsonium ion, this technology does not relate to the redox reaction of arsonium ion, and adsorption efficiency is not high.And face the arsonium ion risk of desorption again under condition of different pH.
The another kind of technology of removing arsenic is to administer by nano zero valence iron particle, and this technology is mainly to improve the governance efficiency of arsenic by the redox reaction of arsonium ion and Zero-valent Iron.Metallic arsenic or the pentavalent arsenic of oxidation or reduction are deposited on iron particle, have reduced the risk of arsenic desorption.But iron has ferromegnetism, in the situation that there is no carrier, nano iron particles can be assembled, and reduces reaction specific surface area, thereby reduces the governance efficiency of arsenic.In addition in the prior art, need to buy the starting material such as molysite, the preparation cost of nano iron particles is all higher, is unfavorable for its promotion and application in the middle of arsenic removal field.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of technique of utilizing industrial red mud waste residue to prepare arsenic removal matrix material, this technique is take industrial red mud waste residue as raw material, economical environment-protective, preparation technology is convenient and swift, be conducive to scale operation, gained matrix material effect of removing arsenic excellence.
The technique of utilizing red mud to prepare arsenic removal matrix material provided by the invention, is take red mud as raw material, comprises the steps:
(1), get red mud slurry, add hydrochloric acid dilute solution, stir after being warming up to 80 ℃～90 ℃;
(2), mixture is cooling after stirring, obtain red mud solid and the filtrate after pickling by filtrations, then to filtration again after red mud solid washing;
(3), to adding reductive agent in described (2) in the red mud solid of washing, filtration after reduction reaction completes, obtains described arsenic removal matrix material.
Preferably, every 10g red mud slurry is joined the hydrochloric acid that 55-65ml concentration is 1mol/L.
Preferably, described reductive agent is sodium borohydride.
Preferably, the sodium borohydride solution reduction that the solid that every 10g red mud slurry obtains after pickling is 1mol/L by 90-110ml concentration.
The time of preferably, stirring in described step (1) is 30-40 minute.
Preferably, this technique also comprises that the arsenic removal matrix material to obtaining in described step (3) washes, and washing times is 2-4 time.
Preferably, filtrate can be used in described step (2), is extracted metallic aluminium.
The technique of utilizing red mud to prepare arsenic removal matrix material provided by the invention, has following beneficial effect:
(1), the ferric oxide in activation and reduction red mud obtains zero-valent iron particle, the nano zero valence iron particulate load making is to the silicon-dioxide in red mud, avoid nano iron particles in carrier free situation to assemble, in keeping the specific surface area of red mud and nano iron particles, redox reaction by nano zero valence iron particle in arsonium ion and silica supports is to improve the governance efficiency of arsenic, the utilization that makes the each composition in red mud obtain comprehensively, coordinate.
(2), utilize industrial red mud waste residue for raw material, turn waste into wealth, reduce red mud pollute, achieve many things at one stroke.
(3), be rich in the light metal elements such as aluminium in the filtrate of red mud after pickling, can therefrom extract metallic aluminium, make spent pickle liquor obtain recycling, economic environmental protection.
(4) technique quickness and high efficiency, cost is low, is conducive to large-scale production, promotion and application.
Embodiment
In order to make those skilled in the art person understand better technical scheme of the present invention, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Pickling: take out 10 milliliters of 37% hydrochloric acid, add 110 ml distilled waters and be diluted to 3% solution (1 mol/L).Take out 10 grams of red mud slurries, add the hydrochloric acid dilute solution of 60 milliliter 3%, adding distil water to 500 milliliter, is heated to 90 degree, fully stirs after 30 minutes and is cooled to room temperature.By filtering to isolate red mud solid and filtrate.Isolated filtrate picks and places that in the container of 500 milliliters, to be cooled to room temperature stand-by.Distillation washing three times for isolated red mud solid, stand-by after filtering.
Reduction: take out 3.8 grams of sodium borohydrides, add 100 ml distilled waters and be diluted to 38 grams per liter solution (1 mol/L).In the isolated stand-by red mud solid of upper step, add the iron in the sodium borohydride solution reduction solid of 50 milliliter of 1 mol/L.After filtration, isolate solid and liquid, distillation washing three times for isolated solid, obtains the arsenic removal matrix material 5g of nano-sized iron oxide particulate load on silicon-dioxide.
Test example 1. compositions and particle form detect
In embodiment 1, SEM test shows that red mud particle is micron particles, and EDS analyzes and shows that red mud main component is iron, aluminium, silicon, sodium and titanium.After persalt washing, most of aluminium and sodium are separated out red mud, and aluminium manufacturer can reclaim these lyes increases the output of aluminium, and concrete recovery and extracting method are conventionally known to one of skill in the art, in the application, repeat no more.After pickling, the main component of red mud is iron, silicon and titanium.The ferric oxide that sodium borohydride can reduce in red mud is prepared Zero-valent Iron, obtains nano zero valence iron/silicon dioxide composite material.
Test example 2. matrix material arsenic removal tests
Get the clean centrifuge tube of 50 milliliters, add metarsenic acid (NaAsO2) reference liquid of 36 ml distilled waters and 9 milliliters to prepare 35ppm sodium metaarsenate solution.Label is that sample A0 is as standard.
The stand-by arsenic removal matrix material finally obtaining in embodiment 1, add 36 ml distilled waters to obtain in red mud water mixture, add 9 milliliters of sodium metaarsenates (NaAsO2) solution to prepare the mixture of 35ppm sodium metaarsenate solution and arsenic removal matrix material, label is sample A1 again.Sample A0, A1 is put on gyrator and rocks.
Sample A0 gets 3 milliliters, adds the nitric acid of 1 mol/L, surveys arsenious concentration as benchmark with ICP.
After 1 hour, sample A1 is centrifugal, gets 3 milliliters of supernatant liquors, adds the nitric acid of 11 mol/L, surveys arsenious concentration with ICP.Sample A1, with hand even, is put back on gyrator.
After 2 hours, sample A1 is centrifugal, gets 3 milliliters of supernatant liquors, adds the nitric acid of 11 mol/L, surveys arsenious concentration with ICP.Sample A1, with hand even, is put back on gyrator.
After 3 hours, sample A1 is centrifugal, gets 3 milliliters of supernatant liquors, adds the nitric acid of 11 mol/L, surveys arsenious concentration with ICP.
ICP test result sees the following form 1.
Table 1.ICP test result
ICP test has shown arsenic removal matrix material absorption provided by the invention after reduction redox most of trivalent arsenic, exceed 80% arsonium ion in 3 hours by matrix material absorption redox.
Above the technique of utilizing red mud to prepare arsenic removal matrix material provided by the present invention is described in detail.Applied specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand core concept of the present invention.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention.These improvement and modification also should fall in the protection domain of the claims in the present invention.
Claims (7)
1. utilize red mud to prepare the technique of arsenic removal matrix material, it is characterized in that, take red mud as raw material, comprise the steps:
(1), get red mud slurry, add hydrochloric acid dilute solution, stir after being warming up to 80 ℃～90 ℃;
(2), stir after mixture is cooling, obtain red mud solid and the filtrate after pickling by filtration, then red mud solid is washed;
(3), to adding reductive agent in described (2) in the red mud solid of washing, filtration after reduction reaction completes, obtains described arsenic removal matrix material.
2. the technique of utilizing red mud to prepare arsenic removal matrix material according to claim 1, is characterized in that, every 10g red mud slurry is joined the hydrochloric acid that 55-65ml concentration is 1mol/L.
3. the technique of utilizing red mud to prepare arsenic removal matrix material according to claim 1, is characterized in that, described reductive agent is sodium borohydride.
4. the technique of utilizing red mud to prepare arsenic removal matrix material according to claim 3, is characterized in that, the sodium borohydride solution reduction that the solid that every 10g red mud slurry obtains after pickling is 1mol/L by 90-110ml concentration.
5. the technique of utilizing red mud to prepare arsenic removal matrix material according to claim 1, is characterized in that, the time of stirring in described step (1) is 30-40 minute.
6. the technique of utilizing red mud to prepare arsenic removal matrix material according to claim 1, is characterized in that, also comprises that the arsenic removal matrix material to obtaining in described step (3) is washed, and washing times is 2-4 time.
7. the technique of utilizing red mud to prepare arsenic removal matrix material according to claim 1, is characterized in that, filtrate can be used in described step (2) extracted metallic aluminium.
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| CN201410140102.3A CN103880143B (en) | 2014-04-09 | 2014-04-09 | Red mud is utilized to prepare the technique of arsenic removal composite |
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| CN201410140102.3A CN103880143B (en) | 2014-04-09 | 2014-04-09 | Red mud is utilized to prepare the technique of arsenic removal composite |
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| CN103880143B CN103880143B (en) | 2016-01-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108998040A (en) * | 2018-05-28 | 2018-12-14 | 上海环科环境评估咨询有限公司 | Arsenic in soil and pollution of chromium based on organic clay load nanometer iron-series repair medicament |
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| CN1981921A (en) * | 2005-12-14 | 2007-06-20 | 中国科学院生态环境研究中心 | High-activity mud adsorbent and its production |
| CN101176840A (en) * | 2006-11-09 | 2008-05-14 | 中国科学院生态环境研究中心 | Application method of iron modified red mud arsenic-removing adsorption agent |
| CN103464091A (en) * | 2013-10-08 | 2013-12-25 | 武汉科技大学 | Modified bentonite load nanometer iron material and preparation method thereof |
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2014
- 2014-04-09 CN CN201410140102.3A patent/CN103880143B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981921A (en) * | 2005-12-14 | 2007-06-20 | 中国科学院生态环境研究中心 | High-activity mud adsorbent and its production |
| CN101176840A (en) * | 2006-11-09 | 2008-05-14 | 中国科学院生态环境研究中心 | Application method of iron modified red mud arsenic-removing adsorption agent |
| CN103464091A (en) * | 2013-10-08 | 2013-12-25 | 武汉科技大学 | Modified bentonite load nanometer iron material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| YIRAN LI等: "Arsenic removal from aqueous solution using ferrous based red mud sludge", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108998040A (en) * | 2018-05-28 | 2018-12-14 | 上海环科环境评估咨询有限公司 | Arsenic in soil and pollution of chromium based on organic clay load nanometer iron-series repair medicament |
| CN108998040B (en) * | 2018-05-28 | 2020-07-03 | 上海建科环境技术有限公司 | Soil arsenic and chromium pollution remediation agent based on organic clay loaded nano iron system |
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| CN103880143B (en) | 2016-01-06 |
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Inventor after: Zheng Tongli Inventor after: Guo Xiaogang Inventor after: Hao Jinglin Inventor after: Zheng Tonghua Inventor before: Zheng Tonghua |
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Effective date of registration: 20200423 Address after: 073000 No.03, district yg-2, high standard industrial park, North (Dingzhou) renewable resources industrial base, Dingzhou City, Baoding City, Hebei Province Patentee after: Beihong kedingzhou New Material Technology Co.,Ltd. Address before: 100070 Beijing Fengtai District Branch Road No. 7 room 616 Patentee before: NORTH HUAYUAN (BEIJING) TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20230620 Address after: 101300 West Yard of Grain Depot, Yanhe Village, Liqiao Town, Shunyi District, Beijing Patentee after: BEIJING AIWUERDE TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: No. 03, Zone YG-2, Gaobiao Industrial Park, North (Dingzhou) Renewable Resources Industrial Base, Dingzhou, Baoding, Hebei, 073000 Patentee before: Beihong kedingzhou New Material Technology Co.,Ltd. |
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