CN103757419B - A kind of from without the method preparing aluminum benzoate calcium chromium slag - Google Patents
A kind of from without the method preparing aluminum benzoate calcium chromium slag Download PDFInfo
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- CN103757419B CN103757419B CN201310737146.XA CN201310737146A CN103757419B CN 103757419 B CN103757419 B CN 103757419B CN 201310737146 A CN201310737146 A CN 201310737146A CN 103757419 B CN103757419 B CN 103757419B
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- chromium
- slag
- filtrate
- chromium slag
- precipitation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a kind of from without the method preparing aluminum benzoate calcium chromium slag, the method comprises the steps: (1) will be broken without calcium chromium ground-slag; (2) add flooding chromium slag, vat liquor is for subsequent use; (3) by the hexavalent chrome reduction in vat liquor be trivalent chromium precipitation; (4) chromium slag separation of iron, aluminum precipitation after step (2) process; (5) by the precipitate and separate aluminum solutions of step (4); (6) in step (5) gained aluminum solutions, add ammonium benzoate solution, generate aluminum benzoate.The inventive method can by containing chromic chromium slag detoxification, and is converted into by the aluminium contained and can utilizes and the higher another kind of aluminum benzoate of added value, thus turns harm into good, and turns waste into wealth.
Description
Technical field
The invention belongs to chromium slag for comprehensive and utilize technical field, in particular to a kind of from without the method preparing aluminum benzoate calcium chromium slag.
Background technology
Chromic salts is important inorganic salt product, in recent years, China produces the producer of chromic salts under departments of government guides, the technique adopted is through technological transformation, most employing calcium-free roasting technique, although comparatively there is calcium sinter process to decrease chromium slag generation, but its chromium slag produced is still containing the poisonous chromic salts of sexavalence, and main moiety is MgO70 ~ 80%, CaO0.5 ~ 1.0%, Fe
2o
36 ~ 12%, SiO
23 ~ 7%, Al
2o
33 ~ 5%, Cr
2o
30.2 ~ 2%, wherein Cr
6+0.2 ~ 0.5%.Owing to having strong toxicity containing excess water-solubility Cr (VI), therefore chromium slag is one of internationally recognized 47 kinds of refuses the most dangerous, is listed in National Hazard refuse.
At present, the hexavalent chrome reduction of poison high in chromium slag, for the technique of the method for disposal majority employing dry reduction of chromium slag, is the trivalent chromium of low toxicity by chromium salt production producer, then as the additive, steel-making agglutinant etc. of manufacture of cement.But be no matter the additive as manufacture of cement or the agglutinant of steel-making, all need and relevant manufacturers collaborative process, often due to problems such as the transport of chromium slag, adding technology, expenses in treating processes, cause cooperation producer not positive, chromium slag after reduction can not obtain disposal enough in time, thus cause the chromium slag muck storage of chromium salt production producer day by day to increase, the pressure grown with each passing day is caused to environment.
Aluminium benzoate has been widely used at field tools such as medicine, chemical industry, food.The over-all propertieies such as the hardness of polypropylene articles, deflection degree, tensile strength, transparency and crystallized temperature can be improved, nucleator aluminum benzoate is often added in production acrylic resin process, aluminium-organic form is also very large on environmental ecology effects impact, show that there is shift function, detoxification and promotion weathering.Therefore, in chromium residue detoxifying process process, the aluminium contained by it is converted into the higher aluminum benzoate of added value, can not only environmental issue be solved, and be that manufacturer increases economic benefit, comprehensive utilization of resources beyond doubt, energy-saving and cost-reducing good method.
Summary of the invention
In view of without in calcium chromium slag except containing except poisonous sexavalence chromic salts also containing a large amount of elements such as magnesium, iron, aluminium, therefore the object of the invention is to by improving chromium slag detoxification technique, thus provide a kind of from without the method preparing aluminum benzoate calcium chromium slag.The method can by containing chromic chromium slag detoxification, and is converted into by the aluminium contained and can utilizes and the higher another kind of aluminum benzoate of added value, thus turns harm into good, and turns waste into wealth.
In order to realize object of the present invention, contriver is studied by lot of experiments and explores, and finally obtains following technical scheme:
From without the method preparing aluminum benzoate calcium chromium slag, comprise the steps:
(1) 250 ~ 320 orders will be broken to without calcium chromium ground-slag;
(2) add flooding chromium slag 2 ~ 3 times, each water consumption is 2 ~ 5 times of the chromium quantity of slag, merges vat liquor, for subsequent use;
(3) vat liquor of step (2) is heated to 60 ~ 70 DEG C, adds sodium sulfide solution, be trivalent chromium precipitation by hexavalent chrome reduction, its reaction formula is: 8CrO
4 2-+ 6S
2-+ 23H
2o=8Cr (OH)
3↓+3S
2o
3 2-+ 22OH
-, cooling, filters out chromium hydroxide precipitation, and filtrate is retained for subsequent use;
(4) the chromium slag after step (2) process, add water after stirring with concentrated hydrochloric acid or vitriol oil acidifying, the pH value of liquid phase is finally made to reach between 1 ~ 3, the filtrate adjust ph of filtering gained acidizing fluid step (3) reaches between 4 ~ 6, make iron ion, aluminum ion produce red precipitate to separate out, filter gained filtrate with between the filtrate adjust ph of step (3) to 9 ~ 10, continue process chromium according to step (3);
(5) red precipitate of step (4) is got, progressively be added under stirring in 10-30% dilute phosphoric acid solution, and constantly adopt dilute phosphoric acid adjustment to make aqueous pH values remain between 1 ~ 3, the red precipitate added progressively dissolves and after being all converted into white precipitate, stop stirring, leave standstill, filter, obtain tertiary iron phosphate wet feed, filtrate is for subsequent use;
(6) in step (5) gained filtrate, add ammonium benzoate solution, generate aluminum benzoate precipitation, its reaction formula is: 3C
5h
5cOONH
4+ Al
3+=Al (C
5h
5cOO)
3↓+3NH
4+, filter, precipitation is dry, obtains aluminum benzoate.
Compared with prior art, what the present invention relates to has the following advantages and marked improvement without the technique tool preparing aluminum benzoate in calcium chromium slag:
(1) isolated iron and aluminium in chromium slag, former technique does not consider the recycling of iron and aluminium;
(2) aluminium is converted into utilizable aluminum benzoate, is separated with iron, chromium etc.;
(3) aluminum benzoate has higher utility value, increases material recycle simultaneously, realizes energy-saving and cost-reducing and improve effects.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of aluminum benzoate prepared by embodiment, and X-coordinate is " wave number ", and ordinate zou is " transmittance ".
Embodiment
Be below specific embodiments of the invention, technical scheme of the present invention is done to describing further, but protection scope of the present invention be not limited to these embodiments.Every do not deviate from the present invention's design change or equivalent substituting include within protection scope of the present invention.
1,100Kg is crushed to 320 orders without calcium chromium slag (being provided by Hubei Zhenhua Chemical Co., Ltd.).
2, first time was with 300Kg water soaking, stirring 2 hours, filtered; Second time 200Kg water soaking, stirring 2 hours, filter, and merges secondary soak solution.
3, upper step alkalescence soak solution is heated to 60 ~ 70 DEG C, the concentration adding new preparation is 30%(mass percent) sodium sulfide solution, it is trivalent chromium precipitation by hexavalent chrome reduction, until do not produce precipitation, the consumption of 30% sodium sulfide solution is 4.5Kg, cooling, filters out chromium hydroxide precipitation, and filtrate is retained for subsequent use.
4, the chromium slag after step 2 processes, adds 200Kg water, and the instillation 60Kg vitriol oil, makes the pH value of acidizing fluid reach between 1 ~ 2.Filter, filtrate is separately deposited.Filter residue adds 200Kg water again and stirs, and instills the vitriol oil, keeps in touch solution ph between 1 ~ 2, and can maintain 2 hours, and consumption vitriol oil 17Kg, filters.Collect the acidizing fluid that merging two step leaches, the alkaline filtrate obtained by step 3 regulates potential of hydrogen, makes its pH value reach between 3 ~ 4, makes iron ion, aluminum ion produce red precipitate and separates out, filter.Filtrate adds the alkaline filtrate adjust ph of step 3 to 9 ~ 10, continues process chromium according to step 3.
5, the red precipitate of step 4 is got, the concentration being progressively added to stirring is 20%(mass percent) dissolve in phosphoric acid, keep between solution ph to 1 ~ 3, pH value raises then appropriateness and supplements dilute phosphoric acid solution and regulate, add red precipitate all to dissolve, and be converted into white precipitate.After red precipitate all adds, continue to keep between solution ph 1 ~ 3, solution is all colourless, and precipitation all changes white into, and reaction completes, and stops stirring, consumes 20% phosphoric acid solution 67Kg, leave standstill, and completely, filter, obtain tertiary iron phosphate wet feed, filtrate is for subsequent use for precipitation.
6, in the filtrate of upper step, slowly adding concentration is 30%(mass percent) ammonium benzoate solution 237Kg, make aluminum ion and its reaction generate aluminum benzoate and precipitate.Filtration drying obtains aluminum benzoate 77.6Kg.Its infrared spectrum is as accompanying drawing 1.
Claims (1)
1., from without the method preparing aluminum benzoate calcium chromium slag, comprise the steps:
(1) 250 ~ 320 orders will be broken to without calcium chromium ground-slag;
(2) add flooding chromium slag 2 ~ 3 times, each water consumption is 2 ~ 5 times of the chromium quantity of slag, merges vat liquor, for subsequent use;
(3) vat liquor of step (2) being heated to 60 ~ 70 DEG C, adding sodium sulfide solution, is trivalent chromium precipitation by hexavalent chrome reduction, cooling, and filter out precipitation, filtrate is for subsequent use;
(4) the chromium slag after step (2) process, add water after stirring with concentrated hydrochloric acid or vitriol oil acidifying, the pH value of liquid phase is finally made to reach between 1 ~ 3, the filtrate adjust ph of filtering gained acidizing fluid step (3) reaches between 4 ~ 6, make iron ion, aluminum ion produce red precipitate to separate out, filter gained filtrate with between the filtrate adjust ph of step (3) to 9 ~ 10, continue process chromium according to step (3);
(5) red precipitate of step (4) is got, progressively be added under stirring in 10%-30% dilute phosphoric acid solution, and constantly adopt dilute phosphoric acid adjustment to make aqueous pH values remain between 1 ~ 3, the red precipitate added progressively dissolves and after being all converted into white precipitate, leave standstill, filter, obtain tertiary iron phosphate wet feed, filtrate is for subsequent use;
(6) in step (5) gained filtrate, add ammonium benzoate solution, generate precipitation, filter, precipitation is dry, obtains aluminum benzoate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310737146.XA CN103757419B (en) | 2013-12-30 | 2013-12-30 | A kind of from without the method preparing aluminum benzoate calcium chromium slag |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310737146.XA CN103757419B (en) | 2013-12-30 | 2013-12-30 | A kind of from without the method preparing aluminum benzoate calcium chromium slag |
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|---|---|
| CN103757419A CN103757419A (en) | 2014-04-30 |
| CN103757419B true CN103757419B (en) | 2015-12-09 |
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| CN201310737146.XA Expired - Fee Related CN103757419B (en) | 2013-12-30 | 2013-12-30 | A kind of from without the method preparing aluminum benzoate calcium chromium slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107201447B (en) * | 2017-06-19 | 2018-12-04 | 江西理工大学 | A method of complex-precipitation separates ferrochrome from electroplating sludge leachate |
| CN109449426B (en) * | 2018-11-29 | 2021-09-21 | 华南理工大学 | Method for preparing lithium ion battery cathode material by using chromium slag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105628A (en) * | 1985-07-06 | 1987-01-14 | 莫玉裔 | The nontoxic processing extraction Ca. and Mg of chromium slag reduction method |
| CN101816829A (en) * | 2010-04-09 | 2010-09-01 | 河南金谷环保工程设备有限公司 | Chromium residue detoxifying process |
| CN102249316A (en) * | 2010-12-21 | 2011-11-23 | 王嘉兴 | Method for preparing chromium hydroxide and co-producing iron chloride and calcium, magnesium and aluminum mixed hydroxide by using chromium residues |
| CN102965506A (en) * | 2012-12-14 | 2013-03-13 | 葛新芳 | Method for removing aluminum from rare earth solution by benzoate precipitation method |
| CN103232068A (en) * | 2012-05-19 | 2013-08-07 | 唐翔 | Recycling and reutilization process for treating chromium slag and wastewater |
-
2013
- 2013-12-30 CN CN201310737146.XA patent/CN103757419B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105628A (en) * | 1985-07-06 | 1987-01-14 | 莫玉裔 | The nontoxic processing extraction Ca. and Mg of chromium slag reduction method |
| CN101816829A (en) * | 2010-04-09 | 2010-09-01 | 河南金谷环保工程设备有限公司 | Chromium residue detoxifying process |
| CN102249316A (en) * | 2010-12-21 | 2011-11-23 | 王嘉兴 | Method for preparing chromium hydroxide and co-producing iron chloride and calcium, magnesium and aluminum mixed hydroxide by using chromium residues |
| CN103232068A (en) * | 2012-05-19 | 2013-08-07 | 唐翔 | Recycling and reutilization process for treating chromium slag and wastewater |
| CN102965506A (en) * | 2012-12-14 | 2013-03-13 | 葛新芳 | Method for removing aluminum from rare earth solution by benzoate precipitation method |
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| CN103757419A (en) | 2014-04-30 |
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