CN101519240A - Method for treating wastewater containing Cr(VI) - Google Patents
Method for treating wastewater containing Cr(VI) Download PDFInfo
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- CN101519240A CN101519240A CN200910046504A CN200910046504A CN101519240A CN 101519240 A CN101519240 A CN 101519240A CN 200910046504 A CN200910046504 A CN 200910046504A CN 200910046504 A CN200910046504 A CN 200910046504A CN 101519240 A CN101519240 A CN 101519240A
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- waste water
- ldh
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- aluminate cement
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Abstract
The invention relates to a method for treating wastewater containing Cr(VI), which belongs to the technical field of environmental engineering wastewater treatment. The method comprises the following steps: putting CaCl2, Ca(OH)2 and aluminate cement into the wastewater containing the Cr(VI) according to a weight ratio of 24:31:45; oscillating the mixture for 10 to 15 hours by a water bath oscillator; and separating the solid from the liquid to achieve the aim of removing the Cr(VI). The method leaves out complex solid-liquid separation and drying operation in the LDH synthetic production so that two separated industrial processes of LDH synthesis and wastewater treatment are finished in a system. Because the CaCl2 and the Ca(OH)2 are applied to the process of hydration reaction of Ac-05, an LDH compound with a Ca/Al structure is finally synthesized, and the Cr(VI) pollution in water is removed simultaneously. The method is a technique for controlling water pollution, which adopts low-price materials, has good removing effect, and has great environmental potential.
Description
Technical field
The present invention is the method that a kind of processing contains Cr (VI) waste water, belongs to the environmental engineering technical field of waste water processing.
Background technology
Sexavalent chrome mainly is chronic murder by poisoning to the people, and it can pass through digestive tube, respiratory tract, skin and mucous membrane and invade human body, mainly accumulates in liver, kidney and the incretory gland in vivo.Then easily accumulate in lung by what respiratory tract entered.Sexavalent chrome has strong oxidation, so chronic poisoning often begins to develop into gradually incurable with local lesion.When respiratory tract is invaded human body, begin to encroach on the upper respiratory tract, cause rhinitis, pharyngitis and laryngitis, bronchitis.
Chromium is mainly from ore processing, heavy metal surface treatment, leather tanning, industries such as printing and dyeing; In addition, urban consumption and life aspect and use chemical fertilizer also are may originate to environmental emission chromium.They can enter underground water source by underground pipeline or osmosis.Industrial production such as ferrochrome smelting, refractory materials, plating, process hides, pigment and chemical industry and fuel combustion are discharged, and to contain chromium waste gas, waste water and waste residue etc. all be the pollution of chromium source.
At present, to the normally following several treatment processs of pollution of chromium.
1. chemical method comprises (1) barium salt process (2) reduction precipitation method; 2. absorption method; 3. electrolytic process; 4. ion exchange method; 5. membrane separation process; 6. biochemical process.
The most frequently used chromic method of processing is ferrous reduction method and ion exchange method at present., but cost-effective Cr (VI) method of wastewater treatment and the technology of containing still is worth further research.
Layered double-hydroxide also claims hydrotalcite, anionic clay.Its basic structure formula is:
M2+xM 3+y (OH) 2x+3y-nz (An-) zmH2O, M2+ and M3+ represent divalence and Tricationic respectively, and An-represents n valency negatively charged ion.LDH has the laminate structure of similar water magnesite, and in the structural unit layer of brucite, the divalent cation part is substituted by Tricationic, produces the structure positive charge, enters structural unit interlayer balanced structure positive charge thereby need to introduce negatively charged ion.Similar with general clay mineral, the negatively charged ion and the structure positive charge that are between structural sheet belong to long-range electrostatic balance, reactive force a little less than, negatively charged ion wherein can be by other anionresin, thereby LDH has excellent anionresin performance.LDH has also been carried out more research as water treatment absorbent, demonstrate boundless application prospect, particularly make oxo-anions such as the phosphorous acid group of sorbent treatment, arsenate, selenate radical, chromate and demonstrate effect well, hydrated calcium chloroaluminate (Friedel compound) is exactly a member wherein.The problem that exists mainly is mostly the LDH that the investigator prepares is to finish under strict experiment condition with chemical reagent at present, and turnout is little, and the cost height is difficult in the actual waste water processing and uses.
Since the interlayer structure of LDHs, anionic interchangeability with and memory effect, the potentiality of very large wastewater treatment are arranged.But generally its synthetic method more complicated has coprecipitation method, the sol-gel method ion exchange method, and the pillared method of roasting etc., but the general condition control ratio is strict or consume energy higherly, and scale operation inconvenience or cost are too high.
Summary of the invention
The purpose of this invention is to provide the method that a kind of cheapness, energy consumption is low and technology is easy processing contain Cr (VI) waste water.Present method is at CaCl
2, Ca (OH)
2With the CA in the aluminate cement, when the common aquation of materials such as C2A forms the LDH mineral, reach the effect of removing sexavalence Cr (VI).
The objective of the invention is to be achieved through the following technical solutions.
A kind of processing contains the method for Cr (VI) waste water, it is characterized in that this method has following technological process:
With CaCl
2, Ca (OH)
2With CA50 type aluminate cement be that 24:31:45 takes by weighing powder by mass ratio, Ca (OH)
2Grind and cross 80 mesh sieves respectively with aluminate cement; Is that the ratio of 1:500~1:50 adds and contains in Cr (VI) waste water with these three kinds of powder and waste water in mass ratio, and the Cr element is with CrO in the waste water
4 2-Or Cr
2O
7 2-Form exists, and shakes 10~15 hours in 15~35 ℃ of water-baths, can reach balance, carries out solid-liquid separation, and solid-liquid separation can be filter paper filtering, membrane filtration or separation method such as centrifugal, promptly obtains removing the waste water of Cr (VI) and contains CrO
4 2-LDH, its chemical formula is 3CaOAl
2O
3CaCrO
410H
2O.
Described CA50 type aluminate cement refers to meet GB GB 201-2000, in aluminate cement the Al element with CA that can aquation, C2A, patterns such as C3A exist.
Present method is an instant synthetic in-situ treatment in containing Cr (VI) waste water.This method has been saved complicated solid-liquid separation and drying operation in the synthetic production of LDH, LDH is synthesized with 2 discrete commercial runs of wastewater treatment finish in a system.Utilize CaCl
2, Ca (OH)
2Participating in the hydration reaction process of aluminate cement, make it form this Ca/Al laminate structure class LDH material---the make a return journey middle Cr (VI) that dewaters of hydrated calcium chloroaluminate pollutes.Be a kind of water pollution control technology, and can obtain LDH derived material 3CaO:Al
2O
3: CaCrO
4: 10H
2O.The Ca/Al structure LDH compound main component chemical formula that these three kinds of raw materials at first obtain is 3CaOAl
2O
3CaCl
210H
2O, and then generate 3CaOAl with sexavalent chrome reaction
2O
3CaCrO
410H
2O.
The invention effect: is that the clearance that contains Cr (VI) in Cr (VI) waste water of 10mg/L, 50mg/L is respectively 99% and 90.5% with the dosage (1:500) of 2g/L to starting point concentration.
In the XRD figure spectrum, as can be seen at 3CaOAl
2O
3CaCl
210H
2Form new peak clearly before first characteristic peak of O (31-0245) material, corresponding with card 41-0478 in the PDF2-2004 database of ICCD (diffraction data International Centre), retrieving material chemical formula is 3CaOAl
2O
3CaCrO
410H
2O.Show that synthetic mechanism is exactly that LDH forms and the interlayer constraint is gone in Cr (VI) exchange.
Characteristics of the present invention: the ingenious CaCl that utilizes of the present invention
2, Ca (OH)
2With the characteristic that contains aluminium thing aluminate cement, CaCl
2Provide calcium source and chlorine source, Ca (OH)
2The calcium source is provided and keeps pH, easy synthetic dexterously LDH mineral are also handled containing Cr (VI).And the present invention adopts cheap raw material, and removal effect is good, and very big environmental potential is arranged.
Description of drawings
Fig. 1 processing technological flow figure
Fig. 2 Cr (VI) removes kinetic curve
Solid XRD figure after the instant synthesizing hydrated calcium chloroaluminate processing waste water containing chrome of Fig. 3
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
With CaCl
2, Ca (OH)
2, CA50 type aluminate cement according to quality be respectively 0.024g, 0.031g, 0.045g weighs up, Ca (OH)
2, aluminate cement grinds and crosses 80 mesh sieves.Again this three raw material is added into 50ml by K
2Cr
2O
7The simulation that is configured to contains in Cr (VI) waste water, and wherein configuration concentration is pressed the Cr element and calculated and to be 10mg/L.25 ℃ are carried out taking out behind the water-bath concussion 12h filter paper filtering, the hydrated calcium chloroaluminate that promptly obtains removing the waste water of Cr (VI) and contain Cr in the water bath chader.Filtrate is detected through ICP, and Cr is lower than detection limit (0.1mg/L).The different time effect is seen Fig. 2.
With CaCl
2, Ca (OH)
2, CA50 type aluminate cement according to quality be respectively 0.024g, 0.031g, 0.045g weighs up, Ca (OH)
2, aluminate cement grinds and crosses 80 mesh sieves.Again this three raw material is added into 50ml by K
2Cr
2O
7The simulation that is configured to contains in Cr (VI) waste water, and wherein configuration concentration is pressed the Cr element and calculated and to be 50mg/L.25 ℃ are carried out taking out behind the water-bath concussion 12h filter paper filtering, the hydrated calcium chloroaluminate that promptly obtains removing the waste water of Cr (VI) and contain Cr in the water bath chader.Filtrate is detected through ICP, and Cr is reduced to 6.3mg/L.The different time effect is seen Fig. 2.
Claims (1)
1, a kind of processing contains the method for Cr (VI) waste water, it is characterized in that this method has following technological process:
With CaCl
2, Ca (OH)
2With CA50 type aluminate cement be that 24:31:45 takes by weighing powder by mass ratio, Ca (OH)
2Grind and cross 80 mesh sieves respectively with aluminate cement; Is that the ratio of 1:500~1:50 adds and contains in Cr (VI) waste water with these three kinds of powder and waste water in mass ratio, and the Cr element is with CrO in the waste water
4 2-Or Cr
2O
7 2-Form exists, and shakes 10~15 hours in 15~35 ℃ of water-baths, carries out solid-liquid separation with centrifugal or filter type, the hydrated calcium chloroaluminate that promptly obtains removing the waste water of Cr (VI) and contain Cr.
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CN103649349A (en) * | 2011-05-10 | 2014-03-19 | 凯米罗总公司 | Methods for removing contaminants from aqueous systems |
CN104016436A (en) * | 2014-06-12 | 2014-09-03 | 南昌大学 | Zinc-containing wastewater treatment method |
CN104026125A (en) * | 2014-06-18 | 2014-09-10 | 厦门大学 | Method for synthesizing sustained-release agent by intercalating pesticide into calcium chloroaluminate hydrate |
CN104984725A (en) * | 2015-07-10 | 2015-10-21 | 常州市宏硕电子有限公司 | Hydrated calcium aluminate and preparation method thereof |
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CN103649349B (en) * | 2011-05-10 | 2016-09-07 | 凯米罗总公司 | For the method removing pollutant from water-based system |
CN103649349A (en) * | 2011-05-10 | 2014-03-19 | 凯米罗总公司 | Methods for removing contaminants from aqueous systems |
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CN104016436A (en) * | 2014-06-12 | 2014-09-03 | 南昌大学 | Zinc-containing wastewater treatment method |
CN104026125A (en) * | 2014-06-18 | 2014-09-10 | 厦门大学 | Method for synthesizing sustained-release agent by intercalating pesticide into calcium chloroaluminate hydrate |
CN104984725A (en) * | 2015-07-10 | 2015-10-21 | 常州市宏硕电子有限公司 | Hydrated calcium aluminate and preparation method thereof |
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CN107867768A (en) * | 2017-09-08 | 2018-04-03 | 张适宜 | A kind of stable process for realizing wastewater zero discharge of desulfurization wastewater solidification |
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CN109896563A (en) * | 2019-04-04 | 2019-06-18 | 四川大学 | A kind of high efficiency method for administering the iron-containing acidic waste water that discarded coal mine generates |
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