CN101712506A - Method for reducing hexavalent chromium in water by biological waste - Google Patents
Method for reducing hexavalent chromium in water by biological waste Download PDFInfo
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- CN101712506A CN101712506A CN200810160897A CN200810160897A CN101712506A CN 101712506 A CN101712506 A CN 101712506A CN 200810160897 A CN200810160897 A CN 200810160897A CN 200810160897 A CN200810160897 A CN 200810160897A CN 101712506 A CN101712506 A CN 101712506A
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- 239000002351 wastewater Substances 0.000 claims abstract description 14
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 241000283690 Bos taurus Species 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
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- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for reducing hexavalent chromium in water by biological waste, comprising the following steps: drying and crushing white spirits distillers' grains and beer distillers' grains produced by a brewery for later use; adjusting the pH value of chromate waste water to be acidic by H2SO4; fully mixing the distillers' grains with waster water according to the solid-liquid ratio of 6-10g/L, and processing for 24h at room temperature; filtering to lead the solid to be separated from the liquid; and measuring Cr(VI) content and the total Cr content in filtered water by analyzing a sample. The invention can effectively remove Cr(VI) (being converted into Cr(III) and/or being absorbed) in water, low the total Cr content (being absorbed), achieves the dual purposes of toxicity attenuation and decontamination, and provides a novel Cr(VI) waste water treatment way. The above processing method has the advantages of simple process, convenient operation, environment protection, cheap raw materials and low running cost and easy popularization, and provides a way for the resource recycling of the distilled grains.
Description
Technical field
The present invention relates to chromic method in the discarded biomaterial reduction of a kind of usefulness treating water, the concrete wine-making industry byproduct vinasse of promptly using are removed conversion of the hexavalent chrome reduction in the water and absorption, and the chromate waste water that belongs to environmental protection technical field is handled.
Background technology
In recent years, along with the fast development of industry, water pollutes constantly aggravation, especially contains the industrial wastewater discharge of chromium heavy metals such as (Cr), serious threat ecotope and human health, and therefore, the improvement of high concentration chrome wastewater becomes the important subject that environmental protection educational circles faces.The Cr element extensively is present in occurring in nature, and the common valence state of its compound has trivalent Cr (III) and sexavalence Cr (VI).The natural origin of Cr mainly is rock decay in the environment, the resultant Cr (III) that mostly is greatly; Because the industrial use of Cr is extensive, the three wastes of industries such as metal processing, plating, process hides, printing and dyeing discharging become the main artificial source that Cr pollutes, and then are mainly Cr (VI) in this type of trade effluent and the waste residue dissolution fluid, as chromate ion (CrO
4 2-).Though one of Cr trace element that to be organism essential, if too high levels, it all is deleterious to people and animals and plants.The toxicity of Cr exists valence state relevant with it, usually the toxicity of Cr (VI) is higher 100 times than Cr (III), and easilier be absorption of human body and accumulate carcinogenic in vivo, therefore one of as priority pollutant is all classified Cr in countries in the world, and Cr (VI) concentration also is decided to be the index of water quality monitoring (WQM) and control, as the various quality of water environment of China and hygienic standard and waste water discharge pollutant all strict regulation of limiting the quantity of: should be lower than 0.05mg L in the Drinking Water (GB 3838-2002)
-1Cr (VI); The concentration limit of Cr is 0.1mg L in surface water (GB 3838-2002) and the underground water (GB/T 14848-93)
-1Cr (VI); The highest permission emission concentration (GB 8978-1996) of sewage is 1.5mg L
-1Cr and 0.5mg L
-1Cr (VI); Thereby water technology had higher requirement, especially the removal of Cr (VI) becomes primary and foremost purpose.
At present, mainly contain reduction-precipitator method, active carbon adsorption, electrolytic process, ion exchange method, membrane separation process, microbial method etc. at the treatment process that contains the employing of Cr waste water, what wherein be most widely used is chemical reduction-precipitator method, promptly be converted into behind the Cr (III) Cr (VI) again by adding reductive agent that neutralization (coagulation) is precipitated out, reclaim or harmlessness disposing.Traditional Cr (VI) method of reducing be mainly under the acidic conditions with ferrous, Zero-valent Iron or at a low price reductibility chemical reagent such as sulphur handle (as EnvironmentalScience ﹠amp; Technology, 2005,39 (16): 6321-6327; Chinese patent CN1556048, " chromate waste water treatment process "), make Cr
2O
7 2-, HCrO
4 -, CrO
4 2-Be reduced into the lower Cr of toxicity
3+, but cost is higher usually.Therefore, the Application and Development of novel reductibility material becomes the research emphasis of Cr wastewater treatment, as the existing report of reductive action (Fuel, 2002,81 (5): 691-698 to Cr (VI) such as some mineral, coal, natural biologic material; Environmental Science ﹠amp; Technology, 2004,38 (18): 4860-4864), and this type of material has absorption property usually concurrently.Recently discarded biomaterial is receiving publicity aspect the heavy metal wastewater thereby improvement with characteristics such as its wide material sources, with low cost and environmental friendliness, research (Journal of Hazardous Materials is removed in the existing absorption that non-living body biomaterials such as agriculture byproduct such as wood chip, bark, pericarp, husk are used for heavy metal ion, 2003,100 (1-3): 53-63; Chemical Engineering Journal, 2008,137:529-541), but the reductive action that may follow in the common less concern treating processes, and they are also limited to the loading capacity of Cr (VI).The byproduct of vinasse after as the grain ferment wine brewing, in China bigger annual production is arranged, only distillers ' grains just reaches tens million of tons, though part is processed as feed, still have partly not add and handle directly discharging and cause environmental pollution, be necessary fully to excavate the purposes of this cheapness biomaterial, as the heavy metal ion Cr (VI) in absorption-reducing property treating water of using vinasse, this research does not appear in the newspapers as yet.
Summary of the invention
The objective of the invention is to the sexavalent chrome in discarded biomaterial reduction conversion and the removal water, so that a kind of waste water Cr (VI) treatment process simple to operate, with low cost to be provided.
The method of Cr (VI) promptly is biomaterial with vinasse, thereby removes Cr (VI) by absorption-reduction under condition such as suitable pH in the discarded biomaterial treating water of a kind of usefulness that the present invention proposes, and its step is as follows:
1) vinasse are prepared: the distillers ' grains of brewery's output or brewer's grains, and crushed after being dried is standby;
2) chromate waste water pH regulator: use H
2SO
4It is acid regulating pH;
3) waste water vinasse combination treatment: the solid-to-liquid ratio of pressing 6～10g/L is at room temperature handled 24h with vinasse and waste water thorough mixing;
4) solid-liquid separation: filter;
5) sampling analysis: measure the Cr (VI) and the total cr content that filter in the water of back respectively;
Inventive point of the present invention is directly to remove Cr (VI) in the water with cheap biomaterial (vinasse) by absorption-reduction, and its principle (accompanying drawing) is:
Cr in the water (VI) negatively charged ion may directly contact with the electron donor group on vinasse surface and be reduced and be converted into Cr (III) positively charged ion, also may by with after the positive charge functional group (as amino) of vinasse combines again by contiguous electron donor group reduction, two kinds of mechanism results all impel the Cr (VI) in the water effectively to be transformed (equation is as follows), and total Cr also removes because of portion C r (VI) and/or Cr (III) are adsorbed to some extent by vinasse.
HCrO
4 -+7H
++3e
-＝Cr
3++4H
2O
The present invention compared with prior art has following distinguishing feature and beneficial effect:
Present method is compared with method of chemical treatment, active carbon adsorption, ion exchange method, electrolytic process etc., and treatment process is simple, and is easy to operate, secondary pollution is little, starting material and running cost are cheap, need not buy materials such as expensive chemical reagent, gac, ion exchange resin, are easy to promote.Vinasse are as byproduct of food industry, and wide material sources are used as the cheap raw material treatment of wastes with processes of wastes against one another of the present invention a kind of approach of recycling just with it.Present method can efficiently transform/remove the Cr (VI) in the water, and can reduce total cr content, reaches the dual purpose of falling poison and decontamination, provides a kind of brand-new waste water Cr to handle means.
Description of drawings
Accompanying drawing be among the present invention vinasse to the biology absorption-reduction removal mechanisms at work of Cr (VI).
Embodiment
Embodiment 1～3: test is scent type, 2 kinds of distillers ' grains of Luzhou-flavor (is main raw material with Cereals such as Chinese sorghums) and a kind of brewer's grains (is major ingredient with the Fructus Hordei Germinatus) with vinasse, take from cattle pen mountain, Beijing strong, colourless liquor distilled from sorghum brewery and factory of Yanjing Brewery respectively, vinasse are adopted back postlyophilization, pulverize, and store for future use.100mg L
-1Cr (VI) treatment sewage be with K
2Cr
2O
7Be dissolved in deionized water and prepare, use H
2SO
4Regulate pH to 2.00.In each 50ml polypropylene centrifuge tube, add 0.15g vinasse (be respectively scent type, aromatic Chinese spirit is poor and 3 kinds of brewer's grains), add the 100mg L of 25ml
-1Cr (VI) sewage, mixing shakes up, under room temperature (25 ℃) with 250rpm rpm level rotational oscillation, take out centrifuging behind the 24h, measure and handle Cr concentration and pH in the water of back, wherein total Cr measures with ICP-OES, and Cr (VI) concentration is measured with diphenyl carbazide spectrophotometry, both differences are Cr (III) concentration, and pH measures by pH meter with the glass combined electrode.
Test-results (as table): distillers ' grains, brewer's grains all have reductibility and adsorptivity concurrently to Cr (VI), 100mg L
-1Cr (VI) sewage pH be 2 o'clock, after primary treatment, scented distillers ' grains, aromatic Chinese spirit are pickled with grains or in wine, brewer's grains are 27,18,48.4% to total Cr clearance (absorption) respectively, Cr (VI) clearance (change into Cr (III) and/or be adsorbed) is then reached 99.7,92.1,77% respectively, and wherein Cr (VI) concentration after scented distillers ' grains is handled is lower than the 0.5mg L that wastewater discharge standard is allowed
-1
Table 1Cr (VI) sewage (100mg L
-1, pH 2) and through vinasse primary treatment result
Can be through the vinasse secondary or repeatedly handle for Cr (VI) and the still below standard waste water of total Cr, make Cr (VI) reduce conversion fully, the Cr of final residual (III) can be removed to qualified discharge, vinasse harmlessness disposing by absorption method or neutralization precipitation method etc.
Claims (2)
1. one kind directly with chromic method in the cheap discarded biomaterial absorption-reduction treating water, it is characterized in that after the vinasse drying of brewery's output, the pulverizing, and uses H
2SO
4Regulate the pH value for the solid-to-liquid ratio thorough mixing of tart chromate waste water by 6～10g/L, at room temperature handle 24h, filter and make solid-liquid separation, sampling analysis measuring filters Cr (VI) and the total cr content in the water of back.
2. the method for claim 1 is characterized in that vinasse are to be the distillers ' grains of main raw material and to be the brewer's grains (through super-dry, pulverizing) of major ingredient with the barley with Cereals such as Chinese sorghums.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810160897 CN101712506B (en) | 2008-10-08 | 2008-10-08 | Method for reducing hexavalent chromium in water by biological waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810160897 CN101712506B (en) | 2008-10-08 | 2008-10-08 | Method for reducing hexavalent chromium in water by biological waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101712506A true CN101712506A (en) | 2010-05-26 |
| CN101712506B CN101712506B (en) | 2013-02-13 |
Family
ID=42416574
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810160897 Active CN101712506B (en) | 2008-10-08 | 2008-10-08 | Method for reducing hexavalent chromium in water by biological waste |
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| Country | Link |
|---|---|
| CN (1) | CN101712506B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101897282A (en) * | 2010-07-14 | 2010-12-01 | 四川农业大学 | Application of wheat straw in rice chromium pollution treatment and method thereof |
| CN102500331A (en) * | 2011-10-19 | 2012-06-20 | 西南科技大学 | Preparation method of distiller's grain adsorbing material for heavy metal ion adsorption |
| CN103100374A (en) * | 2011-11-10 | 2013-05-15 | 西南科技大学 | Distillers' grains alkali modified adsorption material and preparation process thereof |
| CN103100371A (en) * | 2011-11-10 | 2013-05-15 | 西南科技大学 | Distillers' grains acid modified adsorption material and preparation process thereof |
| CN103230780A (en) * | 2013-04-19 | 2013-08-07 | 湖北工业大学 | Heavy-metal absorbent prepared from vinasse and preparation method for same |
| CN104528930A (en) * | 2015-01-08 | 2015-04-22 | 太原工业学院 | Method for degrading organic chromium in dirt water through microorganism immobilization method |
| CN107456950A (en) * | 2017-09-26 | 2017-12-12 | 四川农业大学 | A kind of preparation of brewex's grains charcoal and its application in lead waste water |
| CN113880288A (en) * | 2020-07-02 | 2022-01-04 | 浙江洁呈新材料科技股份有限公司 | Activated carbon adsorption treatment process for non-woven fabric printing and dyeing wastewater |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263685C (en) * | 2004-01-12 | 2006-07-12 | 东风汽车紧固件有限公司 | Chromium containing waste water treatment method |
| CN1689982A (en) * | 2004-04-28 | 2005-11-02 | 宝山钢铁股份有限公司 | Technique and equipment for treating waste liquor containing high concentration chromium by microorganisms |
| CN100545097C (en) * | 2007-04-12 | 2009-09-30 | 同济大学 | A kind of active sludge microorganism that utilizes is removed chromic method in the sewage |
-
2008
- 2008-10-08 CN CN 200810160897 patent/CN101712506B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101897282A (en) * | 2010-07-14 | 2010-12-01 | 四川农业大学 | Application of wheat straw in rice chromium pollution treatment and method thereof |
| CN102500331A (en) * | 2011-10-19 | 2012-06-20 | 西南科技大学 | Preparation method of distiller's grain adsorbing material for heavy metal ion adsorption |
| CN103100374A (en) * | 2011-11-10 | 2013-05-15 | 西南科技大学 | Distillers' grains alkali modified adsorption material and preparation process thereof |
| CN103100371A (en) * | 2011-11-10 | 2013-05-15 | 西南科技大学 | Distillers' grains acid modified adsorption material and preparation process thereof |
| CN103100371B (en) * | 2011-11-10 | 2015-07-22 | 西南科技大学 | Distillers' grains acid modified adsorption material and preparation process thereof |
| CN103100374B (en) * | 2011-11-10 | 2016-04-13 | 西南科技大学 | Vinasse alkali modification sorbing material and technique |
| CN103230780A (en) * | 2013-04-19 | 2013-08-07 | 湖北工业大学 | Heavy-metal absorbent prepared from vinasse and preparation method for same |
| CN104528930A (en) * | 2015-01-08 | 2015-04-22 | 太原工业学院 | Method for degrading organic chromium in dirt water through microorganism immobilization method |
| CN107456950A (en) * | 2017-09-26 | 2017-12-12 | 四川农业大学 | A kind of preparation of brewex's grains charcoal and its application in lead waste water |
| CN113880288A (en) * | 2020-07-02 | 2022-01-04 | 浙江洁呈新材料科技股份有限公司 | Activated carbon adsorption treatment process for non-woven fabric printing and dyeing wastewater |
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| Publication number | Publication date |
|---|---|
| CN101712506B (en) | 2013-02-13 |
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