CN102500325A - Preparation method of adsorption material for hexavalent chromium wastewater treatment - Google Patents
Preparation method of adsorption material for hexavalent chromium wastewater treatment Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for preparing an adsorption material for hexavalent chromium wastewater treatment, which is used for mining and utilizing household garbage to prepare a hexavalent chromium wastewater adsorbent, namely excavating the household garbage (the landfill age is more than 10 years or 15 years) of a landfill to prepare a mineralized garbage adsorption material which is used as the adsorption material for heavy metal wastewater treatment. The stabilized garbage, namely the mineralized garbage, is garbage obtained by long-term humification and stabilization of household garbage in a landfill, 50-60% of organic fine materials can be obtained from each ton of garbage after screening, and the mineralized garbage is a biological medium and an adsorption material with good degradation capability and has the characteristics of small volume weight, high porosity, high organic matter content, large cation exchange capacity, various microorganisms and the like. The mineralized refuse has a good treatment effect on hexavalent chromium removal wastewater, has the advantages of low cost, simplicity in preparation, high yield and the like, is an environment-friendly adsorption material, and achieves double effects of hexavalent chromium removal, waste recycling and the like.
Description
Technical field
The invention belongs to contaminated wastewater control technology field, be specifically related to the sorbing material preparation method that a kind of hexavalent chromium wastewater is handled.
Background technology
Along with developing rapidly of Chinese industrialization and urbanization, some developed regions excess loads to water body discharging high density pollution thing, thereby because water body can't realize that self-cleaning makes water body cause serious pollution.Chromium (Cr) is one of modal heavy metal contaminants of water body, comes from the waste water that plating, process hides, Treatment of Metal Surface and chromate processing are discharged mostly.In water environment, chromium mainly contains two kinds of valence states, Cr (VI) and Cr (III).Compare with Cr (III), Cr (VI) has highly dissoluble, is strong oxidizer and potential carcinogen, mainly with HCrO
4-or Cr
2O
7-wait anion to exist.At present, the chromate waste water processing method mainly comprises reduction back chemical precipitation, ion exchange resin or charcoal absorption, counter-infiltration or electrodialysis etc.Wherein chemical precipitation method mainly is that Cr in the water (VI) is reduced into Cr (III); Regulate the pH value subsequently to neutral, make Cr (III) produce deposition and be able to remove, yet; There are many unfavorable factors in the method, like processing cost height, poor removal effect and a large amount of chromium-bearing sludges of generation.
The absorption method processing waste water containing chrome is one of main method of hexavalent chromium-treatments; Many sorbing materials are studied discovery in succession in the many decades in past; Like kind surplus hazelnut shell, algae, cocoanut shell, banana skin, carbon black, pine tree leaf, grape stalk, wine brewing refuse, the straw etc. 200; These natural biologic materials or trade waste have certain adsorption capacity to Cr (VI), but these materials often generation is less or collect difficulty etc., often can't realize the large scale mining utilization.
Meanwhile, along with China's rapid development of economy, the rapid raising of living standards of the people and the continuous quickening of urbanization process, domestic waste output sharply increases.According to 2007 China Statistical Yearbook data, China's consumer waste innocent disposal amount is 9437.7 ten thousand tons, and keeps the rate increase with annual 10%.At present, existing up to a hundred city life garbage landfills of China and general stockyard have been inserted or the rubbish stacked has up to ten million tons.Follow the raising of Public Environmental Awareness, the appreciation in soil and the reinforcement of national environmental protection; The addressing of sanitary filling field in recent years is more and more difficult; And making an investment in more than 4,000 ten thousand RMB of general landfill yard, and have only 10-15 service life, the landfill yard that has built up is afforested after closing; Can only be as purposes such as greenery patches, parks, land values can't embody.In the face of the thousands of ton house refuses of landfill, domestic temporarily do not have practical ways.
Summary of the invention
The present invention has overcome the deficiency of prior art; The sorbing material preparation method that a kind of hexavalent chromium wastewater is handled has been proposed; Said preparation method exploits utilization to house refuse, is used for preparing the hexavalent chromium wastewater adsorbent, is about to house refuse (landfill age greater than 10 years or the 15 years) excavation of landfill yard; Process the mineralized waste sorbing material, be used for the sorbing material of heavy metal containing wastewater treatment.This stabilisation rubbish is mineralized waste; The house refuse that is landfill yard is through the long-term humification and the rubbish of stabilisation; Rubbish per ton can obtain organic fines of 50%～60% after screening; Be a kind of Biomedia and sorbing material, have that unit weight is less, porosity is high, the content of organic matter is high, cation exchange capacity is big and characteristics such as microbe species is various with good degradation capability.Mineralized waste has good treatment effect to removing hexavalent chromium wastewater, and have cost low, produce simple and advantage such as output is big, be a kind of environmentally friendly sorbing material, reach double effectses such as hexavalent chromium removal and refuse reclamation.
Technical scheme of the present invention is: the sorbing material preparation method that a kind of hexavalent chromium wastewater is handled, and said preparation method utilizes rotary screen and acidified modified pond to prepare sorbing material, and the preparation method is divided into screening and two steps of modification:
1) screening: landfill age is put into rotary screen greater than the mineralized waste in the period of 10 in the excavation household refuse landfill sites, utilizes rotary screen or other types screen cloth to cross the aperture and is the 20-100mm scalping; Remove big foreign material such as stone, after having sieved, carry out natural air drying and handle; The moisture content of control mineralized waste is at 15-40%, and after air-dry, mineralized waste carries out fragmentation; After the 1-2mm dusting cover, the mineralized waste after having sieved is as the mineralized waste sorbing material;
2) modification: in order to improve mineralized waste, it is carried out acidified modified, the last mineralized waste fines that makes of step is inserted acidified modified pond to chromic removal effect; Have hydrochloric acid or sulfuric acid solution in the acidified modified pond, solution usage is advisable with the mineralized waste fines that submerges, and in acidified modified pond, carries out modification; Modification time is 60-90min; Leave standstill the back abandoning supernatant, the room temperature condition air dried is handled, and can obtain sorbing material.
Said sorbing material basic status is: a little aggregate and shot-like particle refer to and can twist into pieces that sand type is strong, does not have peculiar smell, similar soil.
Sorbing material is applicable to the waste water that discharged by hexavalent chromium polluted surface water body or industrial and mining enterprises, and the chromic maximum concentration of removing can reach 25mg/L.
The basic physical property of mineralized waste is: a little aggregate and shot-like particle refer to and can twist into pieces that sand type is stronger, does not have peculiar smell, similar soil.The mineralized waste physicochemical character is as shown in table 1 below.
The basic physicochemical property of table 1 mineralized waste
The present invention can realize the improvement of utilizing again of stabilisation house refuse and heavy metal chromium polluted-water, after treatment as the sorbing material of hexavalent chromium polluted water body, has possessed better adsorption capability and treatment effect.
The present invention has following beneficial effect:
1) the present invention excavated landfill in the landfill yard age greater than the house refuse in 10 years, processed the mineralized waste sorbing material, was used for the sorbing material of heavy metal containing wastewater treatment, turned waste into wealth;
2) material therefor of the present invention is that the house refuse of landfill yard is through the long-term humification and the rubbish of stabilisation; Rubbish per ton can obtain organic fines of 50%～60% after screening; Be a kind of Biomedia and sorbing material, have that unit weight is less, porosity is high, the content of organic matter is high, cation exchange capacity is big and characteristics such as microbe species is various with good degradation capability.Mineralized waste has good treatment effect to removing hexavalent chromium wastewater, and have cost low, produce simple and advantage such as output is big, be a kind of environmentally friendly sorbing material, reach double effectses such as hexavalent chromium removal and refuse reclamation.
3) the present invention can realize the improvement of utilizing again of stabilisation house refuse and heavy metal chromium polluted-water, after treatment as the sorbing material of hexavalent chromium polluted water body, has possessed better adsorption capability and treatment effect.
4) sorbing material that makes of the present invention is applicable to the waste water that discharged by hexavalent chromium polluted surface water body or industrial and mining enterprises, and the chromic maximum concentration of removing can reach 25mg/L.
The specific embodiment
Instance 1: prepare sorbing material required for the present invention with provider's method of the present invention, and use this sorbing material to adopt the Static Adsorption mode to handle the hexavalent chromium of heavy metal wastewater thereby, illustrating respectively aspect different pH values, temperature and the absorption consumption etc. three respectively:
1) to be the prepared mineralized waste sorbing material of 60 these experiments of purpose be respectively 5 with 50mL concentration mixes with the Cr VI solution of 25mg/L with the 5.00g granularity under the condition of different pH; Cr VI solution is regulated the pH value with the hydrochloric acid solution of 0.1mol/L in advance and is respectively 1,2,3,4,5,6,7; Place the vibration of constant temperature shaking table; Adjusting fixedly shaking table temperature is 25 ℃, when hunting speed is 200 ± 5r/min, calculates chromic removal efficient behind the vibration 24h.Mineralized waste to chromic clearance is under the different pH condition: along with the chromic clearance of the increase of pH value reduces gradually.Under low ph condition; Mineralized waste all has good removal effect to the Cr VI of variable concentrations: when hexavalent chromium concentration is 5mg/L; The pH value be 1 and 2 o'clock hexavalent chromium removal rates be respectively 99.91% and 55.63%; When the pH value was 3-7, chromic clearance was between 18.09～26.43%; When hexavalent chromium concentration was 25mg/L, the pH value was that 1 o'clock chromic clearance is also higher, can reach 99.21.
2) in a series of conical flasks, cross 60 purpose mineralized waste 5.000g under the condition of different temperatures respectively; Adding initial hexavalent chromium concentration is the chromium-containing solution 50mL of 10mg/L; Place the vibration of constant temperature shaking table, adjusting fixedly shaking table temperature is divided into 15,25,35 ℃, when hunting speed is 150r/min; Duration of oscillation is 72h, calculates chromic clearance.Different temperatures is removed chromic influence difference to mineralized waste, and temperature is handled chromium-containing solution to mineralized waste and had tangible effect, and its clearance is best when temperature is 25 ℃; Reach 61.60%; When temperature is lower than 25 ℃ when being higher than 25 ℃, clearance obviously reduces, particularly when temperature reaches 35 ℃; Clearance is minimum, is merely 26.87%.This test explanation all can have a negative impact to mineralized waste absorption chromium-containing solution when temperature reduces or raise.
3) in 250ml tool plug glass triangle bottle, add 1.00g, 2.00g, 4.00g, 6.00g, 8.00g, 10.00g mineralized waste respectively under the different amounts condition; Adding 50ml Cr (VI) concentration is the solution of 10mg/L; Place the vibration of constant temperature shaking table; When hunting speed was 200 ± 5r/min, vibration 72h calculated chromic clearance.Hexavalent chromium removal rate under the different mineralized waste consumption conditions is: along with the increase of mineralized waste consumption, chromic clearance is the trend that increases progressively.When the mineralized waste consumption is 4g, when solid-to-liquid ratio was 1: 12.5, chromic clearance was 61.8%, and chromic subsequently clearance increases slowly.When the mineralized waste consumption is 10g, when solid-to-liquid ratio was 1: 5, chromic clearance was 69.7%, and clearance has only increased by 7.9% when being 4g than mineralized waste consumption.See that from economic angle the solid-to-liquid ratio of mineralized waste and Cr VI solution is about 1: 10.
Instance 2: prepare sorbing material required for the present invention with provider's method of the present invention, and use this sorbing material to adopt dynamic suction type to handle the hexavalent chromium of heavy metal wastewater thereby:
Condition control: two kinds of different water intake modes of adverse current and following current are adopted in test; Divide two stages; First stage water inlet hexavalent chromium concentration is 10mg/L, and second stage water inlet hexavalent chromium concentration is 20mg/L, adopts the about 40mm of internal diameter; Highly be the device of the thin footpath of 500mm chromatographic column as reaction bed, mineralized waste reaction bed height is 400mm.Chromatographic column adheres to screen cloth, upwards inserts rubble, fine sand and mineralized waste successively from the chromatographic column bottom, and the effect of inserting rubble and fine sand is as supporting layer.Apparatus hole, chromatographic column top rubber stopper seals, and the lower part outlet place can control with screw switch.Test water all adopts the peristaltic pump water inlet, and water inlet is equipped with water-storage pot.From two stage water outlets of column test hexavalent chromium concentration, the chromic effect of adverse current obviously is better than following current.When the water inlet hexavalent chromium concentration was 10mg/L, the chromic concentration of adverse current water outlet all was lower than detection limit in 36 days, and along with the raising of water inlet hexavalent chromium concentration, the water outlet hexavalent chromium concentration also improves constantly, but adverse current water outlet hexavalent chromium concentration significantly is lower than following current.
The mechanism of mineralized waste adsorbing hexavalent chromium ions:
Chromic adsorption mechanism research mainly is that three aspects such as form of chromium are described respectively after kinetics, adsorption isotherm and the absorption through its adsorption process to the mineralized waste sorbing material to heavy metal:
1) kinetics
Condition control: in a series of 250ml ground triangular flasks; Add 5.00g and remove the back through screening to cross 60 eye mesh screen mineralized wastes be the chromium-containing solution of 10mg/L with the 100ml hexavalent chromium concentration, jump a queue, place the constant temperature shaking table to vibrate; And to regulate the constant temperature oscillator rotating speed be 150r/min, and temperature is 25 ℃.In the different time intervals sampling, behind the centrifugal 10min of 4000r/min, measure hexavalent chromium concentration respectively, calculate adsorbance through supercentrifuge.
Table 2 mineralized waste adsorbing hexavalent chromium kinetics parameter fitting result
*Q
MaxBe maximal absorptive capacity (mg/g); Q
tBe adsorbance (mg/g); T is adsorption time (min);
K is apparent rate of adsorption constant; R is a relative diffusion coefficient; R
2Be relative coefficient.
As shown in table 2, the coefficient R of reaction second-order kinetics equation
2Be 0.9303, be superior to the coefficient R of first _ order kinetics equation
2Be 0.9262, and the Q that calculates via the second-order kinetics equation
eTheoretical value more approaches actual value.This shows that reaction second-order kinetics equation more is applicable to the process of describing the mineralized waste adsorbing hexavalent chromium.
2) adsorption isotherm
Condition control: each 50ml of chromium solution of preparation variable concentrations, added 60 purpose mineralized waste 5.000g, placing vibrates on the shaking table reaches adsorption equilibrium; And regulating the shaking table temperature is 25 ℃; Shaking speed is 150r/min, measures the supernatant hexavalent chromium concentration, calculates chromic adsorbance.Langmuir and Freundlich thermoisopleth fitting result are seen table 3.
Table 3Langmuir and Frendlich equation model parameter
*Langmuir: langmuir's adsorption isotherm model; The sharp uncommon adsorption isotherm line model of Freundlich Freund; Qmax: maximal absorptive capacity (mg/g); B:Langmuir constant (L/mg); K: empirical; N: CI; R2: correlation.
Research through adsorption isotherm shows that this sorbing material is the accords with Langmuir thermoisopleth more, belongs to monolayer absorption, and correlation R2 is 0.985, and maximal absorptive capacity is 0.625mg/g, and constant b is 0.0108.
3) form of mineralized waste absorption back chromium
In order to explain chromic removal mechanism, this part utilizes x-ray photoelectron spectroscopy (XPS) to judge the form that exists of sorbing material surface chromium, and it is main with trivalent chromium mainly that there is form in the chromium on mineralized waste surface.In addition, account for 91.5% of total chromium through chemical determination absorption back mineralized waste surface C r (III) amount, the chromic removal of deducibility act as chromic absorption and reduction thus.
The Main Conclusions of mineralized waste adsorbing hexavalent chromium mechanism research:
(1). the course of reaction of mineralized waste adsorbing hexavalent chromium more meets second-order kinetics, and coefficient R 2 is 0.9303;
(2). adsorption process accords with Langmuir isothermal adsorption equation, coefficient R 2 is 0.985, shows that mineralized waste belongs to monolayer absorption to chromic absorption;
(3). through XPS and chemical method mineralized waste absorption back chromium morphological analysis and solution Cr VI being changed and can find out with total chromium concn, is main with trivalent chromium mainly, can think that thus chromic removal act as chromic absorption and reduction.
Claims (3)
1. the sorbing material preparation method that handles of a hexavalent chromium wastewater, it is characterized in that: said preparation method utilizes rotary screen and acidified modified pond to prepare sorbing material, and the preparation method is divided into screening and two steps of modification:
1) screening: landfill age is put into rotary screen greater than the mineralized waste in the period of 10 in the excavation household refuse landfill sites, utilizes rotary screen or other types screen cloth to cross the aperture and is the 20-100mm scalping; Remove big foreign material such as stone, after having sieved, carry out natural air drying and handle; The moisture content of control mineralized waste is at 15-40%, and after air-dry, mineralized waste carries out fragmentation; After the 1-2mm dusting cover, the mineralized waste after having sieved is as the mineralized waste sorbing material;
2) modification: in order to improve mineralized waste, it is carried out acidified modified, the last mineralized waste fines that makes of step is inserted acidified modified pond to chromic removal effect; Have hydrochloric acid or sulfuric acid solution in the acidified modified pond, solution usage is advisable with the mineralized waste fines that submerges, and in acidified modified pond, carries out modification; Modification time is 60-90min; Leave standstill the back abandoning supernatant, the room temperature condition air dried is handled, and can obtain sorbing material.
2. the sorbing material preparation method that hexavalent chromium wastewater according to claim 1 is handled, it is characterized in that: said sorbing material basic status is: a little aggregate and shot-like particle refer to and can twist into pieces that sand type is strong, does not have peculiar smell.
3. the sorbing material preparation method that hexavalent chromium wastewater according to claim 1 is handled, it is characterized in that: sorbing material is applicable to the waste water that discharged by hexavalent chromium polluted surface water body or industrial and mining enterprises, the chromic maximum concentration of removing can reach 25mg/L.
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Cited By (6)
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| CN102755879A (en) * | 2012-08-13 | 2012-10-31 | 常州大学 | Preparation method of magnetic mineralized refuse for water treatment |
| CN103978025A (en) * | 2013-12-05 | 2014-08-13 | 青岛理工大学 | Landfill method capable of rapidly stabilizing chromium-containing soil and household garbage |
| CN103978024A (en) * | 2013-12-05 | 2014-08-13 | 青岛理工大学 | Landfill method capable of synchronously stabilizing chromium-containing soil and household garbage |
| CN103981875A (en) * | 2013-12-05 | 2014-08-13 | 青岛理工大学 | Landfill method capable of synchronously stabilizing chromium slag and household garbage |
| CN111732155A (en) * | 2020-07-27 | 2020-10-02 | 北京科林威尔环保科技有限责任公司 | Method for removing heavy metals in water by using adsorbing agent Orient Green |
| RU2795001C1 (en) * | 2022-05-04 | 2023-04-27 | Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) | Method for obtaining a composite sorbent |
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