CN105668681A - Method for adsorbing and removing arsenic and hexavalent chromium in water by using modified shaddock peel - Google Patents
Method for adsorbing and removing arsenic and hexavalent chromium in water by using modified shaddock peel Download PDFInfo
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- CN105668681A CN105668681A CN201610047579.6A CN201610047579A CN105668681A CN 105668681 A CN105668681 A CN 105668681A CN 201610047579 A CN201610047579 A CN 201610047579A CN 105668681 A CN105668681 A CN 105668681A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for adsorbing and removing arsenic and hexavalent chromium in water by using modified shaddock peel.The method comprises: washing shaddock peel, drying for 2-6 hours at 85-105 DEG C, and crushing to obtain powder 20-60 in mesh; weighing the shaddock powder and ferric chloride according to a weight ratio of (10-100):1, adding clear water to fully dissolve the ferric chloride, adding the shaddock peel powder into ferric chloride solution, stirring for uniform mixing, drying mixed suspension at 85-105 DEG C for 20-24 h and then cooling, and grinding to obtain powder 20-60 in mesh that is modified shaddock peel powder; adding the modified shaddock peel powder into water containing arsenic or hexavalent chromium, stirring at room temperature, and filtering or centrifugally separating to remove the arsenic and the hexavalent chromium in water.By modifying the shaddock peel, the ability of the shaddock peel to adsorb the arsenic and the hexavalent chromium in the water is improved.
Description
Technical field
The invention belongs to water treatment and water-purifying material technical field, it relates to sexavalent chrome in a kind of modification shaddock skin Adsorption water and the method for arsenic.
Background technology
Chromate waste water is mainly derived from the waste water of chromium plating, plating, process hides, mining, dyestuff and pigment, iron and steel manufacture, tinned pre-industry and the discharge of other industrial production, chromium in waste water mainly exists with the form of trivalent chromium and sexavalent chrome, wherein sexavalent chrome is big to human body toxic action, and its toxicity ratio trivalent chromium exceeds more than 100 times. The method administering chromate waste water at present mainly contains physics, materialization, chemistry, biological method, ion-exchange, membrane sepn, photo catalytic reduction, electrochemistry cohesion etc. The main source that water body arsenic pollutes is: mineral exploitation, the use of agricultural chemicals, non-ferrous metal metallurgy, the fossil oil such as coal and oil the arsenic-containing waste water etc. of burning and exhausting, arsenic also can be used as wood preservative, prepares for dyestuff, pigment, paint industry, glass. The compound of arsenic is all toxic, it is possible to by breathing, skin contact and digestive tube are at people's cylinder accumulation, causing acute or chronic poisoning, long-term drinking is subject to the water that arsenic pollutes, and arsenic will cause arseniasis at people's body accumulation, HUMAN HEALTH is affected, seriously can cause skin carcinoma and lung cancer.
In removal water conventional at present, the method for arsenic has coagulation and filtration method, chemical precipitation method, ion exchange method, membrane separation process, absorption method etc. China is decided to be first kind pollutent chromium and arsenic, and according to China " integrated wastewater discharge standard " (GB8978-2002) regulation, in discharge of wastewater, the maximum permissible concentration of sexavalent chrome is 0.5mg/L, and the maximum permissible concentration of total arsenic is 0.5mg/L.
Absorption method is the one in physics, physico-chemical process, and it is simple that it has equipment, the features such as easy to operate, working cost is low. Wherein it is processed into sorbing material with biomass waste and becomes one of research focus, agro-ecology waste is such as utilized to make low cost, sustainable sorbent material, for water and wastewater treatment, comprise the heavy metal in adsorption treatment waste water, organic pollutant, dyestuff etc. For heavy metal ion, the functional group existed in agricultural wastes biomass, i.e. kharophen, alcohol, carbonyl, phenol, amino, sulfydryls etc. form metal complexes with heavy metal ion or inner complex has substantial connection, the mechanism of adsorption process comprises chemisorption, complexing, surface adsorption, through hole diffusion and ion-exchange etc. The wherein studied sexavalent chrome being used for processing in water of the pericarp of some fruit such as pomegranate rind, Pericarpium Musae and orange peel, the studied arsenic being used in Adsorption water such as cassava skin, green tea slag and rice husk.
Shaddock is the common fruit of south China, and shaddock micromicro is so that about accounting for the half of shaddock total quality, shaddock skin inside is white batt layer, middle containing a large amount of Mierocrystalline celluloses.Usual shaddock skin is not utilized and abandons, and has both caused waste, again contaminate environment. The polymkeric substance that fresh grapefruit skin contains has natural exchange capacity and absorption characteristic such as Mierocrystalline cellulose, hemicellulose, pectin, lignin and protein, shaddock skin carries out wastewater treatment as the typical biomass waste of one is also studied owing to making biomass adsorbent, as removed Pb in water2+, Cu2+, Cd2+, Ni2+, methylene blue, dihydroxyphenyl propane, oil pollution etc. Therefore, shaddock skin this kind of biomass waste can be carried out recycling, develop the frontier of sexavalent chrome and arsenic in its Adsorption water.
Summary of the invention
It is an object of the invention to provide the method for the sexavalent chrome in a kind of modification shaddock skin Adsorption water and arsenic, shaddock skin is carried out modification, it is to increase sexavalent chrome in shaddock skin Adsorption water and the ability of arsenic.
The technical solution adopted in the present invention is, sexavalent chrome in a kind of modification shaddock skin Adsorption water and the method for arsenic, specifically carry out according to following step:
Step 1, cleans fresh grapefruit skin, naturally cools to room temperature, then pulverized into 20 order～60 object powder bodies, obtain shaddock peel powder at the temperature of 85 DEG C～105 DEG C after drying 2 hours～6 hours;
Step 2, it is (10～100) in mass ratio by the shaddock peel powder of step 1 gained and iron(ic) chloride: the ratio of 1 takes, first adding clear water makes iron(ic) chloride dissolve completely, shaddock peel powder is added again in ferric chloride Solution, stirring taking stirring velocity as the speed of 120 revs/min～200 revs/min makes it mix in 10 minutes～20 minutes, room temperature is naturally cooled to after being dried 20 hours～24 hours at the temperature of 85 DEG C～105 DEG C by this mix suspending thing, then worn into 20 order～60 object powder bodies, obtained modification shaddock peel powder;
Step 3, adds the modification shaddock peel powder of step 2 gained in the water containing sexavalent chrome or arsenic, at room temperature stirs 30 minutes～60 minutes with the speed of 120 revs/min～200 revs/min, then filters or centrifugation, namely removes the sexavalent chrome in water and arsenic.
The feature of the present invention is also, in further described step 2, in iron(ic) chloride, iron trichloride massfraction is 95%～99%.
Further, in described step 3, according to 601～655g modification shaddock peel powder join 0.3～1 ton, sexavalent chrome or arsenic concentration be 5～30mg/L water in.
Further, in described step 1, after drying 3 hours at the temperature of 100 DEG C, naturally cool to room temperature.
Further, in described step 2, shaddock peel powder and iron(ic) chloride are in mass ratio for the ratio of 20:1 takes.
Further, in described step 2, stir taking stirring velocity as the speed of 150 revs/min and make it mix in 15 minutes, after being dried 23 hours at the temperature of 90 DEG C by this mix suspending thing, naturally cool to room temperature.
Further, in described step 3, at room temperature stir 40 minutes with the speed of 180 revs/min.
The useful effect of the present invention:
1. fresh grapefruit skin is cleaned, and dries 2 hours～6 hours, naturally cool to room temperature, then pulverized into 20 order～60 object powder bodies, obtain shaddock peel powder at the temperature of 85 DEG C～105 DEG C. This technology feature is adopted to be that shaddock skin is carried out physically modified, form a large amount of fine duct, increase the specific surface area of shaddock skin, remove the outside moisture that fresh grapefruit skin contains, but remain the composition that Mierocrystalline cellulose, hemicellulose, pectin, xylogen and the protein etc. that shaddock skin contains have natural exchange capacity and absorption characteristic, solution is had strong magnetism by the free hydroxyl group in such as Mierocrystalline cellulose, the structure of xylogen also exists many polar groups such as hydroxyl, makes shaddock peel powder possess certain absorption property.
2. the iron(ic) chloride being 95%～99% by shaddock peel powder and iron trichloride massfraction is (10～100) in mass ratio: the ratio of 1 takes, first adding appropriate clear water makes iron(ic) chloride dissolve completely, shaddock peel powder is added again in ferric chloride Solution, stirring taking stirring velocity as the speed of 120 revs/min～200 revs/min makes it mix in 10 minutes～20 minutes, room temperature is naturally cooled to after being dried 20 hours～24 hours at the temperature of 85 DEG C～105 DEG C by this mix suspending thing, then 20 order～60 object powder bodies are worn into, obtain modification shaddock peel powder, this technology feature is that shaddock peel powder is carried out chemical modification further, the Adsorption ability of sexavalent chrome in water and arsenic is greatly improved by modification shaddock skin. this is because iron(ic) chloride has certain oxidisability and corrodibility, certain reaction can be there is in it with the reducing substances in shaddock skin, and the hemicellulose in shaddock skin dissolves in acid, easily degrade in acid condition, xylogen has condensation reaction in acid condition, and this makes, and the fine duct of modified shaddock peel powder is more and fine uniform more. and Fe3+Ion and Cl-Ion attracted to shaddock epidermis face, is evenly coated on shaddock epidermis face. It is coated on the Fe in shaddock epidermis face3+The K that ion and shaddock skin contain itself+Ions etc. all can participate in absorption reaction, creates precipitated metal thing and electrostatic adsorption with the sexavalent chrome in water and arsenic.
Herein, the iron trichloride of more than 99% purity is too expensive, is not suitable for practical application in industry, and the iron trichloride of less than 95% purity may bring other too many impurity into, and especially detrimental impurity causes modification shaddock skin to be polluted.
Shaddock peel powder: iron(ic) chloride mass ratio=(10～100): the useful effect of 1 is: if iron(ic) chloride ratio is too low, modified adsorption effect increases not obvious, and the waste water of process same concentrations to be used a large amount of shaddock skins just can reach and process effect preferably; If iron(ic) chloride ratio is too high, relative cost will improve greatly, is not suitable for practical application in industry.
Owing to be prepared ferric chloride Solution according to actual proportioning and to carry out mix and blend, to form uniform mix suspending thing, the amount of this mix suspending thing has to be had less more, the effect dried 20 hours～24 hours at the temperature of 85 DEG C～105 DEG C dries this mix suspending thing to ensure, to obtain the good shaddock skin of coated even modification further.
3. modification shaddock peel powder is added in the water containing sexavalent chrome and arsenic, at room temperature stir 30 minutes～60 minutes with the speed of 120 revs/min～200 revs/min, then filtering or centrifugation, after process, in water outlet, the index of sexavalent chrome and total arsenic can meet the requirement of " integrated wastewater discharge standard " (GB8978-2002). This technology feature is applied the method for the sexavalent chrome in modification shaddock skin Adsorption water and arsenic, and ferric chloride in aqueous solution acidity is very strong, therefore when modification shaddock skin drops into after in the waste water containing sexavalent chrome and arsenic, due to Fe3+Intense hydrolysis reaction, produce a large amount of H+, can automatically regulate waste water ph, it is possible to the pH value of waste water remained in 2～4.5 so narrower scopes, be conducive to the sexavalent chrome in Adsorption water and arsenic. Because there is CrO containing in the waste water of sexavalent chrome4 2-And Cr2O7 2-Mutual conversion, Cr in water under acidic conditions6+Main with Cr2O7 2-Form exists, and particle number is less, and Cr2O7 2-There is oxidisability, by modification shaddock skin has the radical oxidation of reductibility, can therefore improve Cr6+Clearance.In water hydroxyl then with Fe3+In conjunction with, arsonium ion is then by FeOH and FeOH2+Group is attracted to shaddock epidermis face. And iron(ic) chloride itself is a kind of water treatment flocculant, the partial oxidation iron being therefore coated on modification shaddock skin can play certain throwing out, produces flocculation and co-precipitation with the hexavalent chromium in water and arsonium ion, removes sexavalent chrome and arsenic in water further.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
1000g fresh grapefruit skin is cleaned, naturally cools to room temperature after drying 2 hours at the temperature of 105 DEG C, then pulverized into 20 object powder bodies, obtain 600g shaddock peel powder;
Getting 60g iron trichloride massfraction is the iron(ic) chloride of 95%, first adding appropriate clear water makes iron(ic) chloride dissolve completely, again shaddock peel powder 600g is added in ferric chloride Solution, stirring taking stirring velocity as 120 revs/min of speed makes it mix in 20 minutes, room temperature is naturally cooled to after being dried 20 hours at the temperature of 105 DEG C by this mix suspending thing, then worn into 20 object powder bodies, obtained modification shaddock peel powder 655g.
Modification shaddock peel powder 655g adds 1 ton containing (or containing in water of 30mg/L arsenic) in the water of 30mg/L sexavalent chrome, at room temperature stir 30 minutes with the speed of 200 revs/min, then filtering or centrifugation, after process, in water outlet, the index of sexavalent chrome and total arsenic can meet the requirement of " integrated wastewater discharge standard " (GB8978-2002).
Embodiment 2:
1000g fresh grapefruit skin is cleaned, naturally cools to room temperature after drying 3 hours at the temperature of 100 DEG C, then pulverized into 30 object powder bodies, obtain 600g shaddock peel powder;
Taking 30g iron trichloride massfraction is the iron(ic) chloride of 96%, first adding appropriate clear water makes iron(ic) chloride dissolve completely, again shaddock peel powder 600g is added in ferric chloride Solution, stirring taking stirring velocity as 150 revs/min of speed makes it mix in 15 minutes, room temperature is naturally cooled to after being dried 23 hours at the temperature of 90 DEG C by this mix suspending thing, then worn into 30 object powder bodies, obtained modification shaddock peel powder 625g.
Modification shaddock peel powder 625g adds 0.6 ton containing (or containing in water of 25mg/L arsenic) in the water of 25mg/L sexavalent chrome, at room temperature stir 40 minutes with the speed of 180 revs/min, then filtering or centrifugation, after process, in water outlet, the index of sexavalent chrome and total arsenic can meet the requirement of " integrated wastewater discharge standard " (GB8978-2002).
Embodiment 3:
1000g fresh grapefruit skin is cleaned, naturally cools to room temperature after drying 4 hours at the temperature of 95 DEG C, then pulverized into 40 object powder bodies, obtain 600g shaddock peel powder;
Getting 20g iron trichloride massfraction is the iron(ic) chloride of 97%, first adding appropriate clear water makes iron(ic) chloride dissolve completely, again shaddock peel powder 600g is added in ferric chloride Solution, stirring taking stirring velocity as 150 revs/min of speed makes it mix in 15 minutes, room temperature is naturally cooled to after being dried 22 hours at the temperature of 95 DEG C by this mix suspending thing, then worn into 40 object powder bodies, obtained modification shaddock peel powder 615g.
Modification shaddock peel powder 615g adds 0.5 ton containing (or containing in water of 20mg/L arsenic) in the water of 20mg/L sexavalent chrome, at room temperature stir 50 minutes with the speed of 150 revs/min, then filtering or centrifugation, after process, in water outlet, the index of sexavalent chrome and total arsenic can meet the requirement of " integrated wastewater discharge standard " (GB8978-2002).
Embodiment 4:
1000g fresh grapefruit skin is cleaned, naturally cools to room temperature after drying 5 hours at the temperature of 90 DEG C, then pulverized into 50 object powder bodies, obtain 600g shaddock peel powder;
Taking 12g iron trichloride massfraction is the iron(ic) chloride of 98%, first adding appropriate clear water makes iron(ic) chloride dissolve completely, again shaddock peel powder 600g is added in ferric chloride Solution, stirring taking stirring velocity as 200 revs/min of speed makes it mix in 10 minutes, room temperature is naturally cooled to after being dried 23 hours at the temperature of 90 DEG C by this mix suspending thing, then worn into 50 object powder bodies, obtained modification shaddock peel powder 607g.
Modification shaddock peel powder 607g adds 0.4 ton containing (or containing in water of 10mg/L arsenic) in the water of 10mg/L sexavalent chrome, at room temperature stir 60 minutes with the speed of 120 revs/min, then filtering or centrifugation, after process, in water outlet, the index of sexavalent chrome and total arsenic can meet the requirement of " integrated wastewater discharge standard " (GB8978-2002).
Embodiment 5:
1000g fresh grapefruit skin is cleaned, naturally cools to room temperature after drying 6 hours at the temperature of 85 DEG C, then pulverized into 60 object powder bodies, obtain 600g shaddock peel powder;
Taking 6g iron trichloride massfraction is the iron(ic) chloride of 99%, first adding appropriate clear water makes iron(ic) chloride dissolve completely, again shaddock peel powder 600g is added in ferric chloride Solution, stirring taking stirring velocity as 150 revs/min of speed makes it mix in 15 minutes, room temperature is naturally cooled to after being dried 24 hours at the temperature of 85 DEG C by this mix suspending thing, then worn into 60 object powder bodies, obtained modification shaddock peel powder 601g.
Modification shaddock peel powder 601g adds 0.3t containing (or containing in water of 5mg/L arsenic) in the water of 5mg/L sexavalent chrome, at room temperature stir 60 minutes with the speed of 120 revs/min, then filtering or centrifugation, after process, in water outlet, the index of sexavalent chrome and total arsenic can meet the requirement of " integrated wastewater discharge standard " (GB8978-2002).
Claims (7)
1. the method for the sexavalent chrome in a modification shaddock skin Adsorption water and arsenic, it is characterised in that, specifically carry out according to following step:
Step 1, cleans fresh grapefruit skin, naturally cools to room temperature, then pulverized into 20 order～60 object powder bodies, obtain shaddock peel powder at the temperature of 85 DEG C～105 DEG C after drying 2 hours～6 hours;
Step 2, it is (10～100) in mass ratio by the shaddock peel powder of step 1 gained and iron(ic) chloride: the ratio of 1 takes, first adding clear water makes iron(ic) chloride dissolve completely, shaddock peel powder is added again in ferric chloride Solution, stirring taking stirring velocity as the speed of 120 revs/min～200 revs/min makes it mix in 10 minutes～20 minutes, room temperature is naturally cooled to after being dried 20 hours～24 hours at the temperature of 85 DEG C～105 DEG C by this mix suspending thing, then worn into 20 order～60 object powder bodies, obtained modification shaddock peel powder;
Step 3, adds the modification shaddock peel powder of step 2 gained in the water containing sexavalent chrome or arsenic, at room temperature stirs 30 minutes～60 minutes with the speed of 120 revs/min～200 revs/min, then filters or centrifugation, namely removes the sexavalent chrome in water and arsenic.
2. the method for the sexavalent chrome in a kind of modification shaddock skin Adsorption water according to claim 1 and arsenic, it is characterised in that, in described step 2, in iron(ic) chloride, iron trichloride massfraction is 95%～99%.
3. the method for the sexavalent chrome in a kind of modification shaddock skin Adsorption water according to claim 1 and arsenic, it is characterized in that, in described step 3, according to 601～655g modification shaddock peel powder join 0.3～1 ton, sexavalent chrome or arsenic concentration be 5～30mg/L water in.
4. the method for the sexavalent chrome in a kind of modification shaddock skin Adsorption water according to claim 1 and arsenic, it is characterised in that, in described step 1, after drying 3 hours at the temperature of 100 DEG C, naturally cool to room temperature.
5. the method for the sexavalent chrome in a kind of modification shaddock skin Adsorption water according to claim 1 and arsenic, it is characterised in that, in described step 2, shaddock peel powder and iron(ic) chloride are in mass ratio for the ratio of 20:1 takes.
6. the method for the sexavalent chrome in a kind of modification shaddock skin Adsorption water according to claim 1 and arsenic, it is characterized in that, in described step 2, stirring taking stirring velocity as the speed of 150 revs/min makes it mix in 15 minutes, naturally cools to room temperature after being dried 23 hours by this mix suspending thing at the temperature of 90 DEG C.
7. the method for the sexavalent chrome in a kind of modification shaddock skin Adsorption water according to claim 1 and arsenic, it is characterised in that, in described step 3, at room temperature stir 40 minutes with the speed of 180 revs/min.
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| CN107321311A (en) * | 2017-08-22 | 2017-11-07 | 河海大学 | A kind of phosphoric acid activation pomelo peel matrix activated carbon adsorbent and its preparation and application |
| CN107898762A (en) * | 2017-11-21 | 2018-04-13 | 闽南师范大学 | A kind of shaddock ped cellulose tablet and preparation method thereof |
| CN108529711A (en) * | 2018-04-25 | 2018-09-14 | 温州正城建设有限公司 | A kind of buried town squares rain water collecting system |
| CN109650665A (en) * | 2019-01-24 | 2019-04-19 | 温州立胜建设有限公司 | A kind of energy-saving and emission-reducing town sewage treatment system |
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| CN107898762A (en) * | 2017-11-21 | 2018-04-13 | 闽南师范大学 | A kind of shaddock ped cellulose tablet and preparation method thereof |
| CN107898762B (en) * | 2017-11-21 | 2020-06-09 | 闽南师范大学 | Shaddock peel cellulose tablet and preparation method thereof |
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