CN104556290B - A kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung - Google Patents
A kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung Download PDFInfo
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
A kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung, it comprises the following steps, the 4th charing particle is obtained in first step to the 4th step, in 5th step, the potential of hydrogen of copper-containing wastewater is adjusted to 8, by the poly-p-tert-butylphenol disulphide that the mass ratio adding 50 grams in 1 liter of copper-containing wastewater is 1:2:4, Iron sulfuret and sodium pyrosulfate, stir after 1 hour, the potential of hydrogen of copper-containing wastewater is adjusted to 6.5, be 1:4 polyoxyethylenated alcohol sodium sulfate and clorox mixture by the mass ratio adding 50 grams in 1 liter of copper-containing wastewater, stir and filter after 2 hours, then the potential of hydrogen of copper-containing wastewater is adjusted to 4-6, add 25 grams of described 4th charing particles by 1 liter of copper-containing wastewater in waste water after process and stir 8 hours with the stir speed (S.S.) of 120 turns of per minutes.
Description
Technical field
The invention belongs to copper-containing wastewater purification treatment technology field, particularly a kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung.
Background technology
Along with the development of metallurgical industry and electronic industry, create the ammonia etching wastewater of a large amount of copper powder washing waste water, electroplating wastewater and printed circuit board (PCB) production process, these copper-containing wastewaters have higher economic worth, but have harm to people and environment.Correlative study shows, as the beneficial element that life is necessary, the toxicity of copper own is less, but after human body inhales the excessive copper of people, will stimulate digestion system, causing stomachache vomiting, excessively for a long time causes liver cirrhosis.Copper is also comparatively large to unicellular lower eukaryote and farm crop toxicity, uses copper-containing wastewater irrigated farmland, will make crop damage, greatly affect the growth of farm crop.Organism can make cupric ion enrichment, and it is converted into the larger heavy metal organic compounds of toxicity, enters human body easily via water system.Because avidity that in copper and human body, some is organized is large especially, in conjunction with after can the activity of inhibitory enzyme, thus to human body generation toxic action.So copper-containing wastewater is before discharging if recycling then not only can solve the pollution problem of copper to environment, and economize on resources, there is certain economic benefit.
At present, copper-containing wastewater process generally comprises chemical precipitation method, ion exchange method, extraction process and absorption method.
1. chemical precipitation method
In chemical precipitation method, most widely used general with moderate water-cut stage, the process essence of this method regulates waste water ph, and the pH value precipitated because various metal is best is different, makes removal effect bad; Chemical precipitation method need add chemical agent, there is serious secondary pollution problem, and simultaneously the method can only by cupric ion wastewater treatment to a certain extent, cannot degree of depth deionization, generally needs and subsequent technique combination.
2. ion exchange method
Ion-exchange be by exchanger itself with the ion that can move freely be processed solution in ion realized by ion diffuse.Compared with the precipitator method, it has certain advantage in low concentration wastewater process, but this method is subject to impact and the exchanger kind of the loading capacity of resin, useless impurities in water, produces quantitative limitation, and higher to the pre-processing requirements of waste water, the process of regeneration of ion-exchange resin and regenerated liquid is also an insoluble problem.And due to these resin price costlinesses, production cost is higher, and therefore this method rests on experimental stage mostly, less large-scale application in the industry.
3, solvent extration
Solvent extration is by water insoluble and can add in waste water by the solvent of certain material (claiming solute or extract) in dissolved water, solute is fully dissolved in solvent, and then from waste water, is separated removing or reclaims.Extraction process mainly comprises mixing, is separated and reclaims 3 operations.The key of solvent extration process waste water to use the extraction agent compared with highly selective.Because in the loss of solvent in extraction process and regenerative process, energy consumption is large, the application of this method is limited by very large.
4. absorption method
Absorption method is a kind of method of the unique texture heavy-metal ion removal utilizing sorbent material.Conventional adsorbent has gac, humic acids, polysaccharide resins, quarrel algae soil etc.Facts have proved, use the absorption method of different sorbent material need select suitable sorbent material, general only for the treatment of the low concentration wastewater of trace, which greatly limits its application in practice.
Absorption method is a kind of important method of removal heavy metal, and gac and biological adsorption agent are the sorbent materials of the removal heavy metal based on biomass conventional at present.Due to starting material and the production cost of gac costliness, process lower concentration, big yield heavy metal wastewater thereby time and improper.Although biological adsorption agent cost is lower, lower to low concentration heavy metal water clearance, and it is easy to rotten as biomass and not easily preserves.Therefore seek effective, cost is low, be convenient to simultaneously preserve sorbent material, be an important directions of absorption method removal heavy metal copper.
At present, animal excrement are main composition materials of China's agricultural wastes, annual production is very big, but effective rate of utilization is very low, these can not get the agricultural wastes that effectively utilize usually to burn, the mode of landfill and air storage disposes, the series of environmental problems such as these processing modes can cause environmental pollution, affect view, occupy cultivated land, polluted underground water system, have had a strong impact on environmental quality.Cow dung fertilizer is processed under anoxic and certain temperature condition, obtains charcoal.Biomass after charing are treated, because of its internal gutter distributed architecture be changed, pore texture is flourishing, surperficial degree of roughness increases, specific surface area is large and the physicochemical property of the high uniqueness of ion exchange capacity, charcoal has very high adsorptive capacity to cupric ion, effectively can remove the cupric ion in waste water.Charcoal is a kind of by the biomass rich carbon solid product that pyrolysis produces under anaerobic or anoxia condition.Charcoal prepared by cow dung is the rich carbon product of non-carbonization, and its rich surface is containing carboxyl, hydroxyl, phenolic groups etc., and heavy metal ion and organism have good adsorption effect.Relative to conventional adsorbent gac, raw material sources is extensive, carbonization temperature low (<500 DEG C) in its preparation process, and without the need to follow-up activation step; Its surface functional group rich content, heavy metal clearance is higher.Relative to biological adsorption agent, charcoal prepared by cow dung after pyrolysis carbonization, its stable in properties, not perishable, be easy to preserve.Therefore its abundant raw material of charcoal prepared due to cow dung, with low cost, preparation is simple, be easy to preserve, adsorptive capacity advantages of higher to copper metal.
In prior art, chemical precipitation method need add chemical agent, there is serious secondary pollution problem, the method can only by cupric ion wastewater treatment to a certain extent simultaneously, cannot degree of depth deionization, generally to need and subsequent technique combination, process copper-containing wastewater with being not suitable for extensive high performance cheap; The pre-processing requirements of ion exchange method to waste water is higher, and the process of regeneration of ion-exchange resin and regenerated liquid is also an insoluble problem, processes copper-containing wastewater with being also not suitable for extensive high performance cheap; Solvent extration limits its application in practice compared with the extraction agent of highly selective; Absorption method is general only for the treatment of the low concentration wastewater of trace.
For solving the problem, the invention provides a kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung.Present method overcomes the defect in the defects such as adsorption effect in absorption method is not good and other method, provides a kind of method of Treatment of Copper waste water of high performance cheap.
Summary of the invention
The object of this invention is to provide a kind of method of efficient Treatment of Copper waste water.
Owing to being rich in herbaceous stem fiber in cow dung, the surface roughness of the charcoal particle made is large, specific surface area is large and the physicochemical property of the high uniqueness of ion exchange capacity, and heavy metal positively charged ion has very high adsorptive capacity, effectively can remove the cupric ion in waste water.The present invention have studied cow dung, Ji Dung, human feces etc. and tests various heavy metal adsorption, and result shows, in the absorption of mercury ion, chicken manure is greater than cow dung, and cow dung is greater than human feces; And in the absorption of lead ion, human feces is greater than cow dung, cow dung is greater than chicken manure; And in the absorption of cupric ion, cow dung is just greater than human feces, human feces is greater than chicken manure.The absorption of selecting cow dung to carry out copper residual as charcoal raw material is better than other materials.
According to an aspect of the present invention, provide a kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung, it comprises the following steps.
Prepare a method for the cupric ion in charcoal granular absorption waste water via cow dung, it comprises the following steps:
In a first step,
Cow dung is sent in paddle-dryer the half-dried cow dung being dried to water ratio 40%-50%, described half-dried cow dung and magnesium sulfate powder continue drying-granulating with the quality of 4:1 than being sent in converter after Homogeneous phase mixing, and formation water ratio is 20%-30%, granularity is 100 object circular particles;
Described circular granular is by 100 mesh sieves, the circular granular being greater than sieve aperture returns described converter and continues granulation, in oxygen-free environment, be sent to retort furnace by the circular granular of described sieve and carry out heating charing process, wherein, described retort furnace is first warming up to 200 DEG C makes circular granular be heated evenly, carbonize 2 hours in this temperature, continue to be warming up to 550 DEG C afterwards and continue charing acquisition in 1 hour first charing particle;
In the second step,
It is that the stir speed (S.S.) turning per minute with 200 turns of per minutes to 1000 in the sulfuric acid of 1 mole often liter and nitric acid mixing solutions stirs 12 hours that described first charing particle adds concentration, wherein, first charing granular mass is 1 gram: 30 milliliters to 1 gram: 40 milliliters with described mixed liquor volume ratio, then filter, after described first charing particle distilled water after filtration is washed till neutrality, use isopropanol solvent rinses, and then dries in an oven at temperature 60 to 70 DEG C, forms the second charing particle;
In third step,
Described second charing particle and tin protochloride are added to the water stirring 30 minutes with the mixing of the mass ratio of 1:6, then add hydrochloric acid and enter to carry out temperature rising reflux process, filter, washing, to dry, form the 3rd charing particle;
3rd charing uniform particles is laid on earthenware porcelain receptacle surface, and above it, 80 millimeters of places are provided with power 1 kilowatt, the high voltage mercury lamp fluorescent tube radiation of spectral range 365 to 450 nanometer 16 hours;
In the 4th step,
3rd charing particle is added acetone soln and stirs 3 hours with the stir speed (S.S.) that 50 turns of per minutes to 100 turn per minute, wherein contain 8-10 gram of N-nitroso-group naphthyl azanol ammonium salt in often liter of acetone soln; Vacuumizing described acetone soln makes vacuum tightness 11 × 10
4pa or more, is warming up to 60 DEG C and keeps 6 hours, obtains the 4th charing particle after using deionized water rinsing, filtration;
In the 5th step,
The potential of hydrogen of copper-containing wastewater is adjusted to 8, by the poly-p-tert-butylphenol disulphide that the mass ratio adding 50 grams in 1 liter of copper-containing wastewater is 1:2:4, Iron sulfuret and sodium pyrosulfate, stir after 1 hour, the potential of hydrogen of copper-containing wastewater is adjusted to 6.5, be 1:4 polyoxyethylenated alcohol sodium sulfate and clorox mixture by the mass ratio adding 50 grams in 1 liter of copper-containing wastewater, stir and filter after 2 hours, then the potential of hydrogen of copper-containing wastewater is adjusted to 4-6, add 25 grams of described 4th charing particles by 1 liter of copper-containing wastewater in waste water after process and stir 8 hours with the stir speed (S.S.) of 120 turns of per minutes.
Preferably, cow dung is sent in separation sieve and is separated as foreign material such as stones, owing to being separated foreign material, the impact of foreign material can not being subject in follow-up drying-granulating process, being conducive to the preparation of charcoal particle.
Preferably, described first charing particle can adopt Water-cooled screw pipe to carry out cooling by water, and use cooling by water contributes to the time prepared by shortening charcoal particle, enhances productivity.
Preferably, in the 5th step, regulate the potential of hydrogen of copper-containing wastewater with the sodium hydroxide of the hydrochloric acid of 1 mole often liter and 1 mole often liter.
Preferably, in the second step, it is that the stir speed (S.S.) turning per minute with 400 turns of per minutes to 800 in the sulfuric acid of 1.5 moles often liter and nitric acid mixing solutions stirs 12 hours that described first charing particle adds concentration, contributes to the first charing particle and forms the second charing particle.
More preferably, in third step, described second charing particle and tin protochloride are added to the water stirring 30 minutes with the mixing of the mass ratio of 1:6, then add 1 mole of often liter of hydrochloric acid and enter to carry out temperature rising reflux process.The hydrochloric acid of proper concn contributes to temperature rising reflux process.
More preferably, in the 4th step, the 3rd charing particle is added acetone soln and turns per minute stir speed (S.S.) with 70 turns of per minutes to 90 and stir 2 hours.
Preferably, in the 5th step, the potential of hydrogen of copper-containing wastewater is adjusted to 6.5, adds 250 grams of described 4th charing particles by 1 liter of copper-containing wastewater in the waste water after process and stir 8 hours with 120 turns of per minutes.4th charing particulate absorbent cupric ion is contributed to the adjustment of copper-containing wastewater potential of hydrogen.
The invention provides a kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung, the method is rich in the carboxyl of a large amount of favourable absorption, the cow dung of phenolic hydroxyl group functional group by physico-chemical process process, has made the charcoal particle that surface roughness is large, specific surface area is large and surface negative charge is intensive.Copper-containing wastewater is by after present method process, and copper content can be reduced to below 0.001mg/L.
Accompanying drawing explanation
Fig. 1 is the electronic scanning video picture figure of the 4th charing particle according to method of the present invention;
Fig. 2 is the polluted by copper amount schematic diagram of method according to the present invention under different pH values;
Fig. 3 is the polluted by copper amount schematic diagram of method according to the present invention under different Cu concentration;
Fig. 4 is the polluted by copper rate schematic diagram of method according to the present invention at different charcoal granule content.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with embodiment also with reference to accompanying drawing, the present invention is described in more detail.Should be appreciated that, these describe just exemplary, and do not really want to limit the scope of the invention.In addition, in the following description, the description to known features and technology is eliminated, to avoid unnecessarily obscuring concept of the present invention.
According to an aspect of the present invention, provide a kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung, it comprises the following steps.
In a first step, cow dung is sent in paddle-dryer the half-dried cow dung being dried to water ratio 40%-50%.
Preferably, cow dung is sent in separation sieve and is separated as foreign material such as stones, and then be sent in paddle-dryer and be dried to described dry cow dung.
Described half-dried cow dung and magnesium sulfate powder continue drying-granulating with the quality of 4:1 than being sent in converter after Homogeneous phase mixing, and formation water ratio is 20%-30%, granularity is 100 object circular particles.
Favourable part of the present invention is, by the circular granular obtained with drying after suitable dry cow dung and the mixing of magnesium sulfate opaque amount proportioning, for the pore texture with good surface property and complexity is laid a good foundation.
Described circular granular is by 100 mesh sieves, the circular granular being greater than sieve aperture returns described converter and continues granulation, in oxygen-free environment, be sent to retort furnace by the circular granular of described sieve and carry out heating charing process, wherein, described retort furnace is first warming up to 200 DEG C makes circular granular be heated evenly, carbonize 2 hours in this temperature, continue to be warming up to 550 DEG C afterwards and continue charing acquisition in 1 hour first charing particle.
Preferably, described first charing particle can adopt Water-cooled screw pipe to carry out cooling by water.
In the second step,
It is that the stir speed (S.S.) turning per minute with 200 turns of per minutes to 1000 in the sulfuric acid of 1 mole often liter and nitric acid mixing solutions stirs 12 hours that described first charing particle adds concentration, wherein, first charing granular mass is 1 gram: 30 milliliters to 1 gram: 40 milliliters with described mixed liquor volume ratio, then filter, after described first charing particle distilled water after filtration is washed till neutrality, use isopropanol solvent rinses, and then dries in an oven at temperature 60 to 70 DEG C, forms the second charing particle;
Favourable part of the present invention is carried out suitable mixing match and is optimized with the process of cow dung and the magnesium sulfate powder described particle that is raw material under being suitable concentration, significantly improve the adsorptive power of described second charing particle.
In third step,
Described second charing particle and tin protochloride are added to the water stirring 30 minutes with the mixing of the mass ratio of 1:6, then add hydrochloric acid and enter to carry out temperature rising reflux process, filter, washing, to dry, form the 3rd charing particle;
3rd charing uniform particles is laid on earthenware porcelain receptacle surface, above it, 80 millimeters of places are provided with power 1 kilowatt, the high voltage mercury lamp fluorescent tube radiation of spectral range 365 to 450 nanometer 16 hours, cooling after taking out, irradiates the absorption property that fast and effeciently can improve the 3rd charing particle.Second and third step mainly improves the absorption property carbonizing particle in chemical.
In the 4th step,
3rd charing particle is added acetone soln and stirs 3 hours with the stir speed (S.S.) that 50 turns of per minutes to 100 turn per minute, wherein contain 8-10 gram of N-nitroso-group naphthyl azanol ammonium salt in often liter of acetone soln; Vacuumizing described acetone soln makes vacuum tightness 11 × 10
4pa or more, is warming up to 60 DEG C and keeps 6 hours, obtains the 4th charing particle after using deionized water rinsing, filtration.4th step carries out to the 3rd charing particle the absorption property that complexing further increases the 4th charing particle.
The electronic scanning video picture figure of the 4th charing particle according to method of the present invention as shown in Figure 1, as can be seen from the figure, charcoal particle prepared by method disclosed by the invention has more excellent surface property and pore texture, the duct on the surface of described 4th charing particle is cellular, micropore is evenly distributed, be conducive to the absorption property improving described charcoal particle, further, the process such as the chemical treatment in third and fourth step and irradiation further increases the adsorption effect of described charcoal particle.
In the 5th step,
The potential of hydrogen of copper-containing wastewater is adjusted to 8, by the poly-p-tert-butylphenol disulphide that the mass ratio adding 50 grams in 1 liter of copper-containing wastewater is 1:2:4, Iron sulfuret and sodium pyrosulfate, stir after 1 hour, the potential of hydrogen of copper-containing wastewater is adjusted to 6.5, be 1:4 polyoxyethylenated alcohol sodium sulfate and clorox mixture by the mass ratio adding 50 grams in 1 liter of copper-containing wastewater, stir and filter after 2 hours, then the potential of hydrogen of copper-containing wastewater is adjusted to 4-6, add 25 grams of described 4th charing particles by 1 liter of copper-containing wastewater in waste water after process and stir 8 hours with the stir speed (S.S.) of 120 turns of per minutes.
Standard compliant less than 0.001 milligrams per liter can be dropped to by the copper content of the copper-containing wastewater of method process of the present invention.
Fig. 2 is the polluted by copper amount schematic diagram of method according to the present invention under different pH values, wherein X-coordinate is pH value, ordinate zou is the adsorptive capacity of absorbing copper ions, unit is milligrams per kilogram, in Fig. 2 under different pH values, add 25 grams of described charcoal particles by 1 liter of copper-containing wastewater and stir 8 hours with 120 turns of per minute stir speed (S.S.)s, can learn from Fig. 2, be when 5 at pH, loading capacity is close to maximal absorptive capacity, when pH is 6.5, reach maximal absorptive capacity, charcoal particle is 9081.97 milligrams per kilogram to the maximum adsorption capacity of cupric ion, good adsorption effect can be reached.
Fig. 3 is the polluted by copper amount schematic diagram of method according to the present invention under different Cu concentration, wherein X-coordinate is copper concentration value, ordinate zou is the adsorptive capacity of absorbing copper ions, unit is milligrams per kilogram, wherein, adopt batch null readings, test the absorption property of present method to different Cu concentration, in Fig. 3 under different Cu concentration, add 25 grams of described charcoal particles by 1 liter of copper-containing wastewater and stir 8 hours with 120 turns of per minute stir speed (S.S.)s, can learn from Fig. 3, when copper concentration is greater than 7 milligrams per liter, charcoal particle is 34478.77mg/kg to the loading capacity of cupric ion, when copper concentration is greater than 3 milligrams per liter, charcoal particle is 24440.02mg/kg to the loading capacity of cupric ion, that is, method of the present invention has significant adsorption effect to the copper-containing wastewater that copper concentration is greater than 3 milligrams per liter, and have maximum adsorption effect for the copper-containing wastewater that copper concentration is greater than 7 milligrams per liter, adsorption of the present invention can be given full play to.
Fig. 4 is the polluted by copper rate schematic diagram of method according to the present invention at different charcoal granule content, wherein X-coordinate is charcoal granule content value, ordinate zou is the adsorption rate of absorbing copper ions, wherein, adopt batch null readings, test the absorption property of present method to different charcoal granule content, 250 grams are added by 1 liter of copper-containing wastewater, 200 grams, 100 grams, 50 grams, 25 grams of described charcoal particles stir 8 hours with 120 turns of per minute stir speed (S.S.)s, namely in 200 milliliters of copper-containing wastewaters, 0.5 gram is added in Fig. 4, 1 gram, 1.5 gram, 2 grams and 2.5 grams of charcoal particles, when charcoal particle addition is less than 0.5 gram, adsorption rate and the removal effect of Cu in waste water sharply increase, but after addition is greater than 0.5 gram, the adsorption rate of charcoal particle to Cu in waste water is stablized gradually, that is add 25 grams of charcoal particles in 1 liter of copper-containing wastewater and can give full play to adsorption of the present invention.
According to one embodiment of the invention, in the 5th step, regulate the potential of hydrogen of copper-containing wastewater with the sodium hydroxide of the hydrochloric acid of 1 mole often liter and 1 mole often liter.
According to still another embodiment of the invention, in the second step, it is that the stir speed (S.S.) turning per minute with 400 turns of per minutes to 800 in the sulfuric acid of 1.5 moles often liter and nitric acid mixing solutions stirs 12 hours that described first charing particle adds concentration, contributes to the first charing particle and forms the second charing particle.
According to one embodiment of the invention, in third step, described second charing particle and tin protochloride are added to the water stirring 30 minutes with the mixing of the mass ratio of 1:6, then add 1 mole of often liter of hydrochloric acid and enter to carry out temperature rising reflux process.The hydrochloric acid of proper concn contributes to temperature rising reflux process.
According to another embodiment of the present invention, in the 4th step, the 3rd charing particle is added acetone soln and turns per minute stir speed (S.S.) with 70 turns of per minutes to 90 and stir 2 hours.
According to another embodiment of the present invention, in the 5th step, the potential of hydrogen of copper-containing wastewater is adjusted to 6.5, adds 25 grams of described 4th charing particles by 1 liter of copper-containing wastewater in the waste water after process and stir 8 hours with 120 turns of per minutes.4th charing particulate absorbent cupric ion is contributed to the adjustment of copper-containing wastewater potential of hydrogen.
Should be understood that, above-mentioned embodiment of the present invention only for exemplary illustration or explain principle of the present invention, and is not construed as limiting the invention.Therefore, any amendment made when without departing from the spirit and scope of the present invention, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.In addition, claims of the present invention be intended to contain fall into claims scope and border or this scope and border equivalents in whole change and modification.
Claims (5)
1. prepare a method for the cupric ion in charcoal granular absorption waste water via cow dung, it comprises the following steps:
In a first step,
Cow dung is sent in paddle-dryer the half-dried cow dung being dried to water ratio 40%-50%, described half-dried cow dung and magnesium sulfate powder continue drying-granulating with the quality of 4:1 than being sent in converter after Homogeneous phase mixing, and formation water ratio is 20%-30%, granularity is 100 object circular particles;
Described circular granular is by 100 mesh sieves, the circular granular being greater than sieve aperture returns described converter and continues granulation, in oxygen-free environment, be sent to retort furnace by the circular granular of described sieve and carry out heating charing process, wherein, described retort furnace is first warming up to 200 DEG C makes circular granular be heated evenly, carbonize 2 hours in this temperature, continue to be warming up to 550 DEG C afterwards and continue charing acquisition in 1 hour first charing particle;
In the second step,
It is that the stir speed (S.S.) turning per minute with 200 turns of per minutes to 1000 in the sulfuric acid of 1 mole often liter and nitric acid mixing solutions stirs 12 hours that described first charing particle adds concentration, wherein, first charing granular mass is 1 gram: 30 milliliters to 1 gram: 40 milliliters with described mixed liquor volume ratio, then filter, after described first charing particle distilled water after filtration is washed till neutrality, use isopropanol solvent rinses, and then dries in an oven at temperature 60 to 70 DEG C, forms the second charing particle;
In third step,
Described second charing particle and tin protochloride are added to the water stirring 30 minutes with the mixing of the mass ratio of 1:6, then add hydrochloric acid and carry out temperature rising reflux process, filter, washing, to dry, form the 3rd charing particle;
3rd charing uniform particles is laid on earthenware porcelain receptacle surface, and above it, 80 millimeters of places are provided with power 1 kilowatt, the high voltage mercury lamp fluorescent tube radiation of spectral range 365 to 450 nanometer 16 hours;
In the 4th step,
3rd charing particle is added acetone soln and stirs 3 hours with the stir speed (S.S.) that 50 turns of per minutes to 100 turn per minute, wherein contain 8-10 gram of N-nitroso-group naphthyl azanol ammonium salt in often liter of acetone soln; Vacuumizing described acetone soln makes vacuum tightness 11 × 10
4pa or more, is warming up to 60 DEG C and keeps 6 hours, obtains the 4th charing particle after using deionized water rinsing, filtration;
In the 5th step,
The potential of hydrogen of copper-containing wastewater is adjusted to 8, by the poly-p-tert-butylphenol disulphide that the mass ratio adding 50 grams in 1 liter of copper-containing wastewater is 1:2:4, Iron sulfuret and sodium pyrosulfate, stir after 1 hour, the potential of hydrogen of copper-containing wastewater is adjusted to 6.5, be 1:4 polyoxyethylenated alcohol sodium sulfate and clorox mixture by the mass ratio adding 50 grams in 1 liter of copper-containing wastewater, stir and filter after 2 hours, then the potential of hydrogen of copper-containing wastewater is adjusted to 4-6, add 25 grams of described 4th charing particles by 1 liter of copper-containing wastewater in waste water after process and stir 8 hours with the stir speed (S.S.) of 120 turns of per minutes.
2. method according to claim 1, wherein, is sent to separating sundries in separation sieve by cow dung in a first step, then cow dung is sent in paddle-dryer the half-dried cow dung being dried to water ratio 40%-50%.
3. method according to claim 1, wherein, in the second step, described first charing particle adopts Water-cooled screw pipe to carry out cooling by water, then, described first charing particle adds concentration is that the stir speed (S.S.) turning per minute with 200 turns of per minutes to 1000 in the sulfuric acid of 1 mole often liter and nitric acid mixing solutions stirs 12 hours.
4. method according to claim 1, wherein, regulates the potential of hydrogen of copper-containing wastewater in the 5th step with the sodium hydroxide of the hydrochloric acid of 1 mole often liter and 1 mole often liter.
5. method according to claim 1, wherein, in third step, described second charing particle and tin protochloride are added to the water stirring 30 minutes with the mixing of the mass ratio of 1:6, then add 1 mole of often liter of hydrochloric acid and carry out temperature rising reflux process.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510004832.5A CN104556290B (en) | 2015-01-06 | 2015-01-06 | A kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung |
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| CN201510004832.5A CN104556290B (en) | 2015-01-06 | 2015-01-06 | A kind of method preparing charcoal granular absorption Cu in waste water ion via cow dung |
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