CN104787913B - Cu (II) and the series connection adsorption column of Cr (VI) in a kind of selective enrichment separation electroplating wastewater - Google Patents
Cu (II) and the series connection adsorption column of Cr (VI) in a kind of selective enrichment separation electroplating wastewater Download PDFInfo
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Abstract
The invention provides Cu (II) and the series connection adsorption column of Cr (VI) in a kind of selective enrichment separation electroplating wastewater, including the first adsorption column and the second adsorption column, water inlet and outlet it is provided with on the shell of the first adsorption column and the second adsorption column, equipped with column packing in the shell of the first adsorption column and the second adsorption column, the outlet arranged on first adsorption column shell is connected by arranging water inlet on pipe fitting and the second adsorption column shell, and pipe fitting is provided with control valve；The walnut shell base granular active carbon that column packing is Nitric Acid Modified in first adsorption column shell, the column packing in the second adsorption column shell is the walnut shell base granular active carbon that ilmenite concentrate is modified.Series connection adsorption column of the present invention is capable of carrying out the Cu (II) in electroplating wastewater and Cr (VI) selective absorption, reduces separation, enrichment Cu (II) and the cost of Cr (VI).
Description
Technical field
The invention belongs to electroplating wastewater processing and heavy metal recovery field, particularly to a kind of bivalent cupric ion and series connection adsorption column of hexavalent chromium in selective enrichment separation water sample.
Background technology
Along with developing rapidly of industry, the pollution that discharge of wastewater causes is day by day serious, and China's electroplating industry year waste discharge amount, more than 4,000,000,000 tons, accounts for more than the 1/6 of whole nation industrial wastewater discharge total amount.Because of the not equal reason of plating piece functional requirement, electroplating technical conditions, the water quality of electroplating wastewater is complicated, but pollutant common in electroplating wastewater have based on chromium, copper, the heavy metal ion of nickel, and acid, alkaloids etc., these heavy metal contaminants have the biggest toxicity, there is danger carcinogenic, mutagenic, therefore, equipment and the method, the always study hotspot in electroplating wastewater processing field of heavy metal ions in wastewater is removed and reclaimed to developing low-cost, high efficiency.
The processing method of existing electroplating wastewater mainly has chemical method, ion exchange, electrolysis, membrane separation process, bioanalysis and absorption method etc., wherein, absorption method has that treatment effeciency height, adsorbent renewable repeated use, secondary pollution be little and the feature such as flexible operation degree is big, is a kind of method of effective removal heavy metal out of electroplating wastewater ion.When using absorption method heavy-metal ion removal, many activated carbons directly directly adding powder in waste water carry out adsorption treatment, and research the most few in number carries out adsorption treatment with the adsorption column heavy metal ion filling active carbon filler.Existing adsorption column is often using the activated carbon of single variety as column packing, this type of adsorption column can only adsorb each metal ion species in electroplating wastewater in non-selectivity ground simultaneously, there is the deficiency that cannot directly reclaim valuable heavy metal ion, reclaim to realize the classification of various heavy metal ion, then must increase extra operation sequence the various heavy metal ion adsorbed on adsorption column are separated, but increase operation sequence and directly result in operation complexity and high cost, and be unfavorable for reclaiming the raising of heavy metal ion work efficiency.In addition, the column packing of existing adsorption column is often based on active carbon from coal, such column packing expensive, thus column packing absorption reach saturated after need repeated regeneration to use, but the operation of actifier column filler is complicated, regenerate costly, and cannot realize when regenerating the hybrid piles of absorption is separated, these large-scale promotion the most seriously limiting existing active carbon adsorption column and application.Therefore, develop with low cost, there is selective adsorption capacity, the adsorption column that realize the separation of heavy metal ion, enrichment while electroplating wastewater can processed, the process of electroplating wastewater and the recovery of heavy metal ion are all had great importance.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, Cu (II) and the series connection adsorption column of Cr (VI) in a kind of selective enrichment separation electroplating wastewater is provided, to realize the Cu (II) in electroplating wastewater and Cr (VI) is carried out selective absorption, reduce separation, enrichment Cu (II) and the cost of Cr (VI).
Cu (II) and the series connection adsorption column of Cr (VI) in selective enrichment separation electroplating wastewater of the present invention, including the first adsorption column and the second adsorption column, it is provided with water inlet and outlet on the shell of described first adsorption column and the second adsorption column, equipped with column packing in the shell of described first adsorption column and the second adsorption column, the outlet arranged on first adsorption column shell is connected by arranging water inlet on pipe fitting and the second adsorption column shell, and described pipe fitting is provided with control valve；
The walnut shell base granular active carbon that column packing is Nitric Acid Modified in first adsorption column shell; the preparation method of the walnut shell base granular active carbon of Nitric Acid Modified is: mixed with the nitric acid that concentration is 1～9mol/L by walnut shell matrix activated carbon; 60～80 DEG C of stirrings to being dried; then be washed with water to the pH value of eluate constant after be dried, sieve, concentration is that the consumption of the nitric acid of 1～9mol/L is: every 1kg walnut shell matrix activated carbon adds nitric acid described in 5～15L；
Column packing in second adsorption column shell is the walnut shell base granular active carbon that ilmenite concentrate is modified; the preparation method of the walnut shell base granular active carbon that ilmenite concentrate is modified is: mixed homogeneously with ilmenite concentrate powder by walnut shell particle; then it is mixed with the phosphoric acid that concentration is 10～60wt.%; 400～600 DEG C it are heated under nitrogen protection and at this temperature 30～90min after drying; be washed with water the pH value washed to eluate constant after be dried, sieve, every 1kg walnut shell particle adds phosphoric acid described in 1～3L.
In the technical scheme of above-mentioned series connection adsorption column, being provided with the first glass layer below the column packing of described first adsorption column and the second adsorption column, the column packing of described first adsorption column and the second adsorption column is provided above the second glass layer.
In the technical scheme of above-mentioned series connection adsorption column, the water inlet arranged on described first adsorption column and the second adsorption column shell is positioned at the top of the second glass layer, and the outlet that the first adsorption column and the second adsorption column shell are arranged is positioned at the lower section of the first glass layer；Or, the water inlet that the first adsorption column and the second adsorption column shell are arranged is positioned at the lower section of the first glass layer, and the outlet that the first adsorption column and the second adsorption column shell are arranged is positioned at the top of the second glass layer.
In the technical scheme of above-mentioned series connection adsorption column, described first adsorption column and the second adsorption column shell are provided with the water-locator communicated with described water inlet, are beneficial to be uniformly distributed in column packing into water, improve the utilization rate of column packing.
In the technical scheme of above-mentioned series connection adsorption column, connect and be provided with sample tap on the pipe fitting of the first adsorption column and the second adsorption column, to facilitate the water quality situation of monitoring the first adsorption column water outlet.
In the technical scheme of above-mentioned series connection adsorption column, when preparing the walnut shell base granular active carbon of ilmenite concentrate modification, amount is walnut shell particle quality 0.1%～the 5% of ilmenite concentrate powder interpolation.
In the technical scheme of above-mentioned series connection adsorption column, sieving in the preparation method of the walnut shell base granular active carbon of the preparation method of the walnut shell base granular active carbon of Nitric Acid Modified and ilmenite concentrate modification referred to the sieve of 5～20 mesh.
In the technical scheme of above-mentioned series connection adsorption column, the preparation method of described walnut shell matrix activated carbon is: mixed with the phosphoric acid that concentration is 10～60wt.% by walnut shell particle, at 400～600 DEG C of priming reactions 30～90min, concentration is that the consumption of the phosphoric acid of 10～60wt.% is: every 1kg walnut shell particle adds phosphoric acid described in 1～3L.
In the technical scheme of above-mentioned series connection adsorption column, when preparing the granular active carbon of ilmenite concentrate modification, it is preferred to use temperature is that the water of 70～90 DEG C washs.
In the technical scheme of above-mentioned series connection adsorption column, described in the preparation method of walnut shell base granular active carbon of ilmenite concentrate modification and the preparation method of walnut shell matrix activated carbon, the granular size of walnut shell particle is 5～20 mesh.
In the technical scheme of above-mentioned series connection adsorption column, slurry is preferably distilled water or deionized water.
Compared with prior art, the method have the advantages that
1. the invention provides a kind of novel series connection adsorption column, the Cu (II) in water sample can be optionally adsorbed due to the first adsorption column in this series connection adsorption column, second adsorption column can optionally adsorb the Cr (VI) in water sample, therefore, while using series connection adsorption column of the present invention to process electroplating wastewater, can also realize Cu in electroplating wastewater (II) and Cr (VI) is separated and is enriched with, reclaim valuable heavy metal, not only can simplify the operation reclaiming heavy metal from electroplating wastewater, and the cost of separation and recovery heavy metal can be reduced.
2. it is in series with the second adsorption column of the walnut shell base granular active carbon filling ilmenite concentrate modification by the first adsorption column of walnut shell base granular active carbon filling Nitric Acid Modified due to series connection adsorption column of the present invention, first, the filling kind of the second adsorption column and the series system of the two make electroplating wastewater after the first adsorption column processes, the pH value of its water outlet drops to 2～4 scopes, this pH value range is exactly the optimum condition of the second adsorption column absorption Cr (VI), therefore second adsorption column efficient absorption to Cr (VI) can be directly realized by without regulating waste water acid-base value, the series connection adsorption column separation using the present invention reclaims the Cu (II) in electroplating wastewater and Cr (VI), there is simple to operate and that treatment effeciency is high advantage.
3, the column packing of series connection adsorption column of the present invention is prepared from walnut shell for raw material, walnut shell is a kind of agricultural wastes, with it for raw material production column packing, not only cost is the cheapest, and achieve the recycling of garbage, the treatment of wastes with processes of wastes against one another, owing to production cost is the cheapest, therefore the column packing of the present invention can single use, avoid waste water process and the problem of heavy metal recovery high cost that column packing repeated regeneration causes, thus be advantageously implemented large-scale popularization and application.
Accompanying drawing explanation
Fig. 1 is the first structural representation of series connection adsorption column of the present invention；
Fig. 2 is the second structural representation of series connection adsorption column of the present invention；
Fig. 3 is the third structural representation of series connection adsorption column of the present invention；
Fig. 4 is the stereoscan photograph of the walnut shell base granular active carbon of the Nitric Acid Modified of embodiment 2 preparation；
Fig. 5 is the stereoscan photograph of the walnut shell base granular active carbon of the ilmenite concentrate modification of embodiment 5 preparation；
Fig. 6 is that the walnut shell base granular active carbon of the ilmenite concentrate modification of embodiment 4 preparation under different pH condition is to Cr (VI) clearance curve；
In figure, 1 first adsorption column, 2 second adsorption columns, 3 pipe fittings, 4 control valves, the granular active carbon of 5 Nitric Acid Modified, the granular active carbon of 6 ilmenite concentrates modifications, 7 first glass layers, 8 second glass layers, 9 water-locators, 10 sample taps.
Detailed description of the invention
Combine accompanying drawing by the following examples the series connection adsorption column of Cu (II) and Cr (VI) in a kind of selective enrichment separation electroplating wastewater of the present invention is described further.
In following each embodiment, described ilmenite concentrate is purchased from Yunnan, and XRF analysis shows that in this ilmenite concentrate, the content of various essential elements is: O-37.59wt.%, Fe-25.76wt.%, Ti-24.97wt.%；In described walnut shell, hemicellulose level is 28.3wt.%, and content of lignin is 32.5wt.%, and content of cellulose is 32.47wt.%.
Embodiment 1: the walnut shell base granular active carbon of preparation Nitric Acid Modified
Pulverized by walnut shell, 20 mesh sieves excessively obtain walnut shell particle, are mixed with the phosphoric acid that concentration is 10wt.% by walnut shell particle, add 1L phosphoric acid, obtain walnut shell base granular active carbon at 400 DEG C of priming reaction 90min in every 1kg walnut shell particle；Walnut shell base granular active carbon is mixed with the nitric acid that concentration is 1mol/L; every 1kg walnut shell base granular active carbon adds 5L nitric acid, 60 DEG C of stirrings to being dried, is washed with deionized to the pH value of eluate constant; it is dried in 105 DEG C and removes moisture removal and naturally cool to room temperature, cross 20 mesh sieves and get final product.
Embodiment 2: the walnut shell base granular active carbon of preparation Nitric Acid Modified
Pulverized by walnut shell, 10 mesh sieves excessively obtain walnut shell particle, are mixed with the phosphoric acid that concentration is 40wt.% by walnut shell particle, add 2L phosphoric acid, obtain walnut shell base granular active carbon at 500 DEG C of priming reaction 60min in every 1kg walnut shell particle；Walnut shell base granular active carbon is mixed with the nitric acid that concentration is 6mol/L; every 1kg walnut shell base granular active carbon adds 10L nitric acid; 70 DEG C of stirrings to being dried; it is washed with deionized to the pH value of eluate constant; it is dried in 105 DEG C and removes moisture removal and naturally cool to room temperature, cross 10 mesh sieves and get final product.
The stereoscan photograph of the walnut shell base granular active carbon of Nitric Acid Modified prepared by the present embodiment as shown in Figure 4, carries out Pore Characterization to it, can obtain specific surface area SBET=25.47m2/ g, total hole volume VN2 total=0.16cm3/ g, micropore volume VN2 micro-=0.1808cm3/g。
Embodiment 3: the walnut shell base granular active carbon of preparation Nitric Acid Modified
Pulverized by walnut shell, 5 mesh sieves excessively obtain walnut shell particle, are mixed with the phosphoric acid that concentration is 60wt.% by walnut shell particle, add 3L phosphoric acid, obtain walnut shell base granular active carbon at 600 DEG C of priming reaction 30min in every 1kg walnut shell particle；Walnut shell base granular active carbon is mixed with the nitric acid that concentration is 9mol/L; adding 15L nitric acid in every 1kg walnut shell base granular active carbon, 80 DEG C of stirrings to being dried, the pH value being washed with distilled water to eluate is constant; it is dried in 105 DEG C and removes moisture removal and naturally cool to room temperature, cross 5 mesh sieves and get final product.
Embodiment 4: prepare the walnut shell base granular active carbon that ilmenite concentrate is modified
Walnut shell is pulverized, cross 20 mesh sieves and obtain walnut shell particle, walnut shell particle is mixed homogeneously with ilmenite concentrate powder, the addition of ilmenite concentrate powder is the 0.1% of walnut shell particle quality, then the phosphoric acid that concentration is 10wt.% it is added thereto to, every 1kg walnut shell adds 1L phosphoric acid, it is placed in tube type resistance furnace in 105 DEG C of drying, it is heated to 400 DEG C under nitrogen protection and at this temperature 30min, it is then shut off the power supply of tube type resistance furnace, take out after sample is cooled to room temperature, pH value with the deionized water wash of 70 DEG C to eluate is constant, it is dried in 105 DEG C and removes moisture and naturally cool to room temperature, cross 20 mesh sieves and get final product.
Embodiment 5: prepare the walnut shell base granular active carbon that ilmenite concentrate is modified
Walnut shell is pulverized, cross 10 mesh sieves and obtain walnut shell particle, walnut shell particle is mixed homogeneously with ilmenite concentrate powder body, amount is walnut shell particle quality the 1.5% of ilmenite concentrate powder body powder, then the phosphoric acid that concentration is 40wt.% it is added thereto to, every 1kg walnut shell adds 2L phosphoric acid, it is placed in tube type resistance furnace in 105 DEG C of drying, it is heated to 500 DEG C under nitrogen protection and at this temperature 60min, it is then shut off the power supply of tube type resistance furnace, take out after sample is cooled to room temperature, pH value with the deionized water wash of 80 DEG C to eluate is constant, it is dried in 105 DEG C and removes moisture and naturally cool to room temperature, cross 10 mesh sieves and get final product.
The granular active carbon stereoscan photograph of ilmenite concentrate modification prepared by the present embodiment, as it is shown in figure 5, it is carried out Pore Characterization, can obtain specific surface area SBET=1500.92m2/ g, total hole volume VN2 total=1.387cm3/ g, micropore volume VN2 micro-=0.5895cm3/g。
Embodiment 6: prepare the walnut shell base granular active carbon that ilmenite concentrate is modified
Walnut shell is pulverized, cross 5 mesh sieves and obtain walnut shell particle, walnut shell particle is mixed homogeneously with ilmenite concentrate powder body, amount is walnut shell particle quality the 5% of ilmenite concentrate powder body powder, then the phosphoric acid that concentration is 60wt.% it is added thereto to, every 1kg walnut shell adds 3L phosphoric acid, it is placed in tube type resistance furnace in 105 DEG C of drying, it is heated to 600 DEG C under nitrogen protection and at this temperature 90min, it is then shut off the power supply of tube type resistance furnace, take out after sample is cooled to room temperature, pH value with the distilled water washs of 90 DEG C to eluate is constant, it is dried in 105 DEG C and removes moisture and naturally cool to room temperature, cross 5 mesh sieves and get final product.
Embodiment 7: the absorption property test of column packing
1, the walnut shell base granular active carbon of Nitric Acid Modified is to Cu (II) and the absorption property of Cr (VI)
null(1) take respectively Cu (II) solution of 25mg/L and 25mg/LCr (VI) solution each 5 parts as simulated wastewater，Keep the original ph of each solution，Add the walnut shell base granular active carbon of the Nitric Acid Modified of the most commensurability embodiment 2 preparation the most wherein，4h is adsorbed in 25 DEG C，Then the concentration of Cu (II) in solution after using aas determination to adsorb，The concentration of Cr (VI) in solution after using diphenyl carbazide spectrophotometry mensuration to adsorb，Result shows，When every liter of simulated wastewater adds the walnut shell base granular active carbon of 1g Nitric Acid Modified，The walnut shell base granular active carbon of this Nitric Acid Modified is higher than 92% to the clearance of Cu (II) in Cu (II) solution that initial concentration is 25mg/L，The clearance of Cr (VI) in Cr (VI) solution that initial concentration is 25mg/L is only 18%，Illustrate that the walnut shell base granular active carbon of Nitric Acid Modified of the present invention can optionally Adsorption of Cu (II).
2, the impact of walnut shell base granular active carbon absorption Cr (VI) that pH value is modified on ilmenite concentrate
Take Cr (VI) concentration be 25mg/L, pH value be 1～9 each 50mL of Cr (VI) solution; the granular active carbon of the ilmenite concentrate modification of 0.05g embodiment 5 preparation is added respectively to above-mentioned each solution; 4h is adsorbed in 25 DEG C; then the concentration of Cr (VI) in solution after using diphenyl carbazide spectrophotometry mensuration to adsorb; calculating the ilmenite concentrate modified granular active carbon clearance to Cr (VI), result is as shown in Figure 6.
As shown in Figure 6; the pH value of solution is conducive to the activated carbon absorption to Cr (VI) in the range of 2～4; when the pH value of solution is 3; the modified walnut shell base granular active carbon of ilmenite concentrate is best to the absorption property of Cr (VI), to the clearance of Cr (VI) close to 94%.Illustrating when the pH value containing Cr (VI) waste water is relatively low, the walnut shell base granular active carbon using ilmenite concentrate of the present invention modified can adsorb Cr (VI) efficiently.
3, the walnut shell base granular active carbon that ilmenite concentrate is modified is to Cu (II) and the absorption property of Cr (VI)
nullTake respectively Cu (II) solution of 25mg/L and 25mg/LCr (VI) solution each 5 parts as simulated wastewater，The original ph adjusting each solution is 3，Add the walnut shell base granular active carbon that the ilmenite concentrate of the most commensurability embodiment 5 preparation is modified the most wherein，4h is adsorbed in 25 DEG C，Then the concentration of Cu (II) in solution after using aas determination to adsorb，The concentration of Cr (VI) in solution after using diphenyl carbazide spectrophotometry mensuration to adsorb，Result shows，When every liter of simulated wastewater adds the granular active carbon of 1g ilmenite concentrate modification，The granular active carbon of this ilmenite concentrate modification is about 16% to the clearance of Cu (II) in Cu (II) solution that initial concentration is 25mg/L，And to the clearance of Cr (VI) in Cr (VI) solution that initial concentration is 25mg/L more than 93%，Illustrate that the granular active carbon of ilmenite concentrate modification can selective absorption Cr (VI).
Embodiment 8: series connection adsorption column structure
nullIn the electroplating wastewater of selective enrichment separation described in the present embodiment, the structure of the series connection adsorption column of Cu (II) and Cr (VI) is as shown in Figure 1，Including the first adsorption column 1 and the second adsorption column 2，The internal diameter of the first adsorption column 1 and the second adsorption column 2 is 50mm，It is provided with water inlet on the upper surface of the first adsorption column and the second adsorption column shell、Outlet it is provided with on lower surface，The shell of the first adsorption column and the second adsorption column is respectively arranged with column packing，The outlet of the first adsorption column is connected with the water inlet of the second adsorption column by pipe fitting 3，Control valve 4 it is provided with on pipe fitting 3，The column packing of the first adsorption column is the walnut shell base granular active carbon 5 of the Nitric Acid Modified of embodiment 1 preparation，Its filling thickness is 10cm，The column packing of the second adsorption column is the walnut shell base granular active carbon 6 of the ilmenite concentrate modification of embodiment 4 preparation，Its filling thickness is 10cm；The lower section of the column packing of described first adsorption column and the second absorption is provided with the first glass layer 7 that thickness is 1cm, and the top of the column packing of the first adsorption column and the second adsorption column is provided with the second glass layer 8 that thickness is 1cm.
Embodiment 9: series connection adsorption column structure
nullIn the present embodiment，In described selective enrichment separation electroplating wastewater, the structure of the series connection adsorption column of Cu (II) and Cr (VI) is as shown in Figure 2，Including the first adsorption column 1 and the second adsorption column 2，The internal diameter of the first adsorption column and the second adsorption column is 20mm，It is provided with water inlet on the upper surface of the first adsorption column and the second adsorption column shell、Outlet it is provided with on lower surface，The shell of the first adsorption column and the second adsorption column is respectively arranged with column packing，The outlet of the first adsorption column is connected with the water inlet of the second adsorption column by pipe fitting 3，Control valve 4 it is provided with on pipe fitting 3，The column packing of the first adsorption column is the walnut shell base granular active carbon 5 of the Nitric Acid Modified of embodiment 3 preparation，Its filling thickness is 5cm，The column packing of the second adsorption column is the walnut shell base granular active carbon 6 of the ilmenite concentrate modification of embodiment 6 preparation，Its filling thickness is 5cm；The lower section of the column packing of described first adsorption column 1 and the second absorption 2 is provided with the first glass layer 7 that thickness is 0.5cm, the top of the column packing of the first adsorption column and the second adsorption column is provided with the second glass layer 8 that thickness is 0.5cm, is provided with the water-locator 9 being connected with water inlet in the first adsorption column and the second adsorption column.
Embodiment 10: series connection adsorption column structure
nullIn the present embodiment，In described selective enrichment separation electroplating wastewater, the structure of the series connection adsorption column of Cu (II) and Cr (VI) is as shown in Figure 3，Including the first adsorption column 1 and the second adsorption column 2，The internal diameter of the first adsorption column 1 and the second adsorption column 2 is 10mm，It is provided with water inlet on the upper surface of the first adsorption column and the second adsorption column shell、Outlet it is provided with on lower surface，The shell of the first adsorption column and the second adsorption column is respectively arranged with column packing，The outlet of the first adsorption column is connected with the water inlet of the second adsorption column by pipe fitting 3，Control valve 4 and sample tap 10 it is provided with on pipe fitting 3，The column packing of the first adsorption column is the walnut shell base granular active carbon 5 of the Nitric Acid Modified of embodiment 2 preparation，Its filling thickness is 2cm，The column packing of the second adsorption column is the granular active carbon 6 of the walnut shell base ilmenite concentrate modification of embodiment 5 preparation，Its filling thickness is 2cm；The lower section of the column packing of described first adsorption column 1 and the second absorption 2 is provided with the first glass layer 7 that thickness is 0.2cm, the top of the column packing of the first adsorption column and the second adsorption column is provided with in the second glass layer 8 that thickness is 0.2cm, the first adsorption column 1 and the second adsorption column 2 and is provided with the water-locator 9 being connected with water inlet.
Embodiment 11
In the present embodiment, using the simulation electroplating wastewater that the series connection adsorption column treatment of laboratory in embodiment 10 is prepared, simulation electroplating wastewater is the mixed liquor of bivalent cupric ion and hexavalent chromium, wherein, the concentration C of bivalent cupric ionCu(II)=25mg/L, the concentration C of hexavalent chromiumCr(VI)=25mg/L.
nullControl valve 4 on pipe fitting 3 between first adsorption column 1 and the second adsorption column 2 is opened，Use peristaltic pump that from the entrance of the first adsorption column, simulation electroplating wastewater is pumped into the first adsorption column according to the flow of 10mL/min at 25 DEG C，The water outlet of the first adsorption column is taken from sample tap 10 in different time points，And go the water outlet of the second adsorption column in different time points from the water outlet of the second adsorption column，And measure the first adsorption column and the water quality situation of the second adsorption column water outlet，After dynamic adsorption 90min，First adsorption column is higher than 94% to the clearance of Cu in simulated wastewater (II)，The clearance of Cr (VI) is less than 0.5%，And now，The water outlet of the first adsorption column is after the second adsorption column adsorption treatment，The clearance of the Cr (VI) in simulated wastewater reaches 100%，The clearance of Cu (II) is 95%，I.e. second adsorption column is only 1% to the clearance of Cu (II).This illustrates the first adsorption column energy selective absorption Cu (II), and the second adsorption column energy selective absorption Cr (VI), and both has extraordinary selective adsorption capacity.
Utilize the HNO that 50mL concentration is 0.1mol/L3Solution carries out eluting to the simulation electroplating wastewater absorption column packing of the first adsorption column after saturated, measures the bivalent cupric ion concentration in eluent, and in eluent, Cu (II) concentration is in simulated wastewater 34 times of Cu (II) concentration.
Measure the first adsorption column in different time points sampling and the pH value of simulated wastewater in the second adsorption column exit, result shows: the original ph of simulation electroplating wastewater is about 5.4, after the first adsorption column processes, the pH value of the first adsorption column water outlet is reduced to 2～4, the optimal pH that this pH value range is exactly the second adsorption column absorption Cr (VI) is interval, the second adsorption column is conducive to effectively to adsorb Cr (VI), after the second adsorption column processes, the pH value of the second adsorption column water outlet gos up to 4～6.
Claims (10)
1. Cu (II) and the series connection adsorption column of Cr (VI) in a selective enrichment separation electroplating wastewater, it is characterised in that include first
Adsorption column (1) and the second adsorption column (2), the shell of described first adsorption column and the second adsorption column is provided with water inlet and goes out
The mouth of a river, equipped with column packing in the shell of described first adsorption column and the second adsorption column, the outlet that the first adsorption column shell is arranged
By pipe fitting (3) with on the second adsorption column shell, water inlet be set be connected, described pipe fitting (3) is provided with control valve (4)；
Walnut shell base granular active carbon (5) that column packing is Nitric Acid Modified in first adsorption column shell, the walnut shell of Nitric Acid Modified
The preparation method of base granular active carbon (5) is: mixed with the nitric acid that concentration is 1～9mol/L by walnut shell matrix activated carbon, at 60～80 DEG C
Stirring to being dried, be then washed with water to the pH value of eluate constant after be dried, sieve, concentration is the use of the nitric acid of 1～9mol/L
Amount is: every 1kg walnut shell matrix activated carbon adds nitric acid described in 5～15L；
Column packing in second adsorption column shell is walnut shell base granular active carbon (6) that ilmenite concentrate is modified, the core that ilmenite concentrate is modified
The preparation method of peach shell base granular active carbon (6) is: mixed homogeneously with ilmenite concentrate powder by walnut shell particle, then by it with dense
Degree is the phosphoric acid mixing of 10～60wt.%, is heated to 400～600 DEG C under nitrogen protection and at this temperature after drying
30～90min, be washed with water the pH value washed to eluate constant after be dried, sieve, every 1kg walnut shell particle adds described in 1～3L
Phosphoric acid.
Cu (II) and the series connection adsorption column of Cr (VI) in selective enrichment separation electroplating wastewater the most according to claim 1, it is special
Levy and be below the column packing of described first adsorption column (1) and the second adsorption column (2) to be provided with the first glass layer (7),
The column packing of described first adsorption column (1) and the second adsorption column (2) is provided above the second glass layer (8).
Cu (II) and the series connection adsorption column of Cr (VI) in selective enrichment separation electroplating wastewater the most according to claim 2, it is special
Levy the water inlet being on described first adsorption column and the second adsorption column shell to arrange and be positioned at the top of the second glass layer (8),
The outlet arranged on first adsorption column and the second adsorption column shell is positioned at the lower section of the first glass layer (7)；Or, first
The water inlet arranged on adsorption column and the second adsorption column shell is positioned at the lower section of the first glass layer (7), the first adsorption column and the
The outlet arranged on two adsorption column shells is positioned at the top of the second glass layer (8).
4. according to Cu (II) and Cr (VI) in the selective enrichment separation electroplating wastewater described in any claim in claims 1 to 3
Series connection adsorption column, it is characterised in that described first adsorption column (1) and the second adsorption column (2) shell are provided with described enter
The water-locator (9) that the mouth of a river communicates.
5. according to Cu (II) and Cr (VI) in the selective enrichment separation electroplating wastewater described in any claim in claims 1 to 3
Series connection adsorption column, it is characterised in that connect to be provided with on the pipe fitting (3) of the first adsorption column (1) and the second adsorption column (2) and take
Sample mouth (10).
6. according to Cu (II) and Cr (VI) in the selective enrichment separation electroplating wastewater described in any claim in claims 1 to 3
Series connection adsorption column, it is characterised in that when preparing modified walnut shell base granular active carbon (6) of ilmenite concentrate, ilmenite concentrate powder adds
Amount is the 0.1%～5% of walnut shell particle quality.
7. according to Cu (II) and Cr (VI) in the selective enrichment separation electroplating wastewater described in any claim in claims 1 to 3
Series connection adsorption column, it is characterised in that described in sieve and referred to the sieve of 5～20 mesh.
8. according to Cu (II) and Cr (VI) in the selective enrichment separation electroplating wastewater described in any claim in claims 1 to 3
Series connection adsorption column, it is characterised in that the preparation method of described walnut shell matrix activated carbon is: by walnut shell particle with concentration be
The phosphoric acid mixing of 10～60wt.%, at 400～600 DEG C of priming reactions 30～90min, concentration is that the consumption of the phosphoric acid of 10～60wt.% is:
Every 1kg walnut shell particle adds phosphoric acid described in 1～3L.
Cu (II) and the series connection adsorption column of Cr (VI) in selective enrichment separation electroplating wastewater the most according to claim 8, it is special
Levy and be that the granular size of described walnut shell particle is 5～20 mesh.
10. according to Cu (II) and Cr (VI) in the selective enrichment separation electroplating wastewater described in any claim in claims 1 to 3
Series connection adsorption column, it is characterised in that the granular size of described walnut shell particle is 5～20 mesh.
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| " Walnut shell-based activated carbon with excellent copper (II) adsorption and lower chromium (VI) removal prepared by acid-base modification";Xie R et al.;《Enviromental Progress & Sustainable Energy》;20131231;第32卷(第3期);第688-696页 * |
| "钛铁矿造孔核桃壳基活性炭的制备及其吸附性能";毛佳丽 等;《化工环保》;20131231;第33卷(第4期);第367-371页 * |
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