CN111422942A - Method for synchronously reducing and adsorbing hexavalent chromium in water by using ethylenediamine-based resin - Google Patents
Method for synchronously reducing and adsorbing hexavalent chromium in water by using ethylenediamine-based resin Download PDFInfo
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- CN111422942A CN111422942A CN202010206991.4A CN202010206991A CN111422942A CN 111422942 A CN111422942 A CN 111422942A CN 202010206991 A CN202010206991 A CN 202010206991A CN 111422942 A CN111422942 A CN 111422942A
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- ethylenediamine
- based resin
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229920005989 resin Polymers 0.000 title claims abstract description 122
- 239000011347 resin Substances 0.000 title claims abstract description 122
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 99
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 65
- 238000001179 sorption measurement Methods 0.000 claims abstract description 113
- 238000003795 desorption Methods 0.000 claims abstract description 100
- 239000011651 chromium Substances 0.000 claims abstract description 98
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 56
- 230000008929 regeneration Effects 0.000 claims abstract description 52
- 238000011069 regeneration method Methods 0.000 claims abstract description 52
- 239000000706 filtrate Substances 0.000 claims abstract description 39
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000008213 purified water Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000007864 aqueous solution Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 22
- 229920005990 polystyrene resin Polymers 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 206010042674 Swelling Diseases 0.000 claims description 11
- 230000008961 swelling Effects 0.000 claims description 11
- 229910001430 chromium ion Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract description 18
- 229910020489 SiO3 Inorganic materials 0.000 abstract description 17
- 239000000463 material Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- 239000011521 glass Substances 0.000 description 14
- 230000009467 reduction Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940077449 dichromate ion Drugs 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
Classifications
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin, which comprises the following steps: adjusting the pH value of the hexavalent chromium-containing water body; passing the filtrate through an adsorption tower filled with ethylenediamine-based resin to obtain a deeply purified water body; the skeleton of the ethylenediamine-based resin is polystyrene-divinylbenzene, and ethylenediamine-based groups are grafted on the skeleton; when the adsorption reaches the adsorption leakage point, the alkali liquor is used for desorption, and then the acid liquor is used for desorption, so that the regeneration treatment is carried out. The method treats hexavalent chromium with the polystyrene-divinylbenzene grafted ethylenediamine-based resin, and finds that when the pH value of the water body is 2.0-7.0, high-concentration Cl coexists‑、NO3 ‑、HCO3 ‑、SO4 2‑And SiO3 2‑In the case, the total chromium content of the effluent is still reduced from 0.05-100 mg/L to below 0.01 mg/L, and the desorption solution contains reduced trivalent chromium.
Description
Technical Field
The invention relates to the technical field of sewage treatment and resource recycling, in particular to a method for deeply purifying chromium in a water body, and specifically relates to a method for deeply purifying hexavalent chromium in a water body by using an ethylenediamine-based resin material which has reduction and adsorption capacities on hexavalent chromium (dichromate or chromate ions) and high adsorption capacity and selectivity.
Background
Chromium (Cr) is one of the most toxic heavy metals, and is widely present in industrial wastewater of electroplating, oil refining, alloy manufacturing, battery production, and the like. Cr exists in natural environment mainly in the forms of Cr (III) and Cr (VI), wherein Cr (VI) has stronger toxicity and solubility than Cr (III). Cr (vi) is about five hundred times more toxic than Cr (iii) and is also more susceptible to environmental migration, and is therefore also defined by the united states Environmental Protection Agency (EPA) and the domestic environmental protection agency (EPB) as the highest priority for major pollutants.
The method for removing hexavalent chromium in the water body mainly comprises a biological method, an electrochemical method, an adsorption method, an ion exchange method, a reduction precipitation method and the like, wherein the reduction precipitation method and the adsorption method are mostly applied. However, the traditional reduction precipitation method needs to add a large amount of reducing substances, is only suitable for the conditions of small wastewater flow and no wastewater reuse, and the industrial design of the traditional reduction precipitation method needs a large floor area, so that the problems of high cost, more sludge, difficult sludge treatment, secondary pollution and the like exist; the conventional adsorption method does not change the valence state of hexavalent chromium, but only transfers toxicity, and in addition, the widely applied adsorbent has lower adsorption capacity and higher post-treatment difficulty.
The simultaneous reductive adsorption of cr (vi) contaminants by the adsorbent material is a considerable advantage over these conventional adsorption processes in that it not only enriches cr (vi) but also reduces cr (vi) to cr (iii). In recent years, amino-functionalized materials have received much attention in water treatment applications. In a slightly acidic environment, amino groups are easily protonated and can form electrostatic interaction with Cr (VI) ions with negative charges, meanwhile, Cr (VI) is reduced to Cr (III) after being adsorbed, the amino groups are oxidized to form imino groups, and the Cr (III) ions can be fixed by the coordination of the amino groups or the imino groups; the imino groups can be reduced back to ammonia/amine groups by simple acid treatment.
At present, literature search shows that no method for deeply purifying hexavalent chromium by adopting ethylenediamine-based resin is disclosed.
Disclosure of Invention
Aiming at the problems of low pollutant treatment depth, unreduced toxicity of hexavalent chromium, unstable adsorbent, difficult regeneration and reutilization and the like of the traditional hexavalent chromium purification technology in the water body, the invention provides a method for synchronously reducing and adsorbing hexavalent chromium in the water body by using ethylenediamine-based resin, and the method can compete for anion Cl in the water body-、NO3 -、HCO3 -、SO4 2-、SiO3 2-When the concentration of the chromium is far higher than the target dichromate ion/chromate ion, the chromium content of the effluent reaches the drinking water safety control standard specified by the state.
The specific technical scheme is as follows:
a method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following steps:
(1) adjusting the pH value of the water body containing hexavalent chromium, and filtering to obtain filtrate;
(2) enabling the filtrate obtained in the step (1) to pass through an adsorption tower filled with ethylenediamine-based resin to enable hexavalent chromium in the water body to be adsorbed on the ethylenediamine-based resin, and obtaining a deeply purified water body;
the skeleton of the ethylenediamine-based resin is polystyrene-divinylbenzene, and ethylenediamine-based groups are grafted on the skeleton;
(3) stopping adsorption when the adsorption reaches an adsorption leakage point, and desorbing by using alkali liquor to desorb hexavalent chromium from the ethylene diamine resin which is saturated in adsorption; then, carrying out desorption regeneration by using acid liquor, so that trivalent chromium is desorbed from the ethylenediamine-based resin with saturated adsorption, and realizing amino regeneration; finally, washing with water until the ethylenediamine-based resin is neutral.
The ethylenediamine-based resin adopted by the invention is grafted ethylenediamine (B) on the basis of a polystyrene-divinylbenzene frameworkR-NH-NH2) A group. The ethylenediamine has good biocompatibility, good chemical stability and good thermal stability. Meanwhile, the ethylenediamine contains ammonia/amido (-NH)2The unique electronic doping/dedoping property of the material is good in reducing performance and reusability, so that hexavalent chromium can be reduced into trivalent chromium and adsorbed on ethylenediamine-based resin, and deep treatment of the hexavalent chromium in the water body is realized.
Further, in the step (1), the pH value is 2.0-7.0, the mass concentration of hexavalent chromium ions in the water body is 0.05-100 mg/L by the mass of chromium elements, and the mass concentration of other coexisting anions in the water body is less than 500 times of the mass concentration of the hexavalent chromium ions.
Further, the preparation method of the ethylenediamine-based resin comprises the following steps:
i) adding chloromethylated polystyrene resin into a dimethylformamide swelling agent for swelling treatment;
ii) filtering out the swelling agent, separating to obtain swelled chloromethylated polystyrene resin, adding the swelled chloromethylated polystyrene resin into a mixed solution containing ethylenediamine and ethanol, carrying out grafting reaction under the condition of water bath, and filtering out the mixed solution to obtain the chloromethylated polystyrene resin subjected to grafting treatment;
iii) washing the grafted chloromethylated polystyrene resin with distilled water, extracting with ethanol to remove impurities in the chloromethylated polystyrene resin, and drying in vacuum at room temperature to obtain the ethylenediamine-based resin.
Further, in the step i), the swelling treatment time is 12-24 hours; in the step ii), the volume ratio of the ethylenediamine to the ethanol in the mixed solution is 1: 1; the mass-to-volume ratio of the chloromethylated polystyrene resin to the mixed solution is 1: 2-3.
Further, in the step ii), the temperature of the grafting reaction is 55-65 ℃ and the time is 8-12 h.
Further, in the step (2), the temperature of the filtrate passing through the adsorption tower filled with the ethylenediamine-based resin is 5-40 ℃, and the flow rate of the filtrate is less than 30 resin bed volumes per hour.
Further, in the step (3), the adsorption leakage point is that the mass concentration of total chromium (the sum of hexavalent chromium ions and trivalent chromium ions) in the effluent solution is more than 0.01 mg/L according to the mass of the chromium element.
Further, in the step (3), the alkali liquor is a NaOH aqueous solution with the weight percentage concentration of 2-10%; regenerating the alkali liquor at the flow rate of 1-5 resin bed volumes per hour at the temperature of 15-60 ℃ when the alkali liquor passes through the ethylenediamine-based resin;
further, in the step (3), the acid solution is sulfuric acid aqueous solution or nitric acid aqueous solution with the weight percentage concentration of 1-5%, and regeneration is carried out at the flow rate of 1-5 resin bed volumes per hour at the temperature of 15-60 ℃.
Further, the steps (2) and (3) adopt a single-tower adsorption-desorption or multi-tower series adsorption-single-tower desorption operation mode.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts the resin grafted with ethylenediamine group by taking polystyrene-divinylbenzene as a framework as an adsorbing material to carry out deep purification treatment on hexavalent chromium in the water body, and finds that when the pH value of the water body is 2.0-7.0, high-concentration Cl-and NO coexist3 -、HCO3 -、SO4 2-And SiO3 2-In the case of (2), the total chromium mass concentration (the sum of hexavalent chromium ions and trivalent chromium ions) of the effluent can still be reduced from 0.05-100 mg/L to below 0.01 mg/L, and the desorption solution contains reduced trivalent chromium.
(2) The method has large treatment capacity and stable adsorption material, and can be used for a long time.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are only illustrative of the present invention, but the scope of the present invention is not limited thereto.
The ethylenediamine-based resin related in the following examples is an adsorbing material containing ethylenediamine-based resin on a polystyrene-divinylbenzene structure, and the specific preparation method is as follows:
i) 10ml (about 5g) of chloromethylated polystyrene resin was added to 50m L of Dimethylformamide (DMF) swelling agent, and the swelling treatment was carried out for 12 hours;
ii) filtering out a swelling agent, separating to obtain swelled chloromethylated polystyrene resin, adding the swelled chloromethylated polystyrene resin into a mixed solution (the volume ratio of the chloromethylated polystyrene resin to the mixed solution is 1:2.5) containing ethylenediamine and ethanol (the volume ratio of the ethylenediamine to the ethanol is 1:1), carrying out grafting reaction in a water bath kettle at the temperature of 60 ℃ for 10 hours, and filtering out the mixed solution to obtain the chloromethylated polystyrene resin subjected to grafting treatment;
iii) washing the grafted chloromethylated polystyrene resin with distilled water, extracting with ethanol to remove impurities in the chloromethylated polystyrene resin, and drying in vacuum at room temperature to obtain the ethylenediamine-based resin.
Example 1
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 1ppm, Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of (1) is 100ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 +/-5 ℃ and at the flow rate of 15BV/h, the treatment capacity is more than 10000BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 2
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the adsorption temperature is controlled to be 5 +/-2 ℃, and the adsorption effect and the treatment capacity are basically unchanged.
Example 3
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the adsorption temperature is controlled to be 40 +/-5 ℃, and the adsorption effect and the treatment capacity are basically unchanged.
Example 4
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the flow rate of the filtrate passing through the adsorption column containing the ethylenediamine-based resin bed layer is changed to 5BV/h, and the adsorption effect and the treatment capacity are basically unchanged.
Example 5
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the flow rate of the filtrate passing through the adsorption column containing the ethylenediamine-based resin bed layer is changed to 25BV/h, and the adsorption effect and the treatment capacity are basically unchanged.
Example 6
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 0.2ppm, Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of each is 20ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 +/-5 ℃ and at the flow rate of 15BV/h, the treatment capacity is more than 35000BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 7
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 0.05ppm, Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of each 10ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 20m L (about 10 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 +/-5 ℃ and at a flow rate of 15BV/h, the treatment capacity is about 100000BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 8
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 20ppm and Cl-、NO3 -、HCO3 -、SiO3 2-、SO4 2-The concentration of all the components is 2000ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 200m L (about 100 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 + -5 ℃ at a flow rate of 5BV/h, the treatment capacity is about 600BV, and the total chromium concentration of effluent is reduced to less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 9
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 50ppm, Cl-、NO3 -、HCO3 -、SiO3 2-、SO4 2-The concentration of (1) is 5000ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 200m L (about 100 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 + -5 ℃ at a flow rate of 5BV/h, the treatment capacity is about 250BV, and the total chromium concentration of effluent is reduced to less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 10
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) regulating the concentration of hexavalent chromium-containing water body (Cr (VI)) to 75ppm, Cl-、NO3 -、HCO3 -、SiO3 2-、SO4 2-The concentration of (1) is 5000ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 200m L (about 100 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 + -5 ℃ at a flow rate of 5BV/h, the treatment capacity is about 150BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 11
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 100ppm, Cl-、NO3 -、HCO3 -、SiO3 2-、SO4 2-Is rich inThe degree is 5000ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 200m L (about 100 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 + -5 ℃ at a flow rate of 5BV/h, the treatment capacity is about 100BV, and the total chromium concentration of effluent is reduced to less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 12
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the pH value of the hexavalent chromium-containing water body is adjusted to 2.0, and the adsorption effect and the treatment capacity are basically unchanged.
Example 13
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the pH value of the hexavalent chromium-containing water body is adjusted to 3.0, and the adsorption effect and the treatment capacity are basically unchanged.
Example 14
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the pH value of the hexavalent chromium-containing water body is adjusted to 5.0, and the adsorption effect and the treatment capacity are basically unchanged.
Example 15
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the pH value of the hexavalent chromium-containing water body is adjusted to 6.0, and the adsorption effect and the treatment capacity are basically unchanged.
Example 16
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), the pH value of the hexavalent chromium-containing water body is adjusted to 7.0, and the adsorption effect and the treatment capacity are basically unchanged.
Example 17
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 1ppm, Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of each is 20ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of ethylenediamine-based resin is filled into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 +/-5 ℃ and at the flow rate of 15BV/h, the treatment capacity is more than 20000BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 18
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 1ppm, Cl-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of (1) is 50ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of ethylenediamine-based resin was charged into a jacketed glass adsorption column (. PHI.32 32 × 360mm), and the filtrate obtained in step (1) was passed through the adsorption column containing an ethylenediamine-based resin bed at 25. + -. 5 ℃ at a flow rate of 15BV/h, at a throughput of about 13500BV, with the total chromium concentration in the effluent reduced by 10ppb or less.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 19
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), Cl in the hexavalent chromium-containing water body (namely the Cr (VI) mixed solution)-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of (A) is changed into 200ppm, and the adsorption effect and the treatment capacity are basically unchanged.
Example 20
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (1), Cl in the hexavalent chromium-containing water body (namely the Cr (VI) mixed solution)-、NO3 -、HCO3 -、SO4 2-、SiO3 2-The concentration of the catalyst is changed to 500ppm, and the adsorption effect and the treatment capacity are basically unchanged.
Example 21
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 1ppm, Cl-、NO3 -、HCO3 -All at a concentration of 100ppm) of a pH valueAdjusting to 4.0, and filtering to obtain filtrate;
(2) 50m L (about 25 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), and the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 + -5 ℃ at a flow rate of 15BV/h, with a treatment capacity of about 20000BV, and the total chromium concentration of the effluent is reduced to 10ppb or less.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 22
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) regulating the concentration of hexavalent chromium-containing water body (Cr (VI)) to 1ppm, SO4 2-、SiO3 2-The concentration of (1) is 100ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 + -5 ℃ at a flow rate of 15BV/h, the treatment capacity is about 12000BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 23
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) regulating the concentration of hexavalent chromium-containing water body (Cr (VI)) to 1ppm, HCO3 -、SO4 2-The concentration of (1) is 100ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 +/-5 ℃ and at a flow rate of 15BV/h, the treatment capacity is about 16000BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 24
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 1ppm, Cl-、NO3 -、HCO3 -Concentration 50ppm, SO4 2-、SiO3 2-The concentration of (1) is 100ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 + -5 ℃ at a flow rate of 15BV/h, the treatment capacity is about 12000BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 25
A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin comprises the following specific steps:
(1) adjusting the concentration of hexavalent chromium-containing water (Cr (VI)) to 1ppm, Cl-、NO3 -、HCO3 -In a concentration of 100ppm, SO4 2-、SiO3 2-The concentration of (1) is 50ppm) is adjusted to 4.0, and the filtrate is obtained after filtration;
(2) 50m L (about 25 g) of ethylenediamine-based resin is loaded into a jacketed glass adsorption column (phi 32 × 360mm), the filtrate obtained in step (1) is passed through the adsorption column containing ethylenediamine-based resin bed at 25 + -5 ℃ at a flow rate of 15BV/h, the treatment capacity is about 12000BV, and the total chromium concentration of effluent is reduced by less than 10 ppb.
(3) When the adsorption reaches a leakage point (the total chromium concentration of the adsorbed water is more than 10ppb), the adsorption is stopped, NaOH aqueous solution with the concentration of 5 percent by weight of 300m L is firstly used for carrying out desorption by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, then nitric acid aqueous solution with the concentration of 5 percent by weight of 300m L is used for carrying out desorption regeneration by flowing through the resin bed layer at the temperature of 25 +/-5 ℃ at the flow rate of 1BV/h, the total desorption rate is more than 90 percent, the desorption solution contains Cr (III) which accounts for 10 to 15 percent of the total chromium content of desorption, the desorption solution is washed by water to be neutral for regeneration, and the total regeneration rate of the adsorption material is more than 90 percent.
Example 26
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (3), the weight percentage concentration of the NaOH aqueous solution is 10%, and the desorption effect and the treatment capacity are basically unchanged.
Example 27
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (3), the weight percentage concentration of the NaOH aqueous solution is 2%, and the desorption effect and the treatment capacity are basically unchanged.
Example 28
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (3), the weight percentage concentration of the nitric acid aqueous solution is 1 percent, and the regeneration effect and the treatment capacity are basically unchanged.
Example 29
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (3), the weight percentage concentration of the nitric acid aqueous solution is 3 percent, and the regeneration effect and the treatment capacity are basically unchanged.
Example 30
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (3), the temperature of the two times of desorption is changed to 15 +/-5 ℃, and the desorption effect and the treatment capacity are basically unchanged.
Example 31
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (3), the temperature of the two times of desorption is changed to 40 +/-5 ℃, and the desorption effect and the treatment capacity are basically unchanged.
Example 32
The same method as that of example 1 is adopted to treat hexavalent chromium in the water body, and the difference is that: in the step (3), the temperature of the two desorption steps is changed to 55 +/-5 ℃, and the desorption effect and the treatment capacity are basically unchanged.
Claims (10)
1. A method for synchronously reducing and adsorbing hexavalent chromium in a water body by using ethylenediamine-based resin is characterized by comprising the following steps:
(1) adjusting the pH value of the water body containing hexavalent chromium, and filtering to obtain filtrate;
(2) enabling the filtrate obtained in the step (1) to pass through an adsorption tower filled with ethylenediamine-based resin to enable hexavalent chromium in the water body to be adsorbed on the ethylenediamine-based resin, and obtaining a deeply purified water body;
the skeleton of the ethylenediamine-based resin is polystyrene-divinylbenzene, and ethylenediamine-based groups are grafted on the skeleton;
(3) stopping adsorption when the adsorption reaches an adsorption leakage point, and desorbing by using alkali liquor to desorb hexavalent chromium from the ethylene diamine resin which is saturated in adsorption; then, carrying out desorption regeneration by using acid liquor, so that trivalent chromium is desorbed from the ethylenediamine-based resin with saturated adsorption, and realizing amino regeneration; finally, washing with water until the ethylenediamine-based resin is neutral.
2. The method for synchronously reducing-adsorbing hexavalent chromium in water according to claim 1, wherein the pH value in step (1) is 2.0 to 7.0, the mass concentration of hexavalent chromium ions in the water is 0.05 to 100 mg/L based on the mass of chromium element, and the mass concentration of other coexisting anions in the water is less than 500 times the mass concentration of hexavalent chromium ions.
3. The method for synchronously reducing-adsorbing hexavalent chromium in water by using ethylenediamine-based resin according to claim 1, wherein the method for preparing ethylenediamine-based resin comprises:
i) adding chloromethylated polystyrene resin into a dimethylformamide swelling agent for swelling treatment;
ii) filtering out the swelling agent, separating to obtain swelled chloromethylated polystyrene resin, adding the swelled chloromethylated polystyrene resin into a mixed solution containing ethylenediamine and ethanol, carrying out grafting reaction under the condition of water bath, and filtering out the mixed solution to obtain the chloromethylated polystyrene resin subjected to grafting treatment;
iii) washing the grafted chloromethylated polystyrene resin with distilled water, extracting with ethanol to remove impurities in the chloromethylated polystyrene resin, and drying in vacuum at room temperature to obtain the ethylenediamine-based resin.
4. The method for synchronously reducing-adsorbing hexavalent chromium in water by using ethylenediamine-based resin according to claim 3, wherein in the step i), the swelling treatment time is 12-24 hours; in the step ii), the volume ratio of the ethylenediamine to the ethanol in the mixed solution is 1: 1; the mass-to-volume ratio of the chloromethylated polystyrene resin to the mixed solution is 1: 2-3.
5. The method for synchronously reducing and adsorbing hexavalent chromium in water body by using ethylenediamine-based resin according to claim 3, wherein the temperature of the grafting reaction in step ii) is 55-65 ℃ and the time is 8-12 h.
6. The method for simultaneously reducing-adsorbing hexavalent chromium in water according to claim 1, wherein the temperature of the filtrate passing through the adsorption tower filled with the ethylenediamine-based resin in the step (2) is 5 to 40 ℃, and the flow rate of the filtrate is less than 30 bed volumes per hour of the resin bed.
7. The method for synchronously reducing-adsorbing hexavalent chromium in water bodies by using ethylenediamine-based resin according to claim 1, wherein in the step (3), the adsorption leakage point is that the mass concentration of total chromium in effluent is greater than 0.01 mg/L based on the mass of chromium element.
8. The method for synchronously reducing-adsorbing hexavalent chromium in water by using ethylenediamine-based resin according to claim 1, wherein in the step (3), the alkali solution is an aqueous solution of NaOH with a concentration of 2-10% by weight; when the alkali liquor passes through the ethylenediamine-based resin, regeneration is carried out at the flow rate of 1-5 resin bed volumes per hour at the temperature of 15-60 ℃.
9. The method for synchronously reducing-adsorbing hexavalent chromium in water by using ethylenediamine-based resin according to claim 1, wherein in the step (3), the acid solution is an aqueous solution of sulfuric acid or nitric acid having a concentration of 1-5% by weight, and is regenerated at a flow rate of 1-5 bed volumes of the resin layer per hour at 15-60 ℃.
10. The method for synchronously reducing-adsorbing hexavalent chromium in water body by using ethylenediamine-based resin according to claim 1, wherein the steps (2) and (3) are performed by a single-tower adsorption-desorption or multi-tower series adsorption-single-tower desorption operation.
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| CN113233536A (en) * | 2021-03-31 | 2021-08-10 | 浙江工业大学 | Method for directionally reducing nitrite in water body by using ethylenediamine resin-based zero-valent palladium nano composite material |
| CN114984929A (en) * | 2022-06-06 | 2022-09-02 | 浙江工业大学 | Ethylenediamine resin zero-valent iron-loaded nanocomposite, preparation method thereof and application thereof in synchronous reduction and trapping of hexavalent chromium in water |
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