CN112299602A - Purification system and method for separating nickel and chromium in water - Google Patents
Purification system and method for separating nickel and chromium in water Download PDFInfo
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- CN112299602A CN112299602A CN202011100268.4A CN202011100268A CN112299602A CN 112299602 A CN112299602 A CN 112299602A CN 202011100268 A CN202011100268 A CN 202011100268A CN 112299602 A CN112299602 A CN 112299602A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Abstract
The invention provides a purification system and a purification method for separating nickel and chromium in water, wherein the purification method comprises the following steps: adding acid and a reducing agent into the water containing nickel and chromium, uniformly mixing and reacting to convert the chromium in the water into trivalent chromium ions and convert the nickel in the water into divalent nickel ions; adding strong base to remove NH4 +Adjusting the pH of the water to 2.5-4; mixing with a first-stage ion exchange resin; the primary ion exchange resin contains sulfonic functional groups; and controlling the pH to be 3-5, and mixing with a secondary ion exchange resin, wherein the secondary ion exchange resin contains imino functional groups. The method for separating nickel and chromium in water adopts a two-stage resin adsorption process to adsorb and separate the precipitated asynchronous nickel and chromium in the wastewater, thereby solving the problems of large dosage, multiple valence states and multiple chemical precipitation agents in the conventional physicochemical pretreatment processLow removal rate of morphological heavy metal ions and the like.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a purification system and a purification method for separating nickel and chromium in water.
Background
At the present stage, for the pretreatment of the high-concentration heavy metal wastewater, the alkali liquor is mainly added to be removed by a method of converting the alkali liquor into hydroxide. However, due to the presence of a precipitation-dissolution equilibrium, plus the weight in the wastewaterThe concentration of the metal is higher, so that the concentration of the heavy metal in the treated effluent can not meet the requirement of subsequent biochemical advanced treatment. At present, for the condition, a method of adding 1-2 stages of precipitation is mainly adopted to further precipitate the pretreated effluent. However, this method not only greatly increases the construction amount and the construction cost, but also greatly increases the amount of chemicals added and significantly increases the alkalinity of effluent water as soon as different heavy metals are contained in the precipitate and the required precipitation pH value is greatly different. Therefore, in order to overcome the above-mentioned drawbacks, it is necessary to develop a new advanced effluent purification system. Nickel hydroxide (Ni (OH) at ambient temperature2) Has a solubility product of 5.48X 10-16Chromium hydroxide (Cr (OH)3) Has a solubility product of 6.3X 10-31. It can be seen that the difference between the two is large. This makes the nickel hydroxide start to precipitate first with the addition of the alkali liquor when the two exist together in the water and the concentration is not very different, and the chromium hydroxide is generated when the pH value is raised to a certain degree. The two precipitates are asynchronous, so that the dosage of the medicament is large, and the pH value of effluent is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a purification system and a purification method for separating nickel and chromium in water.
In order to achieve the purpose, the invention adopts the technical scheme that: a process for separating nickel and chromium from water, the process comprising the steps of:
(1) adding acid and a reducing agent into the water containing nickel and chromium, uniformly mixing and reacting to convert the chromium in the water into trivalent chromium ions and convert the nickel in the water into divalent nickel ions;
(2) adding strong base into the water obtained in the step (1) to remove NH4 +Adjusting the pH of the water to 2.5-4;
(3) mixing the water obtained in the step (2) with a first-stage ion exchange resin; the primary ion exchange resin contains sulfonic functional groups;
(4) and (4) controlling the pH of the water obtained in the step (3) to be 3-5, and mixing the water with a secondary ion exchange resin, wherein the secondary ion exchange resin contains imino functional groups.
The method for separating nickel and chromium from water comprises converting nickel and chromium in various forms in water into trivalent chromium ion and divalent nickel ion by adding acid and reducing agent, and removing residual NH after reaction4 +The pH value of water is controlled, trivalent chromium ions in the water are adsorbed by ion exchange resin containing sulfonic functional groups, and divalent nickel ions in the water are adsorbed by ion exchange resin containing imino functional groups, so that the problems of large dosage of medicaments and influence on the pH value of effluent caused by treating nickel and chromium in the water by an alkaline precipitation method are solved, the nickel and chromium content in the nickel and chromium-containing water treated by the method for separating nickel and chromium from water is lower than 0.1mg/L, and a good water treatment effect is achieved; the reaction principle of converting nickel and chromium in various forms in water into trivalent chromium ions and divalent nickel ions by adding acid and a reducing agent is as follows:
Cr2O7 2-+3H2O2+8H+→2Cr3++3O2↑+7H2O
[Ni(NH3)4]2++2OH-+6H+→Ni2++4NH4 ++2H2and O. The method for separating nickel and chromium from water adopts a two-stage resin adsorption process to adsorb and separate the nickel and chromium which are precipitated in the wastewater asynchronously, solves a series of problems of large dosage of a drug-added precipitation medicament, multiple valence states, low removal rate of polymorphic heavy metal ions and the like in the conventional physicochemical pretreatment process, and simultaneously provides a feasible method with low investment and operation cost to realize the deep treatment and resource recovery of recoverable metal ions in the wastewater containing the multi-component heavy metals.
Preferably, in the step (3), the primary ion exchange resin is a primary ion exchange resin column, and the water obtained in the step (2) flows through the primary ion exchange resin column at a rate of 1.1-1.35 resin column volumes/min.
The method for separating nickel and chromium in water adsorbs chromium ions in water in the form of resin columns by the primary ion exchange resin, so that the separation of resin and water is facilitated, and continuous treatment can be realized.
Preferably, the step (3) further comprises regenerating the primary ion exchange resin column, and the regenerated regenerant is sulfuric acid, hydrochloric acid or a sodium chloride solution.
The method is realized by adding HCl and H2SO4Or NaCl, can convert the resin saturated with adsorption to H+Resin and Na+And the resin is used for realizing subsequent reutilization. And mixing Cr3+And Ni2+The regenerated liquid is enriched in the regenerated liquid, can be recycled, and avoids secondary pollution.
Preferably, in the step (4), the secondary ion exchange resin is a secondary ion exchange resin column, and the water obtained in the step (3) flows through the secondary ion exchange resin column at a rate of 1.0-1.2 resin column volumes/min.
The method for separating nickel and chromium from water adsorbs nickel ions in water by the primary ion exchange resin in the form of a resin column, so that the separation of resin and water is facilitated, and continuous treatment can be realized.
Preferably, the step (4) further comprises regenerating the secondary ion exchange resin column, and the regenerated regenerant is sulfuric acid, hydrochloric acid or a sodium chloride solution.
The method is realized by adding HCl and H2SO4Or NaCl, can convert the resin saturated with adsorption to H+Resin and Na+And the resin is used for realizing subsequent reutilization. And mixing Cr3+And Ni2+The regenerated liquid is enriched in the regenerated liquid, can be recycled, and avoids secondary pollution.
Preferably, in the step (1), the acid is sulfuric acid, and the reducing agent is hydrogen peroxide; in the step (2), the strong base is sodium hydroxide.
Preferably, the primary ion exchange resin is T-52H high-grade strong acid type nuclear grade ion exchange resin, and the secondary ion exchange resin is CH-90 weak acid type cation exchange resin.
The invention also provides a purification system for separating nickel and chromium in water, which comprises a reaction container, a primary resin adsorption unit and a secondary resin adsorption unit which are communicated in sequence through pipelines;
the reaction vessel is provided with a wastewater inlet, a dosing hopper and a pH detector, the reaction vessel is communicated with a waste gas treatment unit, the primary resin adsorption unit comprises a primary ion exchange resin column, and the primary ion exchange resin column comprises resin containing sulfonic functional groups; the secondary resin adsorption unit comprises a secondary ion exchange resin column comprising a resin comprising imino-functional groups.
The purification system for separating nickel and chromium from water realizes the continuous operation of the method for separating nickel and chromium from water.
Preferably, the waste gas treatment unit includes the setting at the inside draft hood of reaction vessel, and with the fan of draft hood intercommunication, add the hopper including sulphuric acid loading hopper, hydrogen peroxide loading hopper and sodium hydroxide loading hopper.
The waste gas treatment unit is used for treating ammonia gas generated in the treatment process of the reaction container.
Preferably, the primary resin adsorption unit is communicated with a first eluent input unit, and the secondary resin adsorption unit is communicated with a second eluent input unit.
The invention has the beneficial effects that: the invention provides a purification system and a purification method for separating nickel and chromium from water, the method for separating nickel and chromium from water adopts a two-stage resin adsorption process to adsorb and separate asynchronous nickel and chromium precipitated in wastewater, solves a series of problems of large dosage of a drug-added precipitation agent, multiple valence states, low removal rate of multiple-form heavy metal ions and the like in the conventional physicochemical pretreatment process, and simultaneously provides a feasible method with relatively low investment and operation cost to realize deep treatment and resource recovery of recoverable metal ions in wastewater containing multiple-component heavy metals.
Drawings
FIG. 1 is a schematic flow diagram of a process for separating nickel and chromium from water in accordance with an embodiment of the present invention.
FIG. 2 is a schematic diagram of a purification system for separating nickel and chromium from water according to an embodiment of the present invention.
The device comprises a reaction vessel 1, a reaction vessel 11, a sulfuric acid hopper 12, a hydrogen peroxide hopper 13, a sodium hydroxide hopper 14, a wastewater inlet 15, a dosing hopper and a pH detector 2, a primary resin adsorption unit 21, a secondary ion exchange resin column 22, a first eluent input unit 3, a secondary resin adsorption unit 31, a secondary ion exchange resin column 32, a second eluent input unit 4, an exhaust gas treatment unit 41, a fan 42 and an exhaust hood.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
A method of separating nickel and chromium from water as an embodiment of the invention, the method comprising the steps of:
(1) adding sulfuric acid and hydrogen peroxide into water containing nickel and chromium, uniformly mixing and reacting to convert chromium in the water into trivalent chromium ions and convert nickel in the water into divalent nickel ions;
(2) adding sodium hydroxide into the water obtained in the step (1) to remove NH4 +Adjusting the pH of the water to 2.5-4;
(3) enabling the water obtained in the step (2) to flow through a first-stage ion exchange resin column at the rate of 1.1-1.35 resin column volume/min; the first-stage ion exchange resin column comprises first-stage ion exchange resin containing sulfonic functional groups, and the first-stage ion exchange resin is T-52H high-grade strong acid type nuclear-grade ion exchange resin;
(4) controlling the pH of the water obtained in the step (3) to be 3-5, and then flowing the water through a secondary ion exchange resin column at a rate of 1.0-1.2 resin column volumes/min, wherein the secondary ion exchange resin column comprises a secondary ion exchange resin containing imino functional groups, and the secondary ion exchange resin is a CH-90 weak acid type cation exchange resin;
and regenerating the primary ion exchange resin column and the secondary ion exchange resin column, wherein the regenerated regenerant is sulfuric acid, hydrochloric acid or sodium chloride solution.
T-52H high-grade strong acid type nuclear grade ion exchange resin and CH-90 weak acid type cation exchange resin were purchased from Kohaisi (Beijing) science and technology Co.
The purification system for separating nickel and chromium from water, as shown in fig. 2, includes a reaction vessel 1, a primary resin adsorption unit 2 and a secondary resin adsorption unit 3, which are sequentially communicated by pipelines;
the reaction container is provided with a wastewater inlet 14, a dosing hopper and a pH detector 15, the reaction container 1 is communicated with a waste gas treatment unit 4, the primary resin adsorption unit 2 comprises a primary ion exchange resin column 21, and the primary ion exchange resin column 21 comprises resin containing sulfonic functional groups; the secondary resin adsorption unit 3 comprises a secondary ion exchange resin column 31, the secondary ion exchange resin column 31 comprises a resin containing imino functional groups;
the waste gas treatment unit 4 comprises an air draft hood 42 arranged in the reaction vessel and a fan 41 communicated with the air draft hood, and the dosing hopper comprises a sulfuric acid feeding hopper 11, a hydrogen peroxide feeding hopper 12 and a sodium hydroxide feeding hopper 13;
the primary resin adsorption unit 2 is communicated with a first eluent input unit 22, and the secondary resin adsorption unit 3 is communicated with a second eluent input unit 32.
Effect example 1
The process for the separation of nickel and chromium from water described in example 1 was used to treat nickel and chromium containing wastewater.
The indexes of heavy metals in the wastewater containing nickel and chromium are shown in Table 1:
TABLE 1
| The kind of contaminant | Cr3+ | Cr2O7 2- | Ni2+ | [Ni(NH3)4]2+ |
| Concentration (mg/L) | 12.9 | 4.9 | 11.2 | 2.5 |
According to the reaction formula Cr2O7 2-+3H2O2+8H+→2Cr3++3O2↑+7H2O
[Ni(NH3)4]2++2OH-+6H+→Ni2++4NH4 ++2H2O；
Calculating the theoretical dosage of the sulfuric acid, the hydrogen peroxide and the sodium hydroxide, wherein the actual dosage of the sulfuric acid and the hydrogen peroxide in the step (1) of the example 1 is 110 percent of the theoretical dosage, and the reaction time is 20 minutes; the amount of sodium hydroxide used in step (2) of example 1 was 110%.
Indexes of contaminants in the water obtained in step (1) after the conversion are shown in Table 2.
| The kind of contaminant | Cr3+ | Cr2O7 2- | Ni2+ | [Ni(NH3)4]2+ |
| Concentration (mg/L) | 17.6 | - | 13.8 | - |
Cr is detected in the effluent treated by the method for separating nickel and chromium from water in example 13+Less than 0.1mg/L, and Ni2+＜0.1mg/L。
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A process for separating nickel and chromium from water, the process comprising the steps of:
(1) adding acid and a reducing agent into the water containing nickel and chromium, uniformly mixing and reacting to convert the chromium in the water into trivalent chromium ions and convert the nickel in the water into divalent nickel ions;
(2) adding strong base into the water obtained in the step (1) to remove NH4 +Adjusting the pH of the water to 2.5-4;
(3) mixing the water obtained in the step (2) with a first-stage ion exchange resin; the primary ion exchange resin contains sulfonic functional groups;
(4) and (4) controlling the pH of the water obtained in the step (3) to be 3-5, and mixing the water with a secondary ion exchange resin, wherein the secondary ion exchange resin contains imino functional groups.
2. The method according to claim 1, wherein in the step (3), the primary ion exchange resin is a primary ion exchange resin column, and the water obtained in the step (2) flows through the primary ion exchange resin column at a rate of 1.1-1.35 resin column volumes/min.
3. The method according to claim 2, wherein the step (3) further comprises regenerating the primary ion exchange resin column, and the regenerated regenerant is sulfuric acid, hydrochloric acid or a sodium chloride solution.
4. The method according to claim 1, wherein in the step (4), the secondary ion exchange resin is a secondary ion exchange resin column, and the water obtained in the step (3) flows through the secondary ion exchange resin column at a rate of 1.0-1.2 resin column volumes/min.
5. The method according to claim 2, wherein the step (4) further comprises regenerating the secondary ion exchange resin column, and the regenerated regenerant is sulfuric acid, hydrochloric acid or a sodium chloride solution.
6. The method according to claim 1, wherein in the step (1), the acid is sulfuric acid, and the reducing agent is hydrogen peroxide; in the step (2), the strong base is sodium hydroxide.
7. The method of claim 1, wherein the primary ion exchange resin is a T-52H high strong acid type nuclear grade ion exchange resin and the secondary ion exchange resin is a CH-90 weak acid type cation exchange resin.
8. A purification system for separating nickel and chromium in water is characterized by comprising a reaction container, a primary resin adsorption unit and a secondary resin adsorption unit which are sequentially communicated through pipelines;
the reaction vessel is provided with a wastewater inlet, a dosing hopper and a pH detector, the reaction vessel is communicated with a waste gas treatment unit, the primary resin adsorption unit comprises a primary ion exchange resin column, and the primary ion exchange resin column comprises resin containing sulfonic functional groups; the secondary resin adsorption unit comprises a secondary ion exchange resin column comprising a resin comprising imino-functional groups.
9. The purification system according to claim 8, wherein the exhaust gas treatment unit comprises an exhaust hood disposed inside the reaction vessel, and a blower in communication with the exhaust hood, and the dosing hopper comprises a sulfuric acid hopper, a hydrogen peroxide hopper, and a sodium hydroxide hopper.
10. The purification system of claim 8, wherein the primary resin adsorption unit is in communication with a first eluent input unit and the secondary resin adsorption unit is in communication with a second eluent input unit.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0824853A (en) * | 1994-07-15 | 1996-01-30 | Nippon Denko Kk | Apparatus for purifying and reutilizing waste chromium solution and use thereof |
| CN101428933A (en) * | 2008-12-09 | 2009-05-13 | 中南大学 | Biological agent cooperated hydrolyzation-blowing off treatment process for nickel-ammonia wastewater |
| CN101633538A (en) * | 2009-08-24 | 2010-01-27 | 杭州海拓环境工程有限公司 | Recycling and processing method of electroplating concentrated control zone mixed flow waste water resource |
| WO2014199193A1 (en) * | 2013-06-10 | 2014-12-18 | Trivalent Chrome Cc | Production of chromium oxide |
| CN104609683A (en) * | 2014-12-12 | 2015-05-13 | 浙江工商大学 | Chrome tanning sludge heavy metal chromium regeneration method |
| CN105692768A (en) * | 2016-03-31 | 2016-06-22 | 南京大学 | Method for selectively extracting heavy metals in heavy metal-ammonia complexing wastewater by virtue of chelate resin |
| CN110453074A (en) * | 2019-08-21 | 2019-11-15 | 深圳市祺鑫天正环保科技有限公司 | Nickel recovery method and recovery system in nickeliferous waste liquid |
| CN110563177A (en) * | 2019-09-18 | 2019-12-13 | 重庆耐德环境技术有限公司 | Chromium-containing wastewater online circulating treatment device and method |
-
2020
- 2020-10-14 CN CN202011100268.4A patent/CN112299602A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0824853A (en) * | 1994-07-15 | 1996-01-30 | Nippon Denko Kk | Apparatus for purifying and reutilizing waste chromium solution and use thereof |
| CN101428933A (en) * | 2008-12-09 | 2009-05-13 | 中南大学 | Biological agent cooperated hydrolyzation-blowing off treatment process for nickel-ammonia wastewater |
| CN101633538A (en) * | 2009-08-24 | 2010-01-27 | 杭州海拓环境工程有限公司 | Recycling and processing method of electroplating concentrated control zone mixed flow waste water resource |
| WO2014199193A1 (en) * | 2013-06-10 | 2014-12-18 | Trivalent Chrome Cc | Production of chromium oxide |
| CN104609683A (en) * | 2014-12-12 | 2015-05-13 | 浙江工商大学 | Chrome tanning sludge heavy metal chromium regeneration method |
| CN105692768A (en) * | 2016-03-31 | 2016-06-22 | 南京大学 | Method for selectively extracting heavy metals in heavy metal-ammonia complexing wastewater by virtue of chelate resin |
| CN110453074A (en) * | 2019-08-21 | 2019-11-15 | 深圳市祺鑫天正环保科技有限公司 | Nickel recovery method and recovery system in nickeliferous waste liquid |
| CN110563177A (en) * | 2019-09-18 | 2019-12-13 | 重庆耐德环境技术有限公司 | Chromium-containing wastewater online circulating treatment device and method |
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Application publication date: 20210202 |