CN110407283B - Control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater - Google Patents

Control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater Download PDF

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CN110407283B
CN110407283B CN201910675796.3A CN201910675796A CN110407283B CN 110407283 B CN110407283 B CN 110407283B CN 201910675796 A CN201910675796 A CN 201910675796A CN 110407283 B CN110407283 B CN 110407283B
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vanadium
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resin
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高亚娟
汪林
邵燕
唐凯
朱兆坚
张炜铭
吕振华
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Jiangsu Nju Environmental Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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    • 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
    • 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
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    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/04—Oxidation reduction potential [ORP]
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Abstract

The invention discloses a control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater, belonging to the field of wastewater treatment, and the method comprises the following steps: 1) the reducing agent is added in an amount according to M1 ═ a × ln (ORP)1‑ORP2) Calculated by the formula B, ORP1For initial redox potential, ORP2Is a set post-reduction redox potential; 2) adjusting the pH of the wastewater to 3-4 by using alkaline liquor, and measuring the oxidation-reduction potential ORP3(ii) a 3) Adding an oxidant, and setting an oxidation-reduction potential target value ORP4，ORP4Set between 450 and 550mv, the oxidant is according to M2 ═ C (ORP)4‑ORP3) -a D calculation; 4) and (4) resin adsorption. The pretreatment of the invention can greatly improve the subsequent resin separation efficiency, and simultaneously establish the relationship between the oxidation-reduction potential and the material, thereby achieving the purpose of more accurate control.

Description

Control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater
Technical Field
The invention belongs to the field of wastewater resource utilization, and relates to a control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater.
Background
The vanadium precipitation wastewater is strongly acidic and high-salt wastewater, the pH value of the wastewater is about 2, the salt is mainly sodium sulfate and ammonium sulfate, the content of the ammonium sulfate is about 2.8%, the content of the sodium sulfate is about 14%, the content of organic matters in the wastewater is less than 100mg/L, the heavy metal elements are mainly vanadium and chromium, the content of vanadium is 660-680 mg/L, the content of chromium is about 1900-2500 mg/L, and the contents are high.
For the related applications disclosed in the prior art for treating vanadium-chromium containing wastewater, such as chinese patent application No. CN201510004197.0, published as 2015, 4-month, 29, a method for treating vanadium-chromium containing wastewater is disclosed, which comprises the following steps: 1) adsorption: adopting an adsorption medium to adsorb vanadium and chromium ions in the vanadium and chromium-containing wastewater; 2) and (3) analysis: adding an analytical agent into the adsorption medium containing vanadium and chromium ions obtained in the step 1) for analysis; 3) and (3) vanadium precipitation: adding an alkaline substance into the desorption solution, uniformly stirring, and filtering to obtain a calcium vanadate product and a vanadium precipitation supernatant; 4) and (3) chromium crystallization: evaporating, concentrating, cooling and crystallizing the vanadium precipitation supernatant to obtain a sodium chromate crude product and a crystallization mother liquor; 5) and (3) recrystallization: heating and dissolving the sodium chromate crude product, cooling and crystallizing to obtain a sodium chromate product and a cooling and crystallizing mother liquor; 6) and (3) returning crystallization mother liquor: the crystallization mother liquor is returned to the step 2) to be used as the ingredient of the desorption solution for recycling. The method has the advantages that the recovery rate of vanadium and chromium elements in the wastewater reaches more than 99.9 percent, high-purity calcium vanadate and sodium chromate are obtained, and no wastewater or waste residue is generated in the whole process. The patent realizes the separation of vanadium and chromium in the wastewater in the desorption liquid, but if the valence states of vanadium and chromium in the wastewater are in a mixed state and the pH value in the wastewater rises along with the increase of the adding amount of alkaline substances, the co-precipitation of vanadium and chromium in the wastewater can be caused, and the purpose of vanadium and chromium separation cannot be realized.
At present, the adsorption media commonly used for recovering vanadium in vanadium-chromium wastewater are different types of ion exchange resins, and the principle of the adsorption media is that vanadium ions are diffused to the surface of the resin from water and exchange with ions on the resin, so that the adsorption of the vanadium is achieved.
Upon search, related applications exist in the prior art. For example, the application of Chinese patent application No. 201610239028.X with publication date of 2018, 6, 29 discloses a process for deep purification treatment and vanadium and chromium recovery of vanadium-containing wastewater, wherein the treatment process comprises the steps of adjusting the pH value of the vanadium-containing wastewater to 4-6, and sequentially adopting a resin A and a resin B as adsorption media to adsorb the vanadium-containing wastewater, wherein the resin A is chelate ion exchange resin; the resin B is macroporous weak-base anion exchange resin with polyamine; tail liquid of the vanadium-containing wastewater after adsorption can reach the standard and be discharged. The treatment process of the vanadium-containing wastewater is a novel, efficient and low-cost heavy metal wastewater treatment technology, can simultaneously meet the two-point requirements of harmlessness, reclamation (valuable heavy metal recovery) and water recycling of the vanadium-containing wastewater, also belongs to a new environment-friendly emission reduction and resource recovery technology, can improve the standard of 'clean production' implemented in vanadium metallurgy and vanadium application industries, and has obvious economic benefit and social benefit. The method of the application realizes the resource recycling and standard discharge of vanadium by using a two-stage resin method. The resin A chelating ion exchange resin is mainly used for removing metal cation impurities in the wastewater, and the resin B macroporous weak-base anion exchange resin is used for recovering vanadium. Although the method of the application can realize the separation of vanadium and metal cation impurities in the wastewater, the method cannot realize the separation of vanadium and chromium in the wastewater, however, the method of the application provides a thought for the separation of vanadium and chromium, and if the wastewater can be pretreated to a certain extent, the vanadium and chromium are respectively converted into different valence states or ion forms, so that a powerful way is provided for the resin to separate the vanadium and chromium. No relevant pretreatment mode is reported in the literature at present.
In addition, the precise control of the pretreatment and thus the more efficient control of the separation of the two elements is also a problem faced by those skilled in the art due to the problem of water quality fluctuations during wastewater treatment.
Disclosure of Invention
1. Problems to be solved
Aiming at the defects that vanadium and chromium elements are difficult to effectively separate and cannot be accurately controlled in the prior art, the invention provides a pretreatment method capable of realizing vanadium and chromium element separation, and simultaneously, the material adding amount in the pretreatment process can be accurately controlled.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater, which comprises the following steps:
(1) determination of the initial Oxidation-reduction potential ORP of the wastewater1The ORP1Unit is mv; adding a reducing agent into the vanadium precipitation wastewater in a unit of g/L for reduction after the determination, and setting the oxidation-reduction potential value after the reduction is finished as ORP2The ORP2Unit is mv; the adding amount M of the reducing agent is calculated according to a formula 1:
M1＝A*ln(ORP1-ORP2) -B formula 1;
A＝3±0.3；B＝5.7±0.57；
(2) taking the effluent obtained in the step (1), adjusting the pH value of the wastewater by using alkaline liquor, stirring until the pH value is stabilized to 3-4, and measuring the oxidation-reduction potential ORP after the alkaline adjustment is finished3The ORP3Unit is mv;
(3) taking the effluent in the step (2), adding an oxidant in a unit of ml/L for oxidation, and setting the oxidation-reduction potential target value after the oxidation as ORP4The ORP4Setting the amount of the oxidant M2 to be 450-550 mv, and calculating the addition amount of the oxidant M2 according to the formula 2:
M2＝C*(ORP4-ORP3) -D formula 2;
C＝0.023±0.002；D＝0.75±0.075
(4) and (4) performing resin adsorption on the water sample treated in the step (3) to realize the separation of vanadium and chromium.
The principle of the pretreatment of the invention is as follows: the existing valence state of the vanadium-chromium element in the raw water is complex and exists in a mixed form of a high valence state and a low valence state. Therefore, before resin adsorption, strengthening pretreatment is required to convert vanadium and chromium into different ion forms, and reduction and oxidation pretreatment steps are required in the conversion process.
The main purpose of the reduction is to reduce the vanadium and chromium elements to a low-valence state, and Cr is reduced under acidic conditions6+Is easily reduced into Cr3+. In the reduction reaction, the following reactions mainly occurThe following steps are required:
Cr2O7 2-→Cr3+(reduction from +6 to + 3);
CrO4 2-→Cr3+(reduction from +6 to + 3);
CrO2 -→Cr3+(reduction from +6 to + 3);
the high-valence vanadium element in the wastewater is converted into the low-valence vanadium element, and the following reactions mainly occur:
VO2 +→VO2+(reduction from +5 to + 4);
by simultaneously and accurately controlling the pH value and the oxidation-reduction potential, the vanadium element is finally in the H state2V10O28 4-、HV10O28 5-In the anionic state, the chromium element is Cr3+The cationic state of (a).
After the reduction reaction, the reduced wastewater needs to be oxidized again, the existence form of vanadium under different pH conditions is shown in figure 1, and the vanadium is oxidized to form VO2+→VO2 +(from +4 to +5), and when the oxidation-reduction potential is controlled to be 450-550 mv, the vanadium element is mainly H2V10O28 4-、HV10O28 5-In the form of anions of (A), chromium being Cr3+After pretreatment, the vanadium and chromium elements which are difficult to be separated by the resin are respectively converted into anion form and low-valence cation form, so that great convenience is provided for subsequent resin separation, the resin separation efficiency is improved, and the types of the resin can be selected from anion resin or chelating resin, so that the method has an excellent separation effect.
As a further development of the invention, the resin comprises an anionic resin or a chelating resin.
As a further improvement of the invention, the reducing agent is one or a combination of several of sodium thiosulfate, sodium sulfite and sodium metabisulfite.
As a further improvement of the invention, the lye comprises a sodium hydroxide solution and a potassium hydroxide solution.
As a further improvement of the invention, the resin reducing agent and the oxidizing agent are added in two or more stages;
as a further improvement of the invention, the time of the reduction reaction in the step (1) is 30-120 min.
As a further improvement of the invention, the ORP2Set between 500-620 mv.
As a further improvement of the invention, the type of the oxidant is hydrogen peroxide with the mass concentration of 30%, and the oxidation reaction time is 30-120 min.
As a further improvement of the method, the pH value of the wastewater is maintained to be 3-4 in the oxidation reaction process.
As a further improvement of the invention, the chelating resins include guanidine, pyridine and oxime chelating resins.
3. Advantageous effects
(1) The control method for the resin adsorption separation strengthening pretreatment of the vanadium precipitation wastewater comprises the steps of firstly reducing the vanadium precipitation wastewater, then adding alkali liquor to neutralize the wastewater and controlling the pH value of the wastewater to be 3-4, then carrying out oxidation treatment and controlling the oxidation-reduction potential of the wastewater to be 450-550 mv, and carrying out the pretreatment to ensure that vanadium in the wastewater is H2V10O28 4-、HV10O28 5-In the anionic state, chromium is Cr3+The cationic state of (a); thereby providing great convenience for subsequent resin separation, improving the resin separation efficiency, and selectively adsorbing the vanadium element by selecting the anion resin or the chelating resin, thereby using Cr as the chromium element3+The purpose of keeping the cation state in the wastewater is high separation efficiency.
(2) The control method for the resin adsorption separation strengthening pretreatment of the vanadium precipitation wastewater establishes a formula relationship among an initial oxidation-reduction potential, a reduced target oxidation-reduction potential and a reducing agent, and a formula relationship among an oxidation-reduction potential after finishing alkali adjustment, a set target oxidation-reduction potential and an oxidizing agent, so that the formula relationship can be obtained in a calculation modeThe adding amount of the reducing agent and the oxidizing agent can achieve the purpose of accurate control on one hand: make the water body have H2V10O28 4-、HV10O28 5-In the anionic state, the chromium is mainly Cr3+The state control that exists of cation is more accurate to realize follow-up more efficient separation, on the other hand avoid the treatment effeciency that the volume of throwing of medicament is not enough to bring to reduce or throw the waste that the excessive volume of throwing caused, practice thrift the running cost greatly.
(3) The control method for the resin adsorption separation strengthening pretreatment of the vanadium precipitation wastewater can automatically adjust the adding amount of the reducing agent and the oxidizing agent according to the data of the online redox monitor, thereby being capable of resisting the inconvenience caused by the change of the adding amount of the medicament due to the large water quality fluctuation.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The operation steps of the vanadium precipitation wastewater aimed at in the embodiment are as follows:
(1) taking 1L of vanadium precipitation wastewater, wherein the initial pH of the wastewater is 1.78, and the initial oxidation-reduction potential ORP1684.2 mv;
(2) reducing, adding sodium thiosulfate as reducing agent into raw water, and performing reduction reaction to obtain reduction potential ORP2The adding amount M1 of the reducing agent can be calculated by a calculation formula of the reducing agent, namely, the adding amount is set to be 600 mv:
M1＝A*ln(ORP1-ORP2) -B formula 1;
A＝3±0.3；B＝5.5±0.5；
in the embodiment, 2.7 is taken as A, 6 is taken as B, so that the adding amount of the reducing agent can be calculated to be 6.0g/L, and the reaction time is 60min after the reducing agent is added;
(3) adjusting alkali of the reduced water sample by using sodium hydroxidepH to 3, oxidation-reduction potential ORP after pH stabilization3A value of 351.2 mv;
(4) oxidizing the water sample after alkali adjustment, adding hydrogen peroxide with the mass concentration of 30%, and setting the target oxidation-reduction potential ORP after the oxidation reaction is completed in advance4In this embodiment, ORP is set4With a value of 550mv, the oxidant addition M2 was calculated, i.e.:
M2＝C*(ORP4-ORP3) -D formula 2;
C＝0.023±0.002；D＝0.75±0.075；
in the embodiment, 0.021 is taken as C, 0.825 is taken as D, so that the adding amount of the oxidant can be calculated to be 3.4ml/L, and the reaction time is 60min after the oxidant is added;
(5) in the water sample treated in the step (4), the vanadium element is mainly H2V10O28 4-、HV10O28 5-In the form of anions, chromium being predominantly Cr3+The method adopts pyridine chelating resin for adsorption, has high separation efficiency, keeps the concentration of vanadium in the wastewater unchanged, reduces the concentration of vanadium from 499.8mg/L to 0.62mg/L, and completes the fractional recovery of vanadium and chromium. Table 1 shows the statistics of the concentrations of vanadium and chromium before and after wastewater treatment.
TABLE 1 separation results of V-Cr waste water
Figure BDA0002143216090000051
Example 2
The operation steps of the vanadium precipitation wastewater aimed at in the embodiment are as follows:
(1) taking 1L of vanadium precipitation wastewater, wherein the initial pH of the wastewater is 1.78, and the initial oxidation-reduction potential ORP1684.2 mv;
(2) reducing, adding reducing agent sodium thiosulfate into raw water, and performing oxidation-reduction potential ORP after the reduction reaction is completed2The value is 620mv, and the adding amount M1 of the reducing agent can be calculated by a calculation formula of the reducing agent, namely:
M1＝A*ln(ORP1-ORP2) -B isFormula 1;
A＝3±0.3；B＝5.5±0.5；
in the embodiment, 3.3 is taken as A, 5 is taken as B, so that the adding amount of the reducing agent can be calculated to be 8.7g/L, the reducing agent sodium thiosulfate can be added in a grading manner, 5g is added in the first stage, and the reaction time is 30 min; 3.7g of the second-stage addition, and the reaction time is 30 min.
(3) Adjusting the pH of the reduced water sample to 3.5 by using sodium hydroxide, and adjusting the oxidation-reduction potential ORP after the pH is stable3A value of 400.5 mv;
(4) oxidizing the water sample after alkali adjustment, adding hydrogen peroxide with the mass concentration of 30%, and setting the target oxidation-reduction potential ORP after the oxidation reaction is completed in advance4In this embodiment, ORP is set4The value is 480mv, and the adding amount M2 of the oxidant can be calculated by the calculation formula of the oxidant, namely:
M2＝C*(ORP4-ORP3) -D formula 2;
C＝0.023±0.002；D＝0.75±0.075
in the embodiment, C is 0.025, D is 0.675, so that the adding amount of the oxidant can be calculated to be 1.3ml/L, the pH value of the wastewater is kept stable at 3 in the reaction process, and the reaction time is 60min after the oxidant is added;
(5) in the water sample treated by the step 4), the vanadium element is mainly H2V10O28 4-、HV10O28 5-In the form of anion, the chromium is mainly Cr3+The anion resin is adopted for adsorption, the separation efficiency is high, the concentration of vanadium in the wastewater is unchanged, the concentration of the vanadium is reduced from 499.8mg/L to 48.8mg/L, and the step recovery of vanadium and chromium is completed. Table 2 shows the statistics of the concentrations of vanadium and chromium before and after wastewater treatment.
TABLE 2 separation results of V-Cr waste water
Figure BDA0002143216090000061
Example 3
The operation steps of the vanadium precipitation wastewater aimed at in the embodiment are as follows:
(1) taking 1L of vanadium precipitation wastewater, wherein the initial pH of the wastewater is 1.81, and the initial oxidation-reduction potential ORP1691.2 mv;
(2) carrying out reduction treatment, adding sodium pyrosulfite serving as a reducing agent into raw water, and carrying out ORP (oxidation-reduction potential) on a target oxidation-reduction potential after complete reduction reaction2The value is 550mv, and the addition amount M1 of the reducing agent can be calculated by a calculation formula of the reducing agent, namely:
M1＝A*ln(ORP1-ORP2) -B formula 1;
A＝3±0.3；B＝5.5±0.5；
in the embodiment, 3 is taken as A, 5.5 is taken as B, so that the adding amount of the reducing agent can be calculated to be 9.35g/L, the reducing agent sodium thiosulfate can be added in a grading manner, 6g is added in the first stage, and the reaction time is 30 min; 3g is added in the second stage, the reaction time is 40min, 0.35g is added in the third stage, and the reaction time is 30 min.
(3) Adjusting the pH of the reduced water sample to 3.8 by using sodium hydroxide, and adjusting the oxidation-reduction potential ORP after the pH is stable3A value of 385.6 mv;
(4) oxidizing the water sample after adjusting the alkali, adding hydrogen peroxide with the mass concentration of 30%, and setting the target oxidation-reduction potential ORP after the oxidation reaction is completed in advance4In this embodiment, ORP is set4The value is 500mv, and the adding amount M2 of the oxidant can be calculated by the calculation formula of the oxidant, namely:
M2＝C*(ORP4-ORP3) -D formula 2;
C＝0.023±0.002；D＝0.75±0.075
in the embodiment, 0.023 is taken as C, 0.75 is taken as D, so that the adding amount of the oxidant can be calculated to be 1.9ml/L, the pH value of the wastewater is kept stable at 3.5 in the reaction process, and the reaction time is 100min after the oxidant is added;
(5) in the water sample treated by the step 4), the vanadium element is mainly H2V10O28 4-、HV10O28 5-In the form of anions, chromium being predominantly Cr3+The cationic form of the guanidine chelate resin exists, guanidine chelate resin is adopted for adsorption,the separation efficiency is high, the concentration of vanadium in the wastewater is unchanged, the concentration of vanadium is reduced from 499.8mg/L to 0.61mg/L, and the step recovery of vanadium and chromium is completed. Table 3 shows the statistics of the concentrations of vanadium and chromium before and after wastewater treatment.
TABLE 3 separation results of V-Cr waste water
Figure BDA0002143216090000071
Example 4
The operation steps of the vanadium precipitation wastewater aimed at in the embodiment are as follows:
(1) taking 1L of vanadium precipitation wastewater, wherein the initial pH of the wastewater is 1.50, and the initial oxidation-reduction potential ORP1702.6 mv;
(2) reducing, adding sodium sulfite as reducing agent into raw water, and setting the oxidation-reduction potential ORP after complete reduction reaction2In this embodiment, ORP is set2The value is 500mv, and the addition amount M1 of the reducing agent can be calculated by a calculation formula of the reducing agent, namely:
M1＝A*ln(ORP1-ORP2) -B formula 1;
A＝3±0.3
B＝5.5±0.5
in this example, A was 3.3 and B was 6. Therefore, the adding amount of the reducing agent can be calculated to be 11.5g/L, and the reaction time after the reducing agent is added is 100 min;
(3) adjusting the pH of the reduced water sample to 4 by using sodium hydroxide, and adjusting the oxidation-reduction potential ORP after the pH is stable3A value of 310.3 mv;
(4) oxidizing the water sample after adjusting the alkali, adding hydrogen peroxide with the mass concentration of 30%, and setting the target oxidation-reduction potential ORP after the oxidation reaction is completed4The value is 450mv, and the adding amount M2 of the oxidant can be calculated by the calculation formula of the oxidant, namely:
M2＝C*(ORP4-ORP3) -D formula 2;
C＝0.023±0.002；D＝0.75±0.075
in the embodiment, C is 0.025, D is 0.825, so that the adding amount of the oxidant can be calculated to be 2.7ml/L, the pH value of the wastewater is kept stable at 4 in the reaction process, and the reaction time is 120min after the oxidant is added;
(5) in the water sample treated in the step (4), the vanadium element is mainly H2V10O28 4-、HV10O28 5-In the form of anion, the chromium is mainly Cr3+The method adopts pyridine chelating resin for adsorption, has high separation efficiency, keeps the concentration of vanadium in the wastewater unchanged, reduces the concentration of vanadium from 499.8mg/L to 0.60mg/L, and completes the fractional recovery of vanadium and chromium. Table 4 shows the statistics of the concentrations of vanadium and chromium before and after wastewater treatment.
TABLE 4 separation results of V-Cr waste water
Figure BDA0002143216090000081
Example 5
The operation steps of the vanadium precipitation wastewater aimed at in the embodiment are as follows:
(1) taking 1L of vanadium precipitation wastewater, wherein the initial pH of the wastewater is 1.50, and the initial oxidation-reduction potential ORP1702.6 mv;
(2) reducing, adding sodium sulfite as reducing agent into raw water, and setting the oxidation-reduction potential ORP after complete reduction reaction2In this embodiment, ORP is set2The value is 510mv, and the adding amount M1 of the reducing agent can be calculated by a calculation formula of the reducing agent, namely:
M1＝A*ln(ORP1-ORP2) -B formula 1;
A＝3±0.3；B＝5.5±0.5
in the embodiment, 2.7 is taken as A, 5 is taken as B, so that the adding amount of the reducing agent can be calculated to be 9.2g/L, and the reaction time is 100min after the reducing agent is added;
(3) adjusting the pH of the reduced water sample to 4 by using sodium hydroxide, and adjusting the oxidation-reduction potential ORP after the pH is stable3A value of 330.3 mv;
(4) oxidizing the water sample after adjusting the alkali, adding hydrogen peroxide with the mass concentration of 30 percent, and settingDetermining the target oxidation-reduction potential ORP after the oxidation reaction is completed4The value is 450mv, and the adding amount M2 of the oxidant can be calculated by the calculation formula of the oxidant, namely:
M2＝C*(ORP4-ORP3) -D formula 2;
C＝0.023±0.002；D＝0.75±0.075
in this example, C is 0.021 and D is 0.675. Therefore, the adding amount of the oxidant can be calculated to be 1.8ml/L, the pH value of the wastewater is maintained to be stable at 4 in the reaction process, and the reaction time is 120min after the oxidant is added;
(5) in the water sample treated in the step (4), the vanadium element is mainly H2V10O28 4-、HV10O28 5-In the form of anion, the chromium is mainly Cr3+The method adopts pyridine chelating resin for adsorption, has high separation efficiency, keeps the concentration of vanadium in the wastewater unchanged, reduces the concentration of vanadium from 499.8mg/L to 0.60mg/L, and completes the fractional recovery of vanadium and chromium. Table 5 is the vanadium chromium concentration statistics before and after wastewater treatment.
TABLE 5 separation results of V-Cr waste water
Figure BDA0002143216090000091

Claims (8)

1. A control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) determination of the initial Oxidation-reduction potential ORP of the wastewater1The ORP1Unit is mv; adding a reducing agent into the vanadium precipitation wastewater in a unit of g/L for reduction after the determination, and setting the oxidation-reduction potential value after the reduction is finished as ORP2The ORP2Unit is mv; the adding amount M1 of the reducing agent is calculated according to the formula 1:
M1=A*ln（ORP1-ORP2) -B formula 1;
in the formula: a =3 ± 0.3; b =5.7 ± 0.57;
(2) taking the effluent obtained in the step (1), adjusting the pH value of the wastewater by using alkaline liquor, stirring until the pH value is stabilized to 3-4, and measuring the oxidation-reduction potential ORP after the alkaline adjustment is finished3The ORP3Unit is mv;
(3) taking the effluent in the step (2), adding an oxidant in a unit of ml/L for oxidation, and setting the oxidation-reduction potential target value after the oxidation as ORP4The ORP4Setting the amount of the oxidant M2 to be 450-550 mv, and calculating the addition amount of the oxidant M2 according to the formula 2:
M2=C*（ORP4 - ORP3) -D formula 2;
in the formula: c =0.023 ± 0.002; d =0.75 ± 0.075;
(4) performing resin adsorption on the water sample treated in the step (3) to realize the separation of vanadium and chromium;
subjecting the ORP to2Setting the range between 500mv and 620 mv;
the resin comprises a chelating resin.
2. The control method for the resin adsorption separation reinforcement pretreatment of vanadium precipitation wastewater according to claim 1, characterized in that: the alkali liquor comprises any one of sodium hydroxide solution and potassium hydroxide solution.
3. The control method for the resin adsorption separation reinforcement pretreatment of vanadium precipitation wastewater according to claim 2, characterized in that: the reducing agent is one or more of sodium thiosulfate, sodium sulfite and sodium metabisulfite.
4. The control method for the resin adsorption separation reinforcement pretreatment of vanadium precipitation wastewater according to claim 3, characterized in that: the time of the reduction reaction in the step (1) is 30-120 min.
5. The control method for the resin adsorption separation reinforcement pretreatment of vanadium precipitation wastewater according to claim 1, characterized in that: the oxidant is hydrogen peroxide with the mass concentration of 30%, and the oxidation reaction time is controlled to be 30-120 min.
6. The control method for the resin adsorption separation reinforcement pretreatment of vanadium precipitation wastewater according to claim 5, characterized in that: and maintaining the pH value of the wastewater to be 3-4 in the oxidation reaction process.
7. The control method for the resin adsorption separation reinforcement pretreatment of vanadium precipitation wastewater according to claim 1, characterized in that: the chelating resin comprises guanidine chelating resin, pyridine chelating resin and oxime chelating resin.
8. The control method for the resin adsorption separation reinforcement pretreatment of vanadium precipitation wastewater according to claim 1, characterized in that: and the oxidant and the reducer are respectively added in a grading mode.
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Publication number Priority date Publication date Assignee Title
CN102925686A (en) * 2012-11-14 2013-02-13 重庆大学 Method for selectively separating and extracting vanadium and chromium from solution containing vanadium and chromium
CN103421953A (en) * 2013-07-29 2013-12-04 大连博融新材料有限公司 Method for deep separation of vanadium and molybdenum
CN107190155A (en) * 2017-05-19 2017-09-22 重庆大学 Vanadium, the method for chromium are extracted in a kind of mixed liquor from containing vanadium and chromium

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BRPI1010875A2 (en) * 2009-04-30 2016-03-15 World Resources Co process for the recovery of metals and metal compounds from extracted ore and other metal-containing raw materials

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Publication number Priority date Publication date Assignee Title
CN102925686A (en) * 2012-11-14 2013-02-13 重庆大学 Method for selectively separating and extracting vanadium and chromium from solution containing vanadium and chromium
CN103421953A (en) * 2013-07-29 2013-12-04 大连博融新材料有限公司 Method for deep separation of vanadium and molybdenum
CN107190155A (en) * 2017-05-19 2017-09-22 重庆大学 Vanadium, the method for chromium are extracted in a kind of mixed liquor from containing vanadium and chromium

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