CN110407283A - A kind of control method of vanadium wastewater resin adsorption separation strenuous primary treatment - Google Patents
A kind of control method of vanadium wastewater resin adsorption separation strenuous primary treatment Download PDFInfo
- Publication number
- CN110407283A CN110407283A CN201910675796.3A CN201910675796A CN110407283A CN 110407283 A CN110407283 A CN 110407283A CN 201910675796 A CN201910675796 A CN 201910675796A CN 110407283 A CN110407283 A CN 110407283A
- Authority
- CN
- China
- Prior art keywords
- orp
- vanadium
- control method
- primary treatment
- oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
-
- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/04—Oxidation reduction potential [ORP]
-
- 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
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of control methods of vanadium wastewater resin adsorption separation strenuous primary treatment, belong to field of waste water treatment, the described method comprises the following steps: 1) reducing agent are added, additional amount is according to M1=A*ln (ORP1‑ORP2) calculating of-B formula, ORP1For initial oxidation reduction potential, ORP2For oxidation-reduction potential after the reduction of setting；2) wastewater pH is adjusted to 3~4 with lye, measure oxidation-reduction potential ORP3；3) oxidant is added, sets oxidation-reduction potential target value ORP4, ORP4It is set between 450~550mv, the oxidant is according to M2=C* (ORP4‑ORP3)-D calculating；4) resin adsorption.Pretreatment of the invention is greatly improved subsequent resin separative efficiency, while establishing the relationship between oxidation-reduction potential and material, reaches more accurate control purpose.
Description
Technical field
The invention belongs to utilization of wastewater resource field, it is related to a kind of vanadium wastewater resin adsorption separation strenuous primary treatment
Control method.
Background technique
Vanadium wastewater is a kind of highly acid, high slat-containing wastewater, and the pH of waste water is 2 or so, and salinity is mainly sodium sulphate and sulphur
Sour ammonium, wherein ammonium sulphate content is about 2.8%, and sodium sulphate content is about 14%, and content of organics is less in waste water, is less than
100mg/L, heavy metal element are mainly vanadium chromium, wherein the content of vanadium between 660~680mg/L, the content of chromium 1900~
2500mg/L or so, content are higher.
Processing for vanadium chromium waste water discloses relevant application case, such as Chinese Patent Application No. in the prior art
CN201510004197.0, publication date are that the application case on April 29th, 2015 discloses a kind of side of the processing containing vanadium, chromium waste water
Method is included the following steps: 1) to adsorb: be adsorbed using adsorbing medium to containing vanadium, the chromium ion in vanadium, chromium waste water；2) it solves
Analysis: parsing agent is added to the adsorbing medium containing vanadium, chromium ion that step 1) obtains and is parsed；3) precipitation: into desorbed solution
Alkaline matter is added to filter after mixing evenly, obtains vanadic acid calcium product and precipitation supernatant；4) chromium crystallize: by precipitation supernatant into
Row is concentrated by evaporation and crystallisation by cooling obtains sodium chromate crude product and crystalline mother solution；5) it recrystallizes: sodium chromate crude product heat molten
Solution, crystallisation by cooling obtain sodium chromate product and crystallisation by cooling mother liquor；6) crystalline mother solution returns: crystalline mother solution return step 2) conduct
The recycling of desorbed solution ingredient.The present invention reaches 99.9% or more, while obtaining high-purity to vanadium in wastewater, the chromium rate of recovery
Calcium vanadate and sodium chromate, whole flow process without waste water and dregs generate.The patent realizes point of vanadium in wastewater chromium in desorption liquid
From, if but the valence state of vanadium in wastewater chromium be admixture, and with the dosage of alkaline matter increase waste water in pH rise, meeting
The coprecipitated of vanadium in wastewater chromium is caused, cannot achieve the purpose of vanadium chromium separation.
It is directed to the more common adsorbing medium of recycling of vanadium chromium vanadium in wastewater element at present as the friendship of different types of ion
Resin is changed, principle is to make vanadium ion from diffusing to resin surface in water and exchanging with the ion on resin, to reach
To the absorption of vanadium.
It is retrieved, relevant application case exists in the prior art.It is open such as Chinese Patent Application No. 201610239028.X
Date is that the application case on June 29th, 2018 discloses the technique of a kind of processing of vanadium-containing water deep purifying and recycling vanadium chromium,
Treatment process is adjusted the pH value of vanadium-containing water to 4~6, is successively given up as adsorbing medium to containing vanadium using Resin A and resin B
Water is adsorbed, and Resin A is chelating ion exchange resin；Resin B is the macroreticular weakly base anion exchange with polyamines base
Resin；Tail washings of the vanadium-containing water after adsorbing can qualified discharge.The treatment process of the vanadium-containing water be it is novel, efficient, low at
This heavy metal wastewater thereby Treatment process, can be achieved at the same time that vanadium-containing water is innoxious to follow with recycling (valuable heavy metal recovery) with water
Loopback is required with 2 points, also belongs to environmental emission reduction and resource reclaim new technology, vanadium metallurgy can be improved, vanadium application industry is implemented " clearly
Clean production " standard, there is apparent economic benefit and social benefit.The method of this application realizes vanadium using two-stage resin method
Recycling reuse and qualified discharge.Resin A chelating ion exchange resin resin used in it be mainly used in waste water metal sun from
The removal of sub- impurity carries out the recycling of vanadium using resin B macroporous weakly basic anion exchange resin.The method of this application
Although can be realized the separation of metal cation impurity in vanadium and waste water, point of vanadium in wastewater chromium cannot achieve
From, however the method for this application provides a kind of thinking for the separation of vanadium chromium, if it is possible to waste water is carried out centainly
Pretreatment, makes vanadium chromium transform into different valence state or ionic species respectively, it will separates vanadium chromium for resin and provides
Strong approach.There is not the relevant pretreatment mode of document report at present.
Further, since pretreated accurate control is realized, thus higher in wastewater treatment process the problem of variation water quality
The separation of two kinds of elements of control of efficiency is equally the problem that those skilled in the art need to face.
Summary of the invention
1. to solve the problems, such as
For the defect that vanadium chromium existing in the prior art is difficult to efficiently separate, and can not accurately be controlled, originally
Patent of invention provides a kind of preprocess method that can be realized the separation of vanadium chromium, while can accurately control in preprocessing process
Material dosage.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
The present invention provides a kind of control methods of vanadium wastewater resin adsorption separation strenuous primary treatment, including following step
It is rapid:
(1) the initial oxidation reduction potential ORP of waste water is measured1, the ORP1Unit is mv；After measurement in vanadium wastewater
Reducing agent is added as unit of g/L to be restored, sets the oxidation reduction potential value after the completion of restoring as ORP2, the ORP2It is single
Position is mv；The reducing agent dosage M is calculated according to formula 1:
M1=A*ln (ORP1-ORP2)-B formula 1；
A=3 ± 0.3；B=5.7 ± 0.57；
(2) it takes step (1) to be discharged, adjusts pH value of waste water, stirring to pH stable to 3~4 with lye, alkali tune is surveyed after the completion
Determine oxidation-reduction potential ORP3, the ORP3Unit is mv；
(3) it takes step (2) to be discharged, oxidant is added as unit of ml/L and is aoxidized, the oxidation after the completion of setting oxidation
Reduction potential target value is ORP4, the ORP4It is set between 450~550mv, the additional amount M2 of the oxidant is according to formula
2 calculate:
M2=C* (ORP4-ORP3)-D formula 2；
C=0.023 ± 0.002；D=0.75 ± 0.075
(4) by step (3) treated, water sample carries out resin adsorption, realizes the separation of vanadium chromium.
It is as follows that the present invention carries out pretreated principle: vanadium chromium in raw water that there are valence states is more complicated, with high price
The mixed form of state and lower valency exists.Therefore, it needs to carry out strenuous primary treatment before resin adsorption, by vanadium and chromium member
Element is finally changed into different ionic forms, and reduction and oxidation pre-treatment step are carried out during transformation.
The main purpose of reduction is that vanadium chromium is restored to the form of lower valency, and Cr in acid condition6+It is easy
It is reduced to Cr3+.Following reaction mainly occurs in reduction reaction:
Cr2O7 2-→Cr3+(being reduced to+3 by+6)；
CrO4 2-→Cr3+(being reduced to+3 by+6)；
CrO2 -→Cr3+(being reduced to+3 by+6)；
High price vanadium is changed into low price vanadium in waste water, main that following reaction occurs:
VO2 +→VO2+(being reduced to+4 by+5)；
By being precisely controlled pH value and oxidation-reduction potential simultaneously, vanadium is made to be ultimately at H2V10O28 4-、HV10O28 5-Yin
Ionic condition, chromium Cr3+Cationic state.
After reduction reaction, also need by reduction after waste water re-start oxidation, under condition of different pH vanadium there are shapes
State is as shown in Figure 1, by oxidation processes, and vanadium is by VO2+→VO2 +The form of (being oxidized to+5 by+4), in control redox
When current potential is 450~550mv, vanadium is mainly with H2V10O28 4-、HV10O28 5-Anionic form exist, chromium Cr3+Sun
Ionic condition, method of the invention will be difficult to be separately converted to anion by the vanadium chromium that resin separates after pretreatment
The cationic form of form and lower valency provides a great convenience for the separation of subsequent resin, improves resin separative efficiency, tree
The type of rouge can choose resin anion (R.A.) or chelate resin, all have excellent separating effect.
As further improvement of the present invention, the resin includes resin anion (R.A.) or chelate resin.
As further improvement of the present invention, the type of reducing agent is sodium thiosulfate, sodium sulfite, sodium pyrosulfite
One or more of combination.
As further improvement of the present invention, the lye includes sodium hydroxide solution and potassium hydroxide solution.
As further improvement of the present invention, the resin reducing agent and oxidant are using side more than two-stage or two-stage
Formula adds；
As further improvement of the present invention, the time of reduction reaction is 30~120min in the step (1).
As further improvement of the present invention, the ORP2It is set between 500~620mv.
As further improvement of the present invention, the type of oxidant is the hydrogen peroxide that mass concentration is 30%, and oxidation is anti-
It is 30~120min between seasonable.
As further improvement of the present invention, it is 3~4 that the pH value of waste water is maintained in the oxidation reaction process.
As further improvement of the present invention, the chelate resin includes guanidine, pyridines and oximes chelating resin.
3. beneficial effect
(1) control method of vanadium wastewater resin adsorption separation strenuous primary treatment of the invention, to vanadium wastewater first into
Row reduction, adding lye and neutralizing and control pH value of waste water is 3~4, then carries out oxidation processes and control the redox of waste water
Current potential is between 450~550mv, and by above-mentioned pretreatment, the vanadium in waste water is with H2V10O28 4-、HV10O28 5-Anion shape
State exists, chromium Cr3+Cationic state exist；To provide great convenience for the separation of subsequent resin, resin point is improved
It from efficiency, selects resin anion (R.A.) or chelate resin that can reach and carries out selective absorption for vanadium, thus by chromium member
Element is with Cr3+Cationic state stays in the purpose in waste water, and separative efficiency is high.
(2) control method of vanadium wastewater resin adsorption of the invention separation strenuous primary treatment establishes initial oxidation reduction
Desirable oxidation reduction potential after current potential, reduction and the formula relationship between reducing agent, oxidation-reduction potential after the completion of alkali tune are set
Formula relationship between fixed desirable oxidation reduction potential and oxidant, thus can be obtained according to the mode of calculating reducing agent and
On the one hand the dosage of oxidant can achieve the purpose being precisely controlled: make in water body with H2V10O28 4-、HV10O28 5-Yin from
Sub- state exists, and chromium is mainly with Cr3+Cation existing for state control it is more accurate, to realize subsequent more efficient
Separation, on the other hand avoid the dosage deficiency bring treatment effeciency of medicament from reducing or add waste caused by excess,
Greatly save operating cost.
(3) control method of vanadium wastewater resin adsorption of the invention separation strenuous primary treatment, can be according to on-line oxidation also
The dosage of former monitor data adjust automatically reducing agent, oxidant is thrown so as to fight variation water quality medicament caused greatly
Dosage changes that bring is inconvenient, and the present invention can also will add calculation formula and be embedded into the PLC control device at scene, according to
The monitoring data of line oxidation-reduction potential monitor, realize the automatic operating of added amount of chemical, realize the optimum management at scene.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
The operating procedure for the vanadium wastewater that the present embodiment is directed to is as follows:
(1) 1L vanadium wastewater, initial pH on wastewater 1.78, initial oxidation reduction potential ORP are taken1For 684.2mv；
(2) reduction treatment is carried out, reducing agent sodium thiosulfate, the reduction potential after reduction reaction is complete are added in raw water
ORP2It is set as 600mv, the dosage M1 of reducing agent can be calculated by the calculation formula of reducing agent, it may be assumed that
M1=A*ln (ORP1-ORP2)-B formula 1；
A=3 ± 0.3；B=5.5 ± 0.5；
A takes 2.7, B to take 6 in the present embodiment, and the dosage that thus can calculate reducing agent is 6.0g/L, restores adding of agent
The reaction time is 60min afterwards；
(3) water sample after restoring carries out alkali tune, adjusts oxidation-reduction potential after pH to 3, pH stablizes using sodium hydroxide
ORP3Value is 351.2mv；
(4) water sample after alkali tune is aoxidized, and the hydrogen peroxide that mass concentration is 30% is added, it is complete that oxidation reaction is set in advance
Desirable oxidation reduction potential ORP after complete4, ORP is set in the present embodiment4Value is 550mv, calculates the dosage M2 of oxidant,
That is:
M2=C* (ORP4-ORP3)-D formula 2；
C=0.023 ± 0.002；D=0.75 ± 0.075；
C takes 0.021, D to take 0.825 in the present embodiment, and the dosage that thus can calculate oxidant is 3.4ml/L, oxidation
Agent adds the rear reaction time as 60min；
(5) by step (4) treated water sample, vanadium is mainly with H2V10O28 4-、HV10O28 5-Anionic state
Form exists, and chromium is mainly with Cr3+Cationic form exist, adsorbed using pyridines chelating resin, separative efficiency is high,
Vanadium concentration in waste water is constant, and vanadium concentration is reduced to 0.62mg/L from 499.8mg/L, and the sublevel for completing vanadium chromium returns
It receives.Table 1 is vanadium chromium concentration statistics before and after wastewater treatment.
1 vanadium chromium waste water separating resulting of table
Embodiment 2
The operating procedure for the vanadium wastewater that the present embodiment is directed to is as follows:
(1) 1L vanadium wastewater, initial pH on wastewater 1.78, initial oxidation reduction potential ORP are taken1For 684.2mv；
(2) reduction treatment is carried out, reducing agent sodium thiosulfate is added in raw water, the completely rear desirable oxidation of reduction reaction is also
Former current potential ORP2Value is 620mv, and the dosage M1 of reducing agent can be calculated by the calculation formula of reducing agent, it may be assumed that
M1=A*ln (ORP1-ORP2)-B formula 1；
A=3 ± 0.3；B=5.5 ± 0.5；
A takes 3.3, B to take 5 in the present embodiment, and the dosage that thus can calculate reducing agent is 8.7g/L, and reducing agent sulphur is added
Sodium thiosulfate can be added using classification, and the first order adds 5g, reaction time 30min；The second level adds 3.7g, reaction time
30min。
(3) water sample after restoring carries out alkali tune, adjusts oxidation-reduction potential after pH to 3.5, pH stablizes using sodium hydroxide
ORP3Value is 400.5mv；
(4) water sample after alkali tune is aoxidized, and the hydrogen peroxide that mass concentration is 30% is added, it is complete that oxidation reaction is set in advance
Desirable oxidation reduction potential ORP after complete4, ORP is set in the present embodiment4Value is 480mv, can be calculated by the calculation formula of oxidant
The dosage M2 of oxidant out, it may be assumed that
M2=C* (ORP4-ORP3)-D formula 2；
C=0.023 ± 0.002；D=0.75 ± 0.075
C takes 0.025, D to take 0.675 in the present embodiment, and the dosage that thus can calculate oxidant is 1.3ml/L, anti-
Wastewater pH should be maintained to stablize 3 in the process, oxidant adds the rear reaction time as 60min；
(5) by step 4) treated water sample, vanadium is mainly with H2V10O28 4-、HV10O28 5-Anionic state
Form exists, and chromium is mainly with Cr3+Cationic form exist, adsorbed using resin anion (R.A.), separative efficiency is high,
Vanadium concentration in waste water is constant, and vanadium concentration is reduced to 48.8mg/L from 499.8mg/L, and the sublevel for completing vanadium chromium returns
It receives.Table 2 is vanadium chromium concentration statistics before and after wastewater treatment.
2 vanadium chromium waste water separating resulting of table
Embodiment 3
The operating procedure for the vanadium wastewater that the present embodiment is directed to is as follows:
(1) 1L vanadium wastewater, initial pH on wastewater 1.81, initial oxidation reduction potential ORP are taken1For 691.2mv；
(2) reduction treatment is carried out, reducing agent sodium pyrosulfite is added in raw water, the completely rear desirable oxidation of reduction reaction is also
Former current potential ORP2Value is 550mv, and the dosage M1 of reducing agent can be calculated by the calculation formula of reducing agent, it may be assumed that
M1=A*ln (ORP1-ORP2)-B formula 1；
A=3 ± 0.3；B=5.5 ± 0.5；
Take A that 3, B is taken to take 5.5 in the present embodiment, the dosage that thus can calculate reducing agent is 9.35g/L, and reduction is added
Agent sodium thiosulfate can be added using classification, and the first order adds 6g, reaction time 30min；The second level adds 3g, reaction time
40min, the third level add 0.35g, reaction time 30min.
(3) water sample after restoring carries out alkali tune, adjusts oxidation-reduction potential after pH to 3.8, pH stablizes using sodium hydroxide
ORP3Value is 385.6mv；
(4) water sample after alkali tune is aoxidized, and the hydrogen peroxide that mass concentration is 30% is added, it is complete that oxidation reaction is set in advance
Desirable oxidation reduction potential ORP after complete4, ORP is set in the present embodiment4Value is 500mv, can be counted by the calculation formula of oxidant
Calculate the dosage M2 of oxidant, it may be assumed that
M2=C* (ORP4-ORP3)-D formula 2；
C=0.023 ± 0.002；D=0.75 ± 0.075
C takes 0.023, D to take 0.75 in the present embodiment, and the dosage that thus can calculate oxidant is 1.9ml/L, is reacting
Wastewater pH is maintained to stablize 3.5 in the process, oxidant adds the rear reaction time as 100min；
(5) by step 4) treated water sample, vanadium is mainly with H2V10O28 4-、HV10O28 5-Anionic state
Form exists, and chromium is mainly with Cr3+Cationic form exist, adsorbed using guanidine chelating resin, separative efficiency is high, gives up
Vanadium concentration in water is constant, and vanadium concentration is reduced to 0.61mg/L from 499.8mg/L, completes the sublevel recycling of vanadium chromium.
Table 3 is vanadium chromium concentration statistics before and after wastewater treatment.
3 vanadium chromium waste water separating resulting of table
Embodiment 4
The operating procedure for the vanadium wastewater that the present embodiment is directed to is as follows:
(1) 1L vanadium wastewater, initial pH on wastewater 1.50, initial oxidation reduction potential ORP are taken1For 702.6mv；
(2) carry out reduction treatment, in raw water be added reducing agent sodium sulfite, be set in advance reduction reaction it is complete after oxygen
Change reduction potential ORP2, ORP is set in the present embodiment2Value is 500mv, can calculate reducing agent by the calculation formula of reducing agent
Dosage M1, it may be assumed that
M1=A*ln (ORP1-ORP2)-B formula 1；
A=3 ± 0.3
B=5.5 ± 0.5
A takes 3.3, B to take 6 in the present embodiment.Thus the dosage that reducing agent can be calculated is 11.5g/L, and reduction medicament is thrown
Adding the rear reaction time is 100min；
(3) water sample after restoring carries out alkali tune, adjusts oxidation-reduction potential after pH to 4, pH stablizes using sodium hydroxide
ORP3Value is 310.3mv；
(4) water sample after alkali tune is aoxidized, and the hydrogen peroxide that mass concentration is 30% is added, after setting oxidation reaction is complete
Desirable oxidation reduction potential ORP4Value is 450mv, and the dosage M2 of oxidant can be calculated by the calculation formula of oxidant,
That is:
M2=C* (ORP4-ORP3)-D formula 2；
C=0.023 ± 0.002；D=0.75 ± 0.075
C takes 0.025, D to take 0.825 in the present embodiment, and the dosage that thus can calculate oxidant is 2.7ml/L, anti-
Wastewater pH should be maintained to stablize 4 in the process, oxidant adds the rear reaction time as 120min；
(5) by step (4) treated water sample, vanadium is mainly with H2V10O28 4-、HV10O28 5-Anionic state
Form exists, and chromium is mainly with Cr3+Cationic form exist, adsorbed using pyridines chelating resin, separation effect
Rate is high, and the vanadium concentration in waste water is constant, and vanadium concentration is reduced to 0.60mg/L from 499.8mg/L, completes point of vanadium chromium
Rank recycling.Table 4 is vanadium chromium concentration statistics before and after wastewater treatment.
4 vanadium chromium waste water separating resulting of table
Embodiment 5
The operating procedure for the vanadium wastewater that the present embodiment is directed to is as follows:
(1) 1L vanadium wastewater, initial pH on wastewater 1.50, initial oxidation reduction potential ORP are taken1For 702.6mv；
(2) carry out reduction treatment, in raw water be added reducing agent sodium sulfite, be set in advance reduction reaction it is complete after oxygen
Change reduction potential ORP2, ORP is set in the present embodiment2Value is 510mv, can calculate reducing agent by the calculation formula of reducing agent
Dosage M1, it may be assumed that
M1=A*ln (ORP1-ORP2)-B formula 1；
A=3 ± 0.3；B=5.5 ± 0.5
A takes 2.7, B to take 5 in the present embodiment, and the dosage that thus can calculate reducing agent is 9.2g/L, restores adding of agent
The reaction time is 100min afterwards；
(3) water sample after restoring carries out alkali tune, adjusts oxidation-reduction potential after pH to 4, pH stablizes using sodium hydroxide
ORP3Value is 330.3mv；
(4) water sample after alkali tune is aoxidized, and the hydrogen peroxide that mass concentration is 30% is added, after setting oxidation reaction is complete
Desirable oxidation reduction potential ORP4Value is 450mv, and the dosage M2 of oxidant can be calculated by the calculation formula of oxidant,
That is:
M2=C* (ORP4-ORP3)-D formula 2；
C=0.023 ± 0.002；D=0.75 ± 0.075
C takes 0.021, D to take 0.675 in the present embodiment.Thus the dosage that oxidant can be calculated is 1.8ml/L, anti-
Wastewater pH should be maintained to stablize 4 in the process, oxidant adds the rear reaction time as 120min；
(5) by step (4) treated water sample, vanadium is mainly with H2V10O28 4-、HV10O28 5-Anionic state
Form exists, and chromium is mainly with Cr3+Cationic form exist, adsorbed using pyridines chelating resin, separation effect
Rate is high, and the vanadium concentration in waste water is constant, and vanadium concentration is reduced to 0.60mg/L from 499.8mg/L, completes point of vanadium chromium
Rank recycling.Table 5 is vanadium chromium concentration statistics before and after wastewater treatment.
5 vanadium chromium waste water separating resulting of table
Claims (10)
1. a kind of control method of vanadium wastewater resin adsorption separation strenuous primary treatment, it is characterised in that: the following steps are included:
(1) the initial oxidation reduction potential ORP of waste water is measured1, the ORP1Unit is mv；With g/L in vanadium wastewater after measurement
Reducing agent is added for unit to be restored, sets the oxidation reduction potential value after the completion of restoring as ORP2, the ORP2Unit is
mv；The reducing agent dosage M is calculated according to formula 1:
M1=A*ln (ORP1-ORP2)-B formula 1；
In formula: A=3 ± 0.3；B=5.7 ± 0.57；
(2) it takes step (1) to be discharged, adjusts pH value of waste water, stirring to pH stable to 3~4 with lye, alkali tune measures oxygen after the completion
Change reduction potential ORP3, the ORP3Unit is mv；
(3) it takes step (2) to be discharged, oxidant is added as unit of ml/L and is aoxidized, the redox after the completion of setting oxidation
Current potential target value is ORP4, the ORP4It is set between 450~550mv, the additional amount M2 of the oxidant is counted according to formula 2
It calculates:
M2=C* (ORP4-ORP3)-D formula 2；
In formula: C=0.023 ± 0.002；D=0.75 ± 0.075；
(4) by step (3) treated, water sample carries out resin adsorption, realizes the separation of vanadium chromium.
2. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 1, it is characterised in that:
The resin includes resin anion (R.A.) or chelate resin.
3. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 1 or 2, feature exist
In: the lye include sodium hydroxide solution, any one in potassium hydroxide solution.
4. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 3, it is characterised in that:
The type of reducing agent is the combination of one or more of sodium thiosulfate, sodium sulfite, sodium pyrosulfite.
5. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 4, it is characterised in that:
The time of reduction reaction is 30~120min in the step (1).
6. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 5, it is characterised in that:
By the ORP2It is set between 500~620mv.
7. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 1 or 2, feature exist
In: the oxidant is the hydrogen peroxide that mass concentration is 30%, and the oxidation time control is in 30~120min.
8. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 7, it is characterised in that:
The pH value that waste water is maintained in the oxidation reaction process is 3~4.
9. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 2, it is characterised in that:
The chelate resin includes guanidine, pyridines and oximes chelating resin.
10. the control method of vanadium wastewater resin adsorption separation strenuous primary treatment according to claim 1, feature exist
In: the Oxidizing and Reducing Agents is respectively adopted hierarchical approaches and adds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910675796.3A CN110407283B (en) | 2019-07-25 | 2019-07-25 | Control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910675796.3A CN110407283B (en) | 2019-07-25 | 2019-07-25 | Control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110407283A true CN110407283A (en) | 2019-11-05 |
| CN110407283B CN110407283B (en) | 2022-04-22 |
Family
ID=68363082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910675796.3A Active CN110407283B (en) | 2019-07-25 | 2019-07-25 | Control method for resin adsorption separation strengthening pretreatment of vanadium precipitation wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110407283B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100278686A1 (en) * | 2009-04-30 | 2010-11-04 | Halpin Peter T | Process for recovering metals and metal compounds from mined ore and other metal-bearing raw source materials |
| 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 |
-
2019
- 2019-07-25 CN CN201910675796.3A patent/CN110407283B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100278686A1 (en) * | 2009-04-30 | 2010-11-04 | Halpin Peter T | Process for recovering metals and metal compounds from mined ore and other metal-bearing raw source materials |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 黄渭澄等: "《电镀三废处理》", 31 December 1983, 四川科学技术出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110407283B (en) | 2022-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106882884B (en) | A kind of method of chloride ion in recycling waste water | |
| CN109250856A (en) | It is a kind of low cost ferric phosphate nitrogen-containing wastewater processing and recovery method as resource | |
| CN106282560B (en) | The extraction and cleaning control technique of nickel in acid solution containing nickel | |
| CN109536720A (en) | The removal methods of chlorine in a kind of copper-bath | |
| CN102689975B (en) | Resourceful treatment method for high-salinity wastewater | |
| CN106868544B (en) | A method of the selective removal univalent anion impurity from sulfuric acid system electrolyte | |
| CN108689522A (en) | A kind of Treatment and recovery recovery method of photovoltaic industry nitration mixture waste water | |
| CN103803744B (en) | The treatment process of cupric micro-etched waste liquid | |
| CN103663506A (en) | Preparation method for refined beryllium hydroxide and preparation method for reactor-quality metallic beryllium bead from refined beryllium hydroxide | |
| CN109607705A (en) | A kind of industry water dechlorination method | |
| CN105385851A (en) | Treatment method of acid pickling waste liquid | |
| CN105950865A (en) | Method for separating and extracting vanadium and chromium from high-chromium vanadium leaching liquid | |
| CN110257633A (en) | It is a kind of to handle wet process zinc abstraction copper-cadmium slag, method of the nickel cobalt slag to prepare copper sponge, Spongy Cadmium simultaneously | |
| CN104860465B (en) | Double-tower catalysis thermal-coupling reflux deamination method and deamination device thereof | |
| CN106148725B (en) | A kind of method for detaching refining osmium | |
| CN110407283A (en) | A kind of control method of vanadium wastewater resin adsorption separation strenuous primary treatment | |
| CN112813268A (en) | PCB (printed circuit board) copper electroplating and acid etching copper resource recycling method | |
| CN105461140B (en) | A kind of Tungsten smelting ion-exchange waste water integrated treatment recovery system and method | |
| CN107585789A (en) | A kind of method that high-purity molybdenum trioxide is prepared using hydrometallurgy molybdenum concntrate | |
| CN112047546A (en) | Treatment process for wastewater containing nitrate nitrogen through anodic oxidation | |
| CN217709144U (en) | Ferric phosphate effluent disposal system | |
| CN106966445B (en) | A kind of method for removing arsenic in nickel sulfate solution containing arsenic | |
| CN110436679A (en) | The devices and methods therefor of lithium carbonate wash water comprehensive utilization of resources | |
| CN113402096B (en) | Stripping and hanging waste liquid treatment method for PCB factory | |
| CN105000738A (en) | Method for reducing content of salt in desulfurization waste liquor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |