CN103420520A - Processing method of vanadium-containing aluminum-containing wastewater - Google Patents
Processing method of vanadium-containing aluminum-containing wastewater Download PDFInfo
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Abstract
The invention provides a processing method of vanadium-containing aluminum-containing wastewater. The method comprises the steps that: (1) under vanadium precipitation and aluminum precipitation conditions, vanadium-containing and aluminum-containing wastewater contact an alkaline substance, and a product obtained after contact is subjected to solid-liquid separation, such that vanadium-containing and aluminum-containing solid product and filtrate are obtained; and (2) the filtrate obtained in the step (1) is subjected to a reverse osmosis process, such that a reverse osmosis product and concentrated water are obtained; and the concentrated water is returned to the step (1). With the wastewater processing method provided by the invention, aluminum and vanadium recovery rate can be substantially improved, and good social and economic benefits are provided.
Description
Technical field
The present invention relates to a kind for the treatment of process containing the vanadium aluminium wastewater.
Background technology
Vanadium system is the catalyst system that current suitability for industrialized production ethylene-propylene rubber(EPR) mainly adopts, and because it easily affects the performance of ethylene-propylene rubber(EPR), must be removed processing, has also brought thus the processing problem containing vanadium ethylene-propylene rubber(EPR) waste water containing aluminium.
At present, the method for administering vanadium-containing water both at home and abroad has four classes, i.e. Physical, chemical method, physico-chemical processes and biological process.Physical mainly contains diatomite adsorption method, active carbon adsorption etc.; Chemical method mainly contains the iron filings precipitator method, the sulfurous gas precipitator method, barium salt process etc.; Physico-chemical processes mainly contains reverse osmosis method, ion exchange method, TBP extraction process, electrolytic process etc.; Biological process mainly contains the anaerobic and aerobic biological process.Wherein, chemical precipitation method and ion exchange method application are more.
CN101113062A discloses a kind of vanadium-containing sewage treatment method, and the method comprises the following steps: a) will be adjusted to and be less than 7.0 containing the pH value of chromium and vanadium waste; B) step a gained waste water is crossed to ion exchange resin column; C) in the resin of b step, add strippant to obtain stripping liquid; D) step c gained elutriant is carried out to precipitation, filter and obtain filtrate and filter cake; E) the steps d gained is processed and produced the chromium product containing chromium filtrate; F) steps d molysite precipitation gained filter cake is obtained to vanadium solution be hydrolyzed precipitation or ammonium salt precipitation by aqueous slkali soaking again.CN102070265A discloses a kind for the treatment of process of vanadium extracting waste water, and specifically discloses and adopt the D301 resin to adsorb vanadium ion and chromium ion as adsorption medium.
Yet all more or less there is defect in existing vanadium-containing sewage treatment method.For example, absorption method is applicable to the processing of low-concentration vanadium-containing waste water; Well still cost is high for the ion exchange method treatment effect; The precipitation flco that in chemical method, the ferrous sulfate precipitator method generate is little, and the settling time is longer; Vanadium after the iron filings method is processed is difficult to reach emission standard; The ammonium salt precipitator method, require vanadium solution more than 90 ℃.
The processing of aluminium wastewater generally adopts flocculation agents such as adding poly-aluminium, polyacrylamide to carry out flocculating settling, or take sodium hydroxide and reclaim the aluminium in waste water as precipitation agent.
Summary of the invention
To the objective of the invention is to adopt existing method to containing the limited defect of vanadium aluminium wastewater treatment effect in order overcoming, and a kind for the treatment of process containing the vanadium aluminium wastewater for the treatment of effect excellence to be provided.
The invention provides a kind for the treatment of process containing the vanadium aluminium wastewater, the method comprises the following steps:
(1) under precipitation and heavy aluminium, will contact with alkaline matter containing the vanadium aluminium wastewater, and the product after contact will be carried out to solid-liquid separation, obtain containing vanadium containing aluminium solid product and filtrate;
(2) make step (1) gained filtrate carry out reverse-osmosis treated by reverse osmosis membrane, obtain reverse osmosis product water and dense water, and described dense water is back in step (1).
Treatment process containing the vanadium aluminium wastewater provided by the invention combines the heavy aluminium of precipitation dexterously with reverse osmosis technology, on the one hand, under the heavy aluminium of precipitation of the present invention, alkaline matter can make aluminum precipitation complete, and the alumine hydroxide colloid simultaneously generated can be removed the most of vanadium flocculation in described waste water; On the other hand, can again be recycled through the reverse osmosis product water of described reverse-osmosis treated gained, and the dense water of reverse-osmosis treated is back in step (1) and is processed, realized the zero release of waste water, had prospects for commercial application.A preferred embodiment of the invention, when the washing methods of described reverse osmosis membrane comprises: mix the A agent (1) with water, obtain scavenging solution; Described A agent is hydrazine hydrate; (2) adopt the scavenging solution of step (1) preparation to be cleaned reverse osmosis membrane, and in cleaning process, add the B agent in described scavenging solution, when described B agent is linear alkylbenzene sulfonate and/or alkylsulfonate, described hydrazine hydrate, linear alkylbenzene sulfonate and/or alkylsulfonate can play well collaborative soil-removing action, thereby effectively by the pollutant removal on reverse osmosis membrane, and then better the aluminium in waste water and vanadium are recycled.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
Treatment process containing the vanadium aluminium wastewater provided by the invention comprises the following steps:
(1) under precipitation and heavy aluminium, will contact with alkaline matter containing the vanadium aluminium wastewater, and the product after contact will be carried out to solid-liquid separation, obtain containing vanadium containing aluminium solid product and filtrate;
(2) make step (1) gained filtrate carry out reverse-osmosis treated by reverse osmosis membrane, obtain reverse osmosis product water and dense water, and described dense water is back in step (1).
Treatment process containing the vanadium aluminium wastewater provided by the invention is applicable to all processing that contain v element and aluminium element waste water, is specially adapted to the processing of ethylene-propylene rubber(EPR) factory effluent.In addition, the present invention is not particularly limited containing the v element in the vanadium aluminium wastewater and the content of aluminium element described, but for the effect that makes to process even more ideal, under preferable case, the described content containing aluminium element in the vanadium aluminium wastewater is 1000-7000mg/L, and the content of v element is 100-200mg/L.Wherein, v element and aluminium element exist with ionic species usually.
According to the present invention, the purpose that will contact with alkaline matter containing the vanadium aluminium wastewater is the pH value of regulating described waste water, so that aluminium and vanadium are precipitated out from described waste water.The present invention is not particularly limited kind and the consumption of alkaline matter, but for aluminium and vanadium are precipitated more complete, under preferable case, after the kind of alkaline matter and consumption make step (1) contact, the pH value of the mixture of gained is 6-8.Under this pH value, the aluminium in described waste water can be converted into precipitation fully, and meanwhile, the aluminium hydroxide of generation can be removed most vanadium flocculation, thereby realizes the purpose of the heavy aluminium of precipitation.Described alkaline matter can be the various materials that can precipitate with the reactive aluminum formation containing in the vanadium aluminium wastewater, for example, can be sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood etc.Above-mentioned alkaline matter can directly be used with solid form, also can use with aqueous solution form.While using with the aqueous solution, preferred concentration is that 10 % by weight are to saturation concentration.
According to the present invention, described precipitation and heavy aluminium are known to the skilled person, as long as the aluminium in described waste water and vanadium can be precipitated out, as a rule, described precipitation and heavy aluminium comprise pH value, temperature and time.As mentioned above, described pH value is preferably 6-8.Described temperature can be selected and change in wider scope, and for example, described temperature can be 40-80 ℃, is preferably 60-70 ℃.The described time also can be selected and be changed in wider scope, v element and aluminium element that the prolongation of time is conducive in waste water precipitate more fully, but overlong time is also not obvious to the amplitude of v element and the raising of aluminium element precipitation capacity, therefore, consider sedimentation effect and production efficiency, time is preferably 20-60 minute, more preferably 30-50 minute.
According to the present invention, the solid-liquid separation described in step (1) can be the existing various method that can realize solid phase and liquid phase separation, for example suction filtration, press filtration or centrifugation, and under preferable case, the method for described solid-liquid separation is filter press technique.The present invention is not particularly limited the condition of press filtration, to realize as far as possible fully solid phase and separating of liquid phase, is as the criterion.
As well known to those skilled in the art, reverse osmosis claims again reverse osmosis, is a kind ofly to take pressure difference as impellent, isolates the membrane sepn operation of solvent from solution.Feed liquid to film one side is exerted pressure, and when pressure surpasses its osmotic pressure, solvent can be made inverse osmosis against the direction of naturally osmotic, thus the solvent that obtains seeing through in the low-tension side of film.In the present invention, the after separating from described waste water by the vanadium in described waste water and aluminium, the filtrate of solid-liquid separation is carried out to reverse-osmosis treated, reverse osmosis membrane can further be removed unprecipitated vanadium, colloidalmaterial and the macromole solute in waste water, thereby, effectively by the Impurity removal in described filtrate, reach described waste water is carried out to the purpose further purified.
The present invention is not particularly limited the condition of described reverse-osmosis treated, as long as described waste water can be carried out further purifying, for example, the condition of described reverse-osmosis treated generally includes temperature and pressure.The temperature of described reverse-osmosis treated can be selected and be changed in wider scope, but, in order more to be conducive to the purification of waste water, described temperature can be 15-40 ℃, is preferably 20-30 ℃.The pressure of described reverse osmosis also can be selected and be changed in wider scope, and for example, described pressure can be 0.5-1.8MPa, is preferably 0.8-1.5MPa.
In the present invention, the reverse osmosis membrane that described reverse osmosis is used can be the reverse osmosis membrane of existing various routines, for example, can be polyamide membrane, polycarbonate membrane etc.Described reverse osmosis membrane can be commercially available.
According to the present invention, for the bacterium by described waste water, colloidalmaterial and macromole solute are removed, the rate of recovery with the processing efficiency that further improves described waste water and vanadium, aluminium, under preferable case, the described treatment process containing the vanadium aluminium wastewater also be included in step (1) afterwards, step (2) before, described filtrate is carried out to pre-treatment.Described pretreated method comprises sterilization, micro-filtration and ultrafiltration.The method of described sterilization is generally in described waste water and adds sterilant, and the kind of described sterilant is known to the skilled person, and can be for example DBNPA (DBNPA).Described micro-filtration strainer used can be filtration with manganese sand device, more medium filter, activated charcoal filter, cartridge filter etc.
According to the present invention, in the process of reverse-osmosis treated, reverse osmosis membrane is easily contaminated.Therefore, in order to improve the processing power to described waste water, under preferable case, the method also comprises: in step (2) afterwards, with scavenging solution, reverse osmosis membrane is washed, and scavenging solution is returned in step (1) and processes, can further be reclaimed the v element in described scavenging solution thus.
According to the present invention, the method of described scavenging solution and washing can be the existing various scavenging solutions that pollutent on described reverse osmosis membrane can be peeled off and the method for washing, for example, can adopt one or more in hydrochloric acid, citric acid solution and sodium hydroxide solution to be cleaned reverse osmosis membrane.Under preferable case, described scavenging solution comprises A agent and B agent, and described A agent is hydrazine hydrate, and described B agent is linear alkylbenzene sulfonate and/or alkylsulfonate; The method of described washing comprises the following steps:
(1) the A agent is mixed with water, obtain scavenging solution; Described A agent is hydrazine hydrate;
(2) adopt the scavenging solution of step (1) preparation to be cleaned reverse osmosis membrane, and, in cleaning process, in described scavenging solution, add the B agent, described B agent is linear alkylbenzene sulfonate and/or alkylsulfonate.
According to the present invention, as long as stated above described reverse osmosis membrane is washed although will contain the scavenging solution of described A agent and B agent, just the pollutent on described reverse osmosis membrane can be removed effectively, but in order to improve washing effect, with front and back pressure difference and the product electrical conductivity of water that further reduces reverse osmosis membrane, under preferable case, with respect to the water of 1L, the consumption of described hydrazine hydrate is 200-1000mg, and total consumption of described linear alkylbenzene sulfonate and alkylsulfonate is 1-30g.More preferably in situation, can further regulate according to the pollution situation on reverse osmosis membrane the consumption of hydrazine hydrate, linear alkylbenzene sulfonate and/or alkylsulfonate, for example, when the COD value of described reverse osmosis membrane system water inlet≤50mg/L, water with respect to 1L, the consumption of described hydrazine hydrate can be 200-800mg, and total consumption of described linear alkylbenzene sulfonate and alkylsulfonate can be 1-10g; When the COD value of described reverse osmosis membrane system water inlet>50mg/L, with respect to the water of 1L, the consumption of described hydrazine hydrate can be 500-1000mg, and total consumption of described linear alkylbenzene sulfonate and alkylsulfonate can be 10-30g.Wherein, it should be noted that, while in described scavenging solution, containing described linear alkylbenzene sulfonate and alkylsulfonate, total consumption of described linear alkylbenzene sulfonate and alkylsulfonate refers to the consumption sum of linear alkylbenzene sulfonate and alkylsulfonate simultaneously; While in described scavenging solution, only containing described linear alkylbenzene sulfonate or alkylsulfonate, total consumption of described linear alkylbenzene sulfonate and alkylsulfonate refers to the consumption of linear alkylbenzene sulfonate or alkylsulfonate.
The present invention is not particularly limited the kind of linear alkylbenzene sulfonate and alkylsulfonate, can be existing various water miscible linear alkylbenzene sulfonates and water miscible alkylsulfonate, be generally sodium salt, the carbonatoms of alkyl can be 10-20, but for to make described scavenging solution show better cleaning performance in the process that reverse osmosis membrane is cleaned, described linear alkylbenzene sulfonate is preferably selected from Sodium dodecylbenzene sulfonate, the tetradecyl benzene sulfonic acid sodium salt, one or more in hexadecyl benzene sulfonic acid sodium salt and octadecyl benzene sulfonic acid sodium salt, Sodium dodecylbenzene sulfonate more preferably, described alkylsulfonate is preferably selected from one or more in sodium laurylsulfonate, tetradecyl sodium sulfonate, sodium cetanesulfonate and octadecyl sodium sulfonate, more preferably sodium cetanesulfonate.Described linear alkylbenzene sulfonate and alkylsulfonate all can be commercially available.
According to the present invention, in step (2), to adding the cleaning condition before the B agent in described scavenging solution, can be the cleaning condition of various routines, as long as can be by the pollutant removal on reverse osmosis membrane, for example, described cleaning condition generally includes temperature, pressure and the time of cleaning.In general, in the process that reverse osmosis membrane is cleaned, after scavenging solution is heated to certain temperature, can significantly improve the cleaning performance of scavenging solution to reverse osmosis membrane; Yet, due to the consideration of reverse osmosis membrane material and use range, the temperature of described cleaning is preferably 25-40 ℃.In addition, because lower operating pressure can guarantee essentially no infiltration water, produce, can reduce like this redeposition of booty on film, therefore, the process of described cleaning is preferably carried out under lower operating pressure, and for example, the pressure of cleaning can be 0.1-0.4MPa.The prolongation of scavenging period is conducive to further peeling off of pollutent on reverse osmosis membrane, but therefore the oversize amplitude that described pollutant removal is improved of time not obvious, considers effect and efficiency, and under preferable case, the time of described cleaning is 1-2 hour.
In like manner, in step (2), adding the cleaning condition after the B agent in described scavenging solution can be also the cleaning condition of various routines, under preferable case, in described scavenging solution, add the cleaning condition after the B agent to comprise that the temperature of cleaning is 25-40 ℃, pressure is 0.1-0.4MPa, and the time is 0.5-1 hour.For the pollutent on described reverse osmosis membrane more effectively being removed, under preferable case, in step (2), in described scavenging solution, add the cleaning condition after the B agent also to comprise that the pH value is for 10-12.The method that the pH value of described scavenging solution is adjusted to 10-12 is known to the skilled person.In general, for the reagent of the pH value of regulating described scavenging solution, can be the alkaline matter of various routines, such as thinking sodium hydroxide, potassium hydroxide etc.Above-mentioned alkaline matter can directly be used with solid form, also can use with aqueous solution form.While using with the aqueous solution, preferred concentration is that 10 % by weight are to saturation concentration.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
The invention will be further described by the following examples.
In following examples and Comparative Examples, the reverse osmosis membrane in described reverse osmosis treatment device is polyamide membrane, purchased from Hydranautics Water Management Equipment Ltd., and trade mark ESPA1.
In following examples and Comparative Examples, the total mass of the rate of recovery of aluminium and vanadium (%)=before processing containing the quality ÷ of aluminium in the aluminium solid product and vanadium containing vanadium aluminium and vanadium in waste water * 100%.
Embodiment 1
This embodiment is for illustrating the treatment process that contains the waste water of aluminium containing vanadium provided by the invention.
(1) under 60 ℃, the sodium hydroxide solution that employing concentration is 25 % by weight will be containing vanadium aluminium wastewater (ethylene-propylene rubber(EPR) factory effluent, wherein, the content of aluminium element is 1438mg/L, the content of v element is 135.75mg/L, and the pH value is 3) the pH value be adjusted to 6 and standing 30 minutes, solid-liquid separation, obtain containing aluminium solid product and filtrate containing vanadium, reclaim containing the aluminium solid product containing vanadium described;
(2) add the DBNPA of 10mg/L in described filtrate, and send into successively in filtration with manganese sand device, more medium filter, activated charcoal filter and cartridge filter filtered after ultrafiltration again;
(3) under 20 ℃, 0.8MPa, the ultrafiltrate of step (2) is sent into to reverse osmosis treatment device, obtain reverse osmosis product water and dense water; And described dense water is returned in step (1) and processed;
(4) the 20g hydrazine hydrate is mixed with the 100L deionized water, obtain scavenging solution; This scavenging solution is added in the reverse osmosis membrane processing device reverse osmosis membrane is cleaned, and keeping the temperature of scavenging solution is 40 ℃, and cleaning pressure is wash cycles 1 hour under 0.4MPa; Afterwards, add the 3kg Sodium dodecylbenzene sulfonate in described scavenging solution, and the sodium hydroxide solution that is 25 % by weight by concentration is adjusted to 10 by the pH value of scavenging solution, keeping the cleaning temperature of scavenging solution is 40 ℃, cleaning pressure is wash cycles 0.5 hour under 0.4MPa, and scavenging solution is returned in step (1) and processed.The rate of recovery of aluminium and vanadium is 99.2%.
Embodiment 2
This embodiment is for illustrating the treatment process that contains the waste water of aluminium containing vanadium provided by the invention.
(1) under 70 ℃, adopt the potassium hydroxide solution that concentration is 25 % by weight will contain containing vanadium waste water (the ethylene-propylene rubber(EPR) factory effluent of aluminium, wherein, the content of aluminium element is 6500mg/L, the content of v element is 165mg/L, and the pH value is 2) the pH value be adjusted to 8 and standing 50 minutes, solid-liquid separation, obtain containing aluminium solid product and filtrate containing vanadium, reclaim containing the aluminium solid product containing vanadium described;
(2) add 10mg/LDBNPA in described filtrate, and send into successively in filtration with manganese sand device, more medium filter, activated charcoal filter and cartridge filter filtered after ultrafiltration again;
(3) under 30 ℃, 1.5MPa, the ultrafiltrate of step (2) is sent in reverse osmosis treatment device and carried out reverse-osmosis treated, obtain reverse osmosis product water and dense water; And described dense water is returned in step (1) and processed;
(4) the 100g hydrazine hydrate is mixed with the 100L deionized water, obtain scavenging solution; This scavenging solution is added in the reverse osmosis membrane processing device reverse osmosis membrane is cleaned, and keeping the temperature of scavenging solution is 25 ℃, and cleaning pressure is wash cycles 2 hours under 0.1MPa; Afterwards, add the 100g sodium cetanesulfonate in described scavenging solution, and the sodium hydroxide solution that is 25 % by weight by concentration is adjusted to 11 by the pH value of scavenging solution, keeping the cleaning temperature of scavenging solution is 25 ℃, cleaning pressure is wash cycles 1 hour under 0.1MPa, and scavenging solution is returned in step (1) and processed.The rate of recovery of aluminium and vanadium is 99.5%.
Embodiment 3
This embodiment is for illustrating the treatment process that contains the waste water of aluminium containing vanadium provided by the invention.
(1) under 65 ℃, adopt the potassium hydroxide solution that concentration is 25 % by weight will contain containing vanadium waste water (the ethylene-propylene rubber(EPR) factory effluent of aluminium, wherein, the content of aluminium element is 3580mg/L, the content of v element is 146mg/L, and the pH value is 2.4) the pH value be adjusted to 7 and standing 40 minutes, solid-liquid separation, obtain containing aluminium solid product and filtrate containing vanadium, reclaim containing the aluminium solid product containing vanadium described;
(2) add 10mg/LDBNPA in described filtrate, and send into successively in filtration with manganese sand device, medium filter, activated charcoal filter and cartridge filter filtered after ultrafiltration again;
(3) under 25 ℃, 1.0MPa, the ultrafiltrate of step (2) is sent into to reverse osmosis treatment device and carry out reverse-osmosis treated, obtain reverse osmosis product water and dense water; And described dense water is returned in step (1) and processed;
(4) the 80g hydrazine hydrate is mixed with the 100L deionized water, obtain scavenging solution; This scavenging solution is added in the reverse osmosis membrane processing device reverse osmosis membrane is cleaned, and keeping the temperature of scavenging solution is 35 ℃, and cleaning pressure is wash cycles 1.5 hours under 0.3MPa; Afterwards, add the 1.5kg Sodium dodecylbenzene sulfonate in described scavenging solution, and the sodium hydroxide solution that is 25 % by weight by concentration is adjusted to 12 by the pH value of scavenging solution, keeping the cleaning temperature of scavenging solution is 35 ℃, cleaning pressure is wash cycles 0.8 hour under 0.3MPa, and scavenging solution is returned in step (1) and processed.The rate of recovery of aluminium and vanadium is 99.7%.
Embodiment 4
This embodiment is for illustrating the treatment process that contains the waste water of aluminium containing vanadium provided by the invention.
Method according to embodiment 1 is processed containing the vanadium aluminium wastewater described, and different, described treatment process does not comprise step (2), that is, filtrate is not carried out to pre-treatment, but directly described filtrate is carried out to reverse-osmosis treated.The rate of recovery of aluminium and vanadium is 98.9%.
Embodiment 5
This embodiment is for illustrating the treatment process that contains the waste water of aluminium containing vanadium provided by the invention.
Method according to embodiment 1 is processed containing the vanadium aluminium wastewater, and different, in step (1), it is 9 that the add-on of described sodium hydroxide solution makes the pH value of described waste water.The rate of recovery of aluminium and vanadium is 90.6%.
Embodiment 6
This embodiment is for illustrating the treatment process that contains the waste water of aluminium containing vanadium provided by the invention.
Method according to embodiment 1 is processed containing the vanadium aluminium wastewater, different is, in step (4), the sodium hydroxide solution that it is 0.2 % by weight that the washing methods of described reverse osmosis membrane comprises by concentration is washed the reverse osmosis membrane in the reverse osmosis treatment device of step (3), keeping temperature is 25 ℃, and pressure is to wash 2 hours under 0.4MPa.The rate of recovery of aluminium and vanadium is 82.6%.
Comparative Examples 1
This Comparative Examples is for illustrating the treatment process that contains the waste water of aluminium containing vanadium provided by the invention.
Method according to embodiment 1 is processed containing the vanadium aluminium wastewater, different, in step (1), described waste water is not contacted with alkaline matter (sodium hydroxide solution that concentration is 25 % by weight), and the pH value of described waste water is 3.The rate of recovery of aluminium and vanadium is 9.8%.
As can be seen from the above results, because embodiment 1-6 has adopted method provided by the invention to being processed containing the vanadium aluminium wastewater, the rate of recovery of aluminium and vanadium is apparently higher than Comparative Examples 1.From the contrast of embodiment 1 and embodiment 4, can find out, after the filtrate obtained after solid-liquid separation is carried out to pre-treatment, in waste water, the rate of recovery of aluminium and vanadium is higher.Can find out from the contrast of embodiment 1 and embodiment 5, under the heavy aluminium of the preferred precipitation of the present invention, described waste water be processed, can reclaim better aluminium and vanadium.Can find out from the contrast of embodiment 1 and embodiment 6, adopt the preferred mode of the present invention to be washed reverse osmosis membrane, can more effectively reclaim aluminium and vanadium.To sum up, the present invention can again recycle the aluminium in waste water and vanadium expeditiously when reducing cost for wastewater treatment, has good Social benefit and economic benefit.
Claims (10)
1. the treatment process containing the vanadium aluminium wastewater, the method comprises the following steps:
(1) under precipitation and heavy aluminium, will contact with alkaline matter containing the vanadium aluminium wastewater, and the product after contact will be carried out to solid-liquid separation, obtain containing vanadium containing aluminium solid product and filtrate;
(2) make step (1) gained filtrate carry out reverse-osmosis treated by reverse osmosis membrane, obtain reverse osmosis product water and dense water, and described dense water is back in step (1).
2. method according to claim 1, wherein, in step (1), described precipitation and heavy aluminium comprise that the pH value is for 6-8, and temperature is 40-80 ℃, and the time is 20-60 minute.
3. method according to claim 1 and 2, wherein, in step (1), described alkaline matter is selected from one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.
4. method according to claim 1 and 2, wherein, in step (2), the condition of described reverse-osmosis treated comprises that temperature is 15-40 ℃, pressure is 0.5-1.8MPa.
5. method according to claim 1, wherein, the method also be included in step (1) afterwards, step (2) before, described filtrate is carried out to pre-treatment, described pretreated method comprises sterilization, micro-filtration and ultrafiltration.
6. method according to claim 1, wherein, the method also is included in step (2) afterwards, with scavenging solution, reverse osmosis membrane is washed, and scavenging solution is returned in step (1) and processes.
7. method according to claim 6, wherein, the method for described washing comprises:
(1) the A agent is mixed with water, obtain scavenging solution; Described A agent is hydrazine hydrate;
(2) adopt the scavenging solution of step (1) preparation to be cleaned reverse osmosis membrane, and, in cleaning process, in described scavenging solution, add the B agent, described B agent is linear alkylbenzene sulfonate and/or alkylsulfonate.
8. method according to claim 7, wherein, with respect to the water of 1L, the consumption of described hydrazine hydrate is 200-1000mg, total consumption of described linear alkylbenzene sulfonate and alkylsulfonate is 1-30g.
9. according to the described method of claim 7 or 8, wherein, in step (2), in described scavenging solution, add B agent cleaning condition before to comprise that temperature is 25-40 ℃, pressure is 0.1-0.4MPa, and the time is 1-2 hour; In described scavenging solution, add the cleaning condition after the B agent to comprise that temperature is 25-40 ℃, pressure is 0.1-0.4MPa, and the time is 0.5-1 hour.
10. method according to claim 1, wherein, the described content containing aluminium element in the vanadium aluminium wastewater is 1000-7000mg/L, the content of v element is 100-200mg/L; Preferably, described is the ethylene-propylene rubber(EPR) factory effluent containing the vanadium aluminium wastewater.
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| CN107970910A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of method that spent vanadium catalyst recycles |
| CN109437463A (en) * | 2018-12-29 | 2019-03-08 | 江苏卓博环保科技有限公司 | Coal calcination vanadium extraction high-salt wastewater advanced treatment and reclamation device and application method |
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| CN107970910A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of method that spent vanadium catalyst recycles |
| CN109437463A (en) * | 2018-12-29 | 2019-03-08 | 江苏卓博环保科技有限公司 | Coal calcination vanadium extraction high-salt wastewater advanced treatment and reclamation device and application method |
| CN109437463B (en) * | 2018-12-29 | 2023-09-12 | 江苏卓博环保科技有限公司 | Advanced treatment and recycling device for stone coal blank roasting vanadium extraction high-salt wastewater and using method |
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| CN103420520B (en) | 2015-06-17 |
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