CN105753248A - Evaporation pretreatment method of reverse osmosis concentrated saline solution - Google Patents
Evaporation pretreatment method of reverse osmosis concentrated saline solution Download PDFInfo
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- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
An embodiment of the invention discloses an evaporation pretreatment method of reverse osmosis concentrated saline solution.The reverse osmosis concentrated saline solution is 1-6% in salt content, 100-1000 mg/L in CODCr concentration and 1-10 mg/L in ammonia nitrogen concentration; the method comprises the following steps: 1), measuring pH value of the reverse osmosis concentrated saline solution; adding fixation high-salt-resistance COD degrading bacteria under pH of 5-11, and carrying out continuous aeration for 5-20 h; 2), oxidizing the reverse osmosis concentrated saline solution treated in step 1) until B/C of the solution is >/=0.2; 3), measuring pH of the reverse osmosis concentrated saline solution treated in step 2), treating by a biological membrane process under pH of 5-11 for 4-50 h, and collecting outflow that is evaporation pretreated outflow.The most process of the method provided herein uses the biological process and is low in cost.
Description
Technical field
The present invention relates to technical field of waste water processing, particularly to a kind of reverse osmosis concentrated salt evaporation of water pre-treating method.
Background technology
Reverse osmosis technology is the feature utilizing reverse osmosis membrane to have selective penetrated property, is filtered concentration to surface water or through the sewage of advanced treating, filters the salt in water, Organic substance and other granule foreign, it is achieved the purpose of purification of water quality or Treated sewage reusing.Reverse-osmosis treated process can produce substantial amounts of strong brine, the salt content of these strong brines up to 1%～6%, CODCr(adopt potassium dichromate (K2Cr2O7) COD (ChemicalOxygenDemand that determines as oxidant, COD)) it is 100～1000mg/L, ammonia-nitrogen content is extremely low, and biodegradability (BiochemicalOxygenDemand/ChemicalOxygenDemand, B/C) is poor.
Industrial generally by reverse osmosis concentrated saline evaporative crystallization salt manufacturing.But before evaporative crystallization, the COD in strong brine need to be removed, because if the COD in strong brine is higher, strong brine can be formed containing higher organic still liquid when evaporation, still liquid accumulates in evaporation crystallization equipment, is enriched with, forms thick liquid, produce substantial amounts of foam material and scale forming matter, affect evaporation crystallization equipment and the separating effect of follow-up carnallite, cause that carnallite processing cost raises.
Owing in reverse osmosis concentrated saline, salt content is high, conventional microbiological can not enduring high-concentration salinity, therefore currently mainly adopt advanced oxidation processes to remove the COD in strong brine.Advanced oxidation processes refers to the chemical oxidation techniques utilizing hydroxyl radical free radical to remove the organic pollution in waste water.But adopt the COD that advanced oxidation processes is removed in waste water relatively costly, especially when COD concentration is higher than 200mg/L.Such as: ozonation technology is often removed 1kgCOD and taken around cost 20～40 yuan；Fenton method is often removed 1kgCOD and is taken around cost 25～60 yuan；Supercritical water oxidation method is often removed 1kgCOD and is taken around cost 50～60 yuan.And adopt bioanalysis to remove the COD advantage of lower cost in waste water, often remove 1kgCOD and take around cost 2～15 yuan.
Summary of the invention
The embodiment of the invention discloses a kind of reverse osmosis concentrated salt evaporation of water pre-treating method, remove relatively costly problem for solving COD in strong brine.Technical scheme is as follows:
A kind of reverse osmosis concentrated salt evaporation of water pre-treating method, the salt content of described reverse osmosis concentrated saline is 1%～6%, CODCrConcentration is 100～1000mg/L, and ammonia nitrogen concentration is 1～10mg/L, comprises the following steps:
1) pH value of reverse osmosis concentrated saline, is measured；When the pH value of reverse osmosis concentrated saline is 5～11, add immobilization height salt tolerant COD degradation bacterium, carry out continuous aeration simultaneously, process 5～20h；
Described immobilization height salt tolerant COD degradation bacterium, by preparing fixing for high salt tolerant COD degradation bacterium in the carrier；The dosage of described immobilization height salt tolerant COD degradation bacterium is 10～100g/L；
Described high salt tolerant COD degradation bacterium, is be placed in the saline of salt content >=2% by COD degradation bacterium to tame acquisition step by step；
2), to step 1) process after reverse osmosis concentrated saline carry out oxidation processes, until B/C >=0.2 of solution；
3), measuring process 2) process after the pH value of reverse osmosis concentrated saline, when the pH value of above-mentioned reverse osmosis concentrated saline is 5～11, adopt biomembrance process to process, after processing 4～50h, collect water outlet, water outlet is evaporation pre-treatment water outlet.
In the preferred embodiment of the present invention, described high salt tolerant COD degradation bacterium tames acquisition by the following method:
S101: take salt lake high salt water sample, be diluted, after dilution, the salt content of water sample is 2%；
S102: add COD degradation bacterium solution in the water sample after described dilution, be simultaneously introduced nutrient substance；
Wherein, the volume ratio of the water sample after described COD degradation bacterium solution and described dilution is 1:10000～100:10000；In described COD degradation bacterium solution, the strain concentration of COD degradation bacterium is 109～1011cells/mL；
Described nutrient substance includes: carbamide or at least one in ammonium salt, carbohydrate and phosphate；Carbon in described nutrient substance, nitrogen, P elements mass ratio be 100:5:1；
S103: continuous aeration 3～5h, keep dissolved oxygen at 3～6mg/L, stand 1～2h afterwards again；Repeat this step until the clearance of COD is more than 80% in water sample；
S104: judge that whether the salt content of water sample is be more than or equal to 6%；
If it has, then terminate domestication；
If it has not, then the salt content of water sample is raised 0.5%, add described nutrient substance；Return to S103；
In described domestication process, the temperature of water sample is maintained at 30 DEG C～40 DEG C.
One in the present invention is more highly preferred in embodiment, and described ammonium salt includes: at least one in ammonium nitrate, ammonium sulfate, ammonium chloride, diammonium phosphate.
One in the present invention is more highly preferred in embodiment, and described carbohydrate includes: at least one in monosaccharide, polysaccharide.
One in the present invention is more highly preferred in embodiment, and described phosphate includes: soluble phosphate, it is preferred at least one in sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, diammonium phosphate.
One in the present invention is more highly preferred in embodiment, described immobilization height salt tolerant COD degradation bacterium, be adopt one or more combinations in embedding, crosslinking, absorption and covalent bond means, prepares fixing for high salt tolerant COD degradation bacterium in the carrier.
One in the present invention is more highly preferred in embodiment, and described immobilization height salt tolerant COD degradation bacterium is to adopt following methods to prepare:
Sodium alginate or polyvinyl alcohol being added to the water, heating, to 50～120 DEG C, stirs, and prepares mixed serum；Wherein, described sodium alginate is 0.1:100～5:100g/mL with the ratio of described water；The ratio of described polyvinyl alcohol and described water is 1:100～20:100g/mL；
After the temperature of described mixed serum is down to 30～45 DEG C, in mixed serum, add high salt tolerant COD degradation bacterium, stirring, make the mixed serum containing high salt tolerant COD degradation bacterium；
Mixed serum containing high salt tolerant COD degradation bacterium is added dropwise in firming agent, stands 2～24h at 0～10 DEG C, obtain high salt tolerant COD degradation bacterium embedded particles；Wherein, described firming agent is made up of calcium chloride, Pulvis Talci and saturated boric acid solution, and based on the gross mass of described firming agent, the mass fraction of described calcium chloride is 1%～20%, and described talcous mass fraction is 0.1%～1%；
High salt tolerant COD degradation bacterium embedded particles is rinsed, it is thus achieved that immobilization height salt tolerant COD degradation bacterium with water or NaCl aqueous solution；Wherein, in described NaCl aqueous solution the mass fraction of NaCl less than or equal to 0.9%.
One in the present invention is more highly preferred in embodiment, and in described immobilization height salt tolerant COD degradation bacterium, the concentration of high salt tolerant COD degradation bacterium is 105～107cells/g。
One in the present invention is more highly preferred in embodiment, step 2) in oxidation processes be at least one in photochemical oxidation process, CWO process, sonochemical oxidation process, ozone Oxidation Treatment, electrochemicial oxidation and Fenton reagent oxidation processes.
One in the present invention is more highly preferred in embodiment, and described biomembrance process is at least one in biological fluidized bed technology, biofilter technology, biological contact oxidation pond technology, biological rotating disk technology.
The reverse osmosis concentrated salt evaporation of water pre-treating method of one provided by the invention, first adopt immobilization height salt tolerant COD degradation bacterium that reverse osmosis concentrated saline carries out strengthening biochemical treatment, high salt tolerant COD degradation bacterium is resistant to high concentration salinity, and in immobilization height salt tolerant COD degradation bacterium, strain concentration is higher, can be effectively reduced the COD in reverse osmosis concentrated saline；Then more reverse osmosis concentrated saline is carried out oxidation processes, reduce the bio-toxicity of reverse osmosis concentrated saline, the hard-degraded substance in reverse osmosis concentrated saline is aoxidized further simultaneously, improve the biodegradability of reverse osmosis concentrated saline；Finally adopting high salt tolerant COD degradation bacterium to be carried out a biological disposal upon by biomembrance process, after process, water outlet is evaporation pre-treatment water outlet.
In method provided by the invention, most processing procedure adopts bioanalysis to replace advanced oxidation processes that reverse osmosis concentrated saline is evaporated pre-treatment, because bioanalysis is less costly relative to advanced oxidation processes, so the method all adopting advanced oxidation processes relative to whole process, method provided by the invention is less costly.
Detailed description of the invention
The invention provides a kind of reverse osmosis concentrated salt evaporation of water pre-treating method, the salt content of described reverse osmosis concentrated saline is 1%～6%, CODCrConcentration is 100～1000mg/L, and ammonia nitrogen concentration is 1～10mg/L, comprises the following steps:
1) pH value of reverse osmosis concentrated saline, is measured；When the pH value of reverse osmosis concentrated saline is 5～11, add immobilization height salt tolerant COD degradation bacterium, carry out continuous aeration simultaneously, process 5～20h (hour)；
Described immobilization height salt tolerant COD degradation bacterium, by preparing fixing for high salt tolerant COD degradation bacterium in the carrier；The dosage of described immobilization height salt tolerant COD degradation bacterium is 10～100g/L；
Described high salt tolerant COD degradation bacterium, is be placed in the saline of salt content >=2% by COD degradation bacterium to tame acquisition step by step；
2), to step 1) process after reverse osmosis concentrated saline carry out oxidation processes, until B/C >=0.2 of solution；
3), measuring process 2) process after the pH value of reverse osmosis concentrated saline, when the pH value of above-mentioned reverse osmosis concentrated saline is 5～11, adopt biomembrance process to process, after processing 4～50h, collect water outlet, water outlet is evaporation pre-treatment water outlet.
In experimentation, inventor have found that, COD degradation bacterium is by obtaining high salt tolerant COD degradation bacterium after taming step by step when high saliferous.In an alternate embodiment of the present invention where, described high salt tolerant COD degradation bacterium can tame acquisition by the following method:
S101: take salt lake high salt water sample, be diluted, after dilution, the salt content of water sample is 2%；
S102: add COD degradation bacterium solution in the water sample after described dilution, be simultaneously introduced nutrient substance；
S103: continuous aeration 3～5h, keep dissolved oxygen at 3～6mg/L, stand 1～2h afterwards again；Repeat this step until the clearance of COD is more than 80% in water sample；
S104: judge that whether the salt content of water sample is be more than or equal to 6%；
If it has, then terminate domestication；
If it has not, then the salt content of water sample is raised 0.5%, add described nutrient substance；Return to S103.
The domestication step by step of COD degradation bacterium is from salt content 2%, and salt content raises 0.5% every time afterwards, is till 6% until salt content, specifically the salt content in water sample can be made to increase by adding appropriate salt lake high salt water sample.Described salt lake is the one in salt water lake；Described salt lake high salt water sample refers to the water sample being taken from salt lake and salt content more than 6%.
Domestication process performs step S103 until the activity that in water sample, the clearance of COD is to ensure that in water sample more than 80% COD degradation bacterium is good, when COD clearance is more than 80%, represent that in water sample, the activity of COD degradation bacterium is good, it is possible to raise the salt content of water sample；Otherwise, represent that in water sample, the activity of COD degradation bacterium is bad, it is necessary to proceed Air Exposure.
The volume ratio of COD degradation bacterium solution described in domestication process and the water sample after described dilution is 1:10000～100:10000；In described COD degradation bacterium solution, the strain concentration of COD degradation bacterium is 109～1011cells/mL.Described nutrient substance includes: carbamide or at least one in ammonium salt, carbohydrate and phosphate；Wherein, described ammonium salt includes: at least one in ammonium nitrate, ammonium sulfate, ammonium chloride, diammonium phosphate, described carbohydrate includes: at least one in monosaccharide, polysaccharide, described phosphate includes: soluble phosphate, it is preferred at least one in sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, diammonium phosphate.Carbon in described nutrient substance, nitrogen, P elements mass ratio be 100:5:1, and in domestication process, the temperature of water sample is maintained at 30 DEG C～40 DEG C, is beneficial to the domestication of COD degradation bacterium.
The high salt tolerant COD degradation bacterium obtained by above method domestication is resistant to high concentration salinity, therefore can survive in reverse osmosis concentrated saline.Wherein, COD degradation bacterium refers to the antibacterial of the COD in degrading waste water, for instance bacillus subtilis.
The inventors have also found that, being concentrated by the high salt tolerant COD degradation bacterium of domestication gained, after concentration, strain concentration is 107～1011Cells/mL, then adopts immobilized microorganism technique, and being fixed by the high salt tolerant COD degradation bacterium after concentration and making strain concentration in the carrier is 105～107The immobilization height salt tolerant COD degradation bacterium of cells/g, is added to this immobilization height salt tolerant COD degradation bacterium in the reverse osmosis concentrated saline that pH value is 5～11, can be effectively reduced the COD in strong brine.In actual applications, it is possible to the high salt tolerant COD degradation bacterium of domestication gained is first carried out amplification culture, then concentrates again, it is also possible to the high salt tolerant COD degradation bacterium of domestication gained is made directly concentration, and this is not construed as limiting by the present invention.Wherein, concentration generally includes membrance concentration, centrifugal concentrating etc., concentrates as this area routine techniques means, and the present invention is not especially limited at this.Immobilized microorganism technique be by elite Microorganism incubation on carrier so that it is highly dense also keeps biological activity, the biotechnology can bred quickly, in a large number under optimum conditions；Concrete, immobilized microorganism technique can adopt one or more combinations in embedding, crosslinking, absorption and covalent bond means, high salt tolerant COD degradation bacterium is fixed in the carrier, described carrier is be not decomposed by the microorganisms and the carrier material of not polluted water, can be the natural macromolecular materials such as sodium alginate, can also be the synthesis macromolecular materials such as polyvinyl alcohol, it is also possible to being the material such as zeolite, activated carbon, this is not construed as limiting by the present invention.
In an alternate embodiment of the present invention where, described immobilization height salt tolerant COD degradation bacterium is to adopt following methods to prepare:
Sodium alginate or polyvinyl alcohol being added to the water, heating, to 50～120 DEG C, stirs, and prepares mixed serum；Wherein, described sodium alginate is 0.1:100～5:100g/mL with the ratio of described water；The ratio of described polyvinyl alcohol and described water is 1:100～20:100g/mL；
After the temperature of described mixed serum is down to 30～45 DEG C, in mixed serum, add high salt tolerant COD degradation bacterium, stirring, make the mixed serum containing high salt tolerant COD degradation bacterium；
Mixed serum containing high salt tolerant COD degradation bacterium is added dropwise in firming agent, stands 2～24h at 0～10 DEG C, obtain high salt tolerant COD degradation bacterium embedded particles；Wherein, described firming agent is made up of calcium chloride, Pulvis Talci and saturated boric acid solution, and based on the gross mass of described firming agent, the mass fraction of described calcium chloride is 1%～20%, and described talcous mass fraction is 0.1%～1%；
High salt tolerant COD degradation bacterium embedded particles is rinsed, it is thus achieved that immobilization height salt tolerant COD degradation bacterium with water or NaCl aqueous solution；Wherein, in described NaCl aqueous solution the mass fraction of NaCl less than or equal to 0.9%.
In technical scheme, high salt tolerant COD degradation bacterium is suitable existence when pH value is 5～11, and pH value is too high or too low is all unfavorable for that it is survived.If the pH value of reverse osmosis concentrated saline is not in the scope of 5～11, those skilled in the art can use acid or alkali to regulate the pH value of reverse osmosis concentrated saline, and making pH value is 5～11.
In technical scheme, described high salt tolerant COD degradation Pseudomonas is in aerobic bacteria, it is necessary to oxygen could be survived.Therefore, need to carry out continuous aeration when reverse osmosis concentrated saline being carried out a biological disposal upon with high salt tolerant COD degradation bacterium, increase the dissolved oxygen in solution, so that high salt tolerant COD degradation bacterium can survive and play a role.The gas of described continuous aeration is air or oxygen, it is preferred to air.Those skilled in the art according to the difference of the water quality of handled reverse osmosis concentrated saline and the water yield, can determine gas flow and the aerator quantity of described continuous aeration, and the present invention is not especially limited at this.
Inventor have found that, after reverse osmosis concentrated saline immobilization height salt tolerant COD degradation bacterium is processed a period of time, the B/C value of reverse osmosis concentrated saline can decline, when B/C is < when 0.2, immobilization height salt tolerant COD degradation bacterium is poor to organic pollutant degradation effect, and as B/C, < when 0.1, immobilization height salt tolerant COD degradation bacterium cannot degradable organic pollutant again, generally in step 1) process after 5～20h, immobilization height salt tolerant COD degradation bacterium just cannot degradable organic pollutant again.Now, reverse osmosis concentrated saline is carried out oxidation processes again, the B/C value of solution can be improved.Wherein, described oxidation processes can adopt advanced oxidation processes conventional in prior art to carry out, and described advanced oxidation processes refers to the chemical oxidation techniques utilizing hydroxyl radical free radical to remove the organic pollution in reverse osmosis concentrated saline；Concrete, advanced oxidation processes can be at least one in photochemical oxidation method, catalytic wet air oxidation, sonochemical oxidation, Ozonation, electrochemical oxidation process and Fenton reagent oxidizing process.Having been reported that owing to advanced oxidation processes more, the technique of advanced oxidation processes and device are known, and those skilled in the art easily know how these technology are implemented, operated, and the present invention does not repeat at this.Those skilled in the art can select suitable advanced oxidation processes to step 1 according to the concrete composition of the pollutant in existing report and reverse osmosis concentrated saline and content) process after reverse osmosis concentrated saline carry out oxidation processes.
Inventor have found that, when B/C >=0.2 of solution, high salt tolerant COD degradation bacterium can be adopted again by biomembrance process, reverse osmosis concentrated saline to be processed, to reduce the COD in reverse osmosis concentrated saline further.Concrete, those skilled in the art can pass through rate-determining steps 2) process time of oxidation processes, make B/C >=0.2 of the reverse osmosis concentrated saline after process.
Those skilled in the art are it is understood that step 2) in different oxidation treatment methods the pH value of reverse osmosis concentrated saline is had different requirements, therefore cause that the pH value of reverse osmosis concentrated saline obtained after different method for oxidation process is different.So, when step 2) oxidation processes terminate after, before adopting biomembrance process to process, it is necessary to first measure through step 2) process after the pH value of reverse osmosis concentrated saline, it is judged that whether this pH value in the scope of 5～11, to ensure effective generation of biochemical reaction, if this pH value is in the scope of 5～11, biomembrance process can be adopted to process, if this pH value is not in the scope of 5～11, those skilled in the art can use acid or alkali to regulate pH value, and making pH value is 5～11.
Biomembrance process described in technical solution of the present invention refers to and utilizes the high salt tolerant COD degradation bacterium being attached on filler to remove the biological oxidation technology of the organic pollution in reverse osmosis concentrated saline；Described filler can be activated carbon, pelelith, it is also possible to for common stone etc., this is not construed as limiting by the present invention.Concrete, biomembrance process can be at least one in biological fluidized bed technology, biofilter technology, biological contact oxidation pond technology, biological rotating disk technology.Having been reported that owing to biomembrance process more, the technique of biomembrance process and device are known, and those skilled in the art easily know how these technology are implemented, operated, and the present invention does not repeat at this.Those skilled in the art can select suitable biomembrance process that reverse osmosis concentrated saline is processed according to the concrete composition of the pollutant in existing report and reverse osmosis concentrated saline and content.
It should be noted that the salt content in the present invention refers to the ratio of the gross mass of various salt and saline gross mass in saline；Wherein, salt refers to the compound that metal ion or ammonium radical ion are combined with acid ion or nonmetallic ion, for instance sodium chloride, potassium chloride, magnesium chloride, potassium sulfate etc..
Below in conjunction with specific embodiment, technical scheme being described, described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
Microorganism used in BAF in embodiment is high salt tolerant COD degradation bacterium, and COD degradation bacterium is placed in Halite water sample domestication step by step and obtains by research and development centre of this high salt tolerant COD degradation Jun Shi Poten Environment Group Co., Ltd.；Concrete steps include:
Taking salt lake high salt water sample (salt content is 8%), be diluted, after dilution, water sample salt content is 2%；
Taking the water sample after 1L dilution, regulate water temperature to 30 DEG C, adding concentration is 109～1011The COD degradation bacterium solution 10mL of cells/mL, is simultaneously introduced glucose 5.5g, carbamide 0.24g and potassium dihydrogen phosphate 0.098g；
Continuous air aeration 3h, air mass flow is 20L/min (minute), stands 1h afterwards again；After repeating this step 3 time, measuring the clearance of COD in water sample is 87.5%；
After staticly settling, discharge supernatant 100mL, add 87.5mL salt lake high salt water sample and 12.5mL tap water, make the salinity of water sample be adjusted to 2.5%, add glucose 5g, carbamide 0.218g and potassium dihydrogen phosphate 0.089g；
Continuous air aeration 5h, air mass flow is 20L/min, stands 1h afterwards again；After repeating this step 3 time, measuring the clearance of COD in water sample is 83.6%；
After staticly settling, discharge supernatant 100mL, add 82.5mL salt lake high salt water sample and 17.5mL tap water, make the salinity of water sample be adjusted to 3%, add glucose 5g, carbamide 0.218g and potassium dihydrogen phosphate 0.089g；
Continuous air aeration 5h, air mass flow is 20L/min, stands 1h afterwards again；After repeating this step 3 time, measuring the clearance of COD in water sample is 85.6%；
After staticly settling, discharge supernatant 100mL, add 100mL salt lake high salt water sample, make the salinity of water sample be adjusted to 3.5%, add glucose 5g, carbamide 0.218g and potassium dihydrogen phosphate 0.089g；
Continuous air aeration 5h, air mass flow is 20L/min, stands 1h afterwards again；After repeating this step 4 time, measuring the clearance of COD in water sample is 93.4%；
After staticly settling, discharge supernatant 150mL, add 128mL salt lake high salt water sample and 22mL tap water, make the salinity of water sample be adjusted to 4%, add glucose 5g, carbamide 0.218g and potassium dihydrogen phosphate 0.089g；
Continuous air aeration 4h, air mass flow is 20L/min, stands 1h afterwards again；After repeating this step 4 time, measuring the clearance of COD in water sample is 85.8%；
After staticly settling, discharge supernatant 150mL, add 138mL salt lake high salt water sample and 12mL tap water, make the salinity of water sample be adjusted to 4.5%, add glucose 5g, carbamide 0.218g and potassium dihydrogen phosphate 0.089g；
Continuous air aeration 4h, air mass flow is 20L/min, stands 1h afterwards again；After repeating this step 5 time, measuring the clearance of COD in water sample is 87.4%；
After staticly settling, discharge supernatant 150mL, add 147mL salt lake high salt water sample and 3mL tap water, make the salinity of water sample be adjusted to 5%, add glucose 5g, carbamide 0.218g and potassium dihydrogen phosphate 0.089g；
Continuous air aeration 3h, air mass flow is 20L/min, stands 1h afterwards again；After repeating this step 5 time, measuring the clearance of COD in water sample is 88.9%；
After staticly settling, discharge supernatant 200mL, add 188mL salt lake high salt water sample and 12mL tap water, make the salinity of water sample be adjusted to 5.5%, add glucose 5g, carbamide 0.218g and potassium dihydrogen phosphate 0.089g；
Continuous air aeration 3h, air mass flow is 20L/min, stands 1h afterwards again；After repeating this step 5 time, measuring the clearance of COD in water sample is 91.5%；
After staticly settling, discharge supernatant 200mL, add 200mL salt lake high salt water sample, make the salinity of water sample be adjusted to 6%, add glucose 5g, carbamide 0.218g and potassium dihydrogen phosphate 0.089g；
Continuous air aeration 4h, air mass flow is 20L/min, stands 1h afterwards again；After repeating this step 5 time, measuring the clearance of COD in water sample is 93.5%, terminates domestication, obtains high salt tolerant COD degradation bacterium.
The high salt tolerant COD degradation bacterium 1000mL above-mentioned domestication obtained is placed in 1m3The saline that salt content is 6% in amplification culture, regulate water temperature to 30 DEG C, be simultaneously introduced glucose 5.5kg, carbamide 240g and potassium dihydrogen phosphate 98g；
Continuous air aeration 4h, air mass flow is 70L/min, stands 1h afterwards again；After repeating this step 3 time, measuring the clearance of COD in water sample is 86.4%；
Bacterium solution after above-mentioned amplification culture is carried out membrance concentration, and after making concentration, in bacterium solution, strain concentration is 107～1011Cells/mL, thus the high salt tolerant COD degradation bacterium after being concentrated.
Immobilization height salt tolerant COD degradation bacterium used in embodiment is to adopt sodium alginate-calcium chloride embedding techniques that the high salt tolerant COD degradation bacterium after above-mentioned concentration carries out embedding to granulate, and in the immobilization height salt tolerant COD degradation bacterium prepared, the strain concentration of high salt tolerant COD degradation bacterium is 105～107cells/g；Concrete steps include:
Preparation firming agent: boric acid is joined and dissolves prepared saturated boric acid solution in 2000mL distilled water, weigh 80gCaCl2, 8g Pulvis Talci, join in saturated boric acid solution, prepare firming agent.
Immobilization is prepared by height salt tolerant COD degradation bacterium: adding 25g sodium alginate in 500mL water, heating is to 70 DEG C, with the rotating speed continuous stirring 100min of 60rpm, prepares mixed serum.After the temperature of mixed serum is down to 35 DEG C, in mixed serum, adds the high salt tolerant COD degradation bacterium after 25mL concentration, continue stirring, make the mixed serum containing high salt tolerant COD degradation bacterium.Drawing the mixed serum containing high salt tolerant COD degradation bacterium with the 50mL syringe with syringe needle, then be added dropwise in firming agent, syringe needle and firming agent liquid level distance are 30cm, stand 24h, obtain high salt tolerant COD degradation bacterium embedded particles at 0 DEG C.High salt tolerant COD degradation bacterium embedded particles is taken out, and after washing, i.e. the high salt tolerant COD degradation bacterium of being fixed.
Reagent used in embodiment is all commercially.
Embodiment 1
The Raw performance of reverse osmosis concentrated saline: CODCrConcentration is 416.8mg/L, and salt content is 2.67%, and ammonia nitrogen concentration is 8.9mg/L.
Taking the reverse osmosis concentrated saline of 10L, measure its pH value, pH value is 7.8, adds 400g immobilization height salt tolerant COD degradation bacterium, passes into air simultaneously and carry out continuous aeration, and the flow of air is 30L/min, processes 5h.The pH value of reverse osmosis concentrated saline is adjusted to 2.5 after terminating by process.Fenton oxidation process unit adds 900mgFeSO4And 600mgH2O2, the reverse osmosis concentrated saline of modulated good pH value is passed in above-mentioned Fenton oxidation process unit, after processing 60min, end processes, and collects the water outlet of Fenton oxidation process unit.18h is placed in this water outlet, makes H2O2Fully precipitate out.Measuring the pH value of water outlet, pH value is 2, regulates the pH value of above-mentioned water outlet to 7.4 with NaOH, passes into BAF, collects water outlet after processing 24h.
Effluent index: CODCrConcentration is 35.8mg/L.
Embodiment 2
The Raw performance of reverse osmosis concentrated saline: CODCrConcentration is 416.8mg/L, and salt content is 2.67%, and ammonia nitrogen concentration is 8.9mg/L.
Taking the reverse osmosis concentrated saline of 10L, measure its pH value, pH value is 5, adds 400g immobilization height salt tolerant COD degradation bacterium, passes into air simultaneously and carry out continuous aeration, and the flow of air is 30L/min, processes 10h.The pH value of reverse osmosis concentrated saline is adjusted to 11.4 after terminating by process.Photochemical oxidation process device adds 1980mgH2O2, the reverse osmosis concentrated saline of modulated good pH value is passed in above-mentioned photochemical oxidation process device, uses the UV wavelength of 254nm to process, after processing 2h, end processes, and collects the water outlet of photochemical oxidation process device.24h is placed in this water outlet, makes H2O2Fully precipitate out.Measuring the pH value of above-mentioned water outlet, pH value is 10, passes into BAF, collects water outlet after processing 30h.
Effluent index: CODCrConcentration is 33.9mg/L.
Embodiment 3
The Raw performance of reverse osmosis concentrated saline: CODCrConcentration is 416.8mg/L, and salt content is 2.67%, and ammonia nitrogen concentration is 8.9mg/L.
Taking the reverse osmosis concentrated saline of 10L, measure its pH value, pH value is 12, with sulfur acid for adjusting pH value to 8.9, adds 400g immobilization height salt tolerant COD degradation bacterium, passes into air simultaneously and carry out continuous aeration, and the flow of air is 30L/min, processes 20h.Process terminates to pass into ozone in backward reverse osmosis concentrated saline, and the concentration of ozone is 10g/L, after processing 10min, stops passing into ozone and terminates to process.Reverse osmosis concentrated saline is placed 20h, makes ozone fully precipitate out.Measuring the pH value of reverse osmosis concentrated saline, pH value is 8.3, and reverse osmosis concentrated saline passes into BAF, collects water outlet after processing 4h.
Effluent index: CODCrConcentration is 37.2mg/L.
From above-described embodiment, the reverse osmosis concentrated salt evaporation of water pre-treating method of one provided by the invention, first adopt immobilization height salt tolerant COD degradation bacterium that reverse osmosis concentrated saline carries out strengthening biochemical treatment, high salt tolerant COD degradation bacterium is resistant to high concentration salinity, and in immobilization height salt tolerant COD degradation bacterium, strain concentration is higher, can be effectively reduced the COD in reverse osmosis concentrated saline；Then more reverse osmosis concentrated saline is carried out oxidation processes, reduce the bio-toxicity of reverse osmosis concentrated saline, the hard-degraded substance in reverse osmosis concentrated saline is aoxidized further simultaneously, improve the biodegradability of reverse osmosis concentrated saline；High salt tolerant COD degradation bacterium is finally adopted to be carried out a biological disposal upon by biomembrance process, the COD of water outlet after processCrConcentration, lower than 40mg/L, can be made directly evaporative crystallization.
In method provided by the invention, most processing procedure adopts bioanalysis to replace advanced oxidation processes that reverse osmosis concentrated saline is evaporated pre-treatment, because bioanalysis is less costly relative to advanced oxidation processes, so the method all adopting advanced oxidation processes relative to whole process, method provided by the invention is less costly.
Above the reverse osmosis concentrated salt evaporation of water pre-treating method of one provided by the present invention is described in detail.Principles of the invention and embodiment are set forth by specific embodiment used herein, and the explanation of above example is only intended to help to understand method and the central idea thereof of the present invention.It should be pointed out that, for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify the protection also falling into the claims in the present invention.
Claims (10)
1. a reverse osmosis concentrated salt evaporation of water pre-treating method, the salt content of described reverse osmosis concentrated saline is 1%～6%, CODCrConcentration is 100～1000mg/L, and ammonia nitrogen concentration is 1～10mg/L, it is characterised in that comprise the following steps:
1) pH value of reverse osmosis concentrated saline, is measured；When the pH value of reverse osmosis concentrated saline is 5～11, add immobilization height salt tolerant COD degradation bacterium, carry out continuous aeration simultaneously, process 5～20h；
Described immobilization height salt tolerant COD degradation bacterium, by preparing fixing for high salt tolerant COD degradation bacterium in the carrier；The dosage of described immobilization height salt tolerant COD degradation bacterium is 10～100g/L；
Described high salt tolerant COD degradation bacterium, is be placed in the saline of salt content >=2% by COD degradation bacterium to tame acquisition step by step；
2), to step 1) process after reverse osmosis concentrated saline carry out oxidation processes, until B/C >=0.2 of solution；
3), measuring process 2) process after the pH value of reverse osmosis concentrated saline, when the pH value of above-mentioned reverse osmosis concentrated saline is 5～11, adopt biomembrance process to process, after processing 4～50h, collect water outlet, water outlet is evaporation pre-treatment water outlet.
2. evaporate pre-treating method as claimed in claim 1, it is characterised in that described high salt tolerant COD degradation bacterium tames acquisition by the following method:
S101: take salt lake high salt water sample, be diluted, after dilution, the salt content of water sample is 2%；
S102: add COD degradation bacterium solution in the water sample after described dilution, be simultaneously introduced nutrient substance；
Wherein, the volume ratio of the water sample after described COD degradation bacterium solution and described dilution is 1:10000～100:10000；In described COD degradation bacterium solution, the strain concentration of COD degradation bacterium is 109～1011cells/mL；
Described nutrient substance includes: carbamide or at least one in ammonium salt, carbohydrate and phosphate；Carbon in described nutrient substance, nitrogen, P elements mass ratio be 100:5:1；
S103: continuous aeration 3～5h, keep dissolved oxygen at 3～6mg/L, stand 1～2h afterwards again；Repeat this step until the clearance of COD is more than 80% in water sample；
S104: judge that whether the salt content of water sample is be more than or equal to 6%；
If it has, then terminate domestication；
If it has not, then the salt content of water sample is raised 0.5%, add described nutrient substance；Return to S103；
In described domestication process, the temperature of water sample is maintained at 30 DEG C～40 DEG C.
3. evaporate pre-treating method as claimed in claim 2, it is characterised in that described ammonium salt includes: at least one in ammonium nitrate, ammonium sulfate, ammonium chloride, diammonium phosphate.
4. evaporate pre-treating method as claimed in claim 2, it is characterised in that described carbohydrate includes: at least one in monosaccharide, polysaccharide.
5. evaporate pre-treating method as claimed in claim 2, it is characterised in that described phosphate includes: soluble phosphate, it is preferred at least one in sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, diammonium phosphate.
6. evaporate pre-treating method as claimed in claim 1, it is characterized in that, described immobilization height salt tolerant COD degradation bacterium, be adopt one or more combinations in embedding, crosslinking, absorption and covalent bond means, prepares fixing for high salt tolerant COD degradation bacterium in the carrier.
7. evaporate pre-treating method as claimed in claim 6, it is characterised in that described immobilization height salt tolerant COD degradation bacterium is to adopt following methods to prepare:
Sodium alginate or polyvinyl alcohol being added to the water, heating, to 50～120 DEG C, stirs, and prepares mixed serum；Wherein, described sodium alginate is 0.1:100～5:100g/mL with the ratio of described water；The ratio of described polyvinyl alcohol and described water is 1:100～20:100g/mL；
After the temperature of described mixed serum is down to 30～45 DEG C, in mixed serum, add high salt tolerant COD degradation bacterium, stirring, make the mixed serum containing high salt tolerant COD degradation bacterium；
Mixed serum containing high salt tolerant COD degradation bacterium is added dropwise in firming agent, stands 2～24h at 0～10 DEG C, obtain high salt tolerant COD degradation bacterium embedded particles；Wherein, described firming agent is made up of calcium chloride, Pulvis Talci and saturated boric acid solution, and based on the gross mass of described firming agent, the mass fraction of described calcium chloride is 1%～20%, and described talcous mass fraction is 0.1%～1%；
High salt tolerant COD degradation bacterium embedded particles is rinsed, it is thus achieved that immobilization height salt tolerant COD degradation bacterium with water or NaCl aqueous solution；Wherein, in described NaCl aqueous solution the mass fraction of NaCl less than or equal to 0.9%.
8. evaporate pre-treating method as claimed in claim 1, it is characterised in that in described immobilization height salt tolerant COD degradation bacterium, the concentration of high salt tolerant COD degradation bacterium is 105～107cells/g。
9. evaporate pre-treating method as claimed in claim 1, it is characterized in that, step 2) in oxidation processes be at least one in photochemical oxidation process, CWO process, sonochemical oxidation process, ozone Oxidation Treatment, electrochemicial oxidation and Fenton reagent oxidation processes.
10. evaporate pre-treating method as claimed in any one of claims 1-9 wherein, it is characterised in that described biomembrance process is at least one in biological fluidized bed technology, biofilter technology, biological contact oxidation pond technology, biological rotating disk technology.
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Denomination of invention: Evaporation pretreatment method of reverse osmosis concentrated saline solution Effective date of registration: 20200511 Granted publication date: 20190118 Pledgee: Beijing urban construction and development branch of China Construction Bank Co., Ltd Pledgor: POTEN ENVIRONMENT GROUP Co.,Ltd.|Poten Industrial Technology (Beijing) Co., Ltd Registration number: Y2020990000453 |