CN105645599A - Biological treatment method for reverse osmosis strong brine - Google Patents
Biological treatment method for reverse osmosis strong brine Download PDFInfo
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Abstract
An embodiment of the invention disclosed a biological treatment method for reverse osmosis strong brine. The salt content of the reverse osmosis strong brine is 1 percent to 6 percent, the CODCr concentration is 100 to 1000mg/L, the ammonia concentration is 1 to 10mg/L, and the ratio of B/L is lower than 0.2. The biological treatment method comprises the steps of measuring the pH value of the reverse osmosis strong brine, under the condition that the pH value of the reverse osmosis strong brine is 5 to 11, adding immobilized high salt tolerant COD degrading bacteria, performing continuous aeration at the same time, processing for 5 to 20h, then adding a composite synergistic component, performing aeration treatment continuously for 20 to 60h, and then collecting effluent; or adding the composite synergistic component while adding the immobilized high salt tolerant COD degrading bacteria, performing aeration treatment continuously, processing for 5 to 80h, and then collecting effluent. A method provided by the invention belongs to a biological method, and is low in cost relative to an advanced oxidation process.
Description
Technical field
The present invention relates to technical field of waste water processing, particularly to the bioremediation of a kind of reverse osmosis concentrated saline.
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 the bioremediation of a kind of reverse osmosis concentrated saline, remove relatively costly problem for solving COD in strong brine. Technical scheme is as follows:
The bioremediation of a kind of reverse osmosis concentrated saline, the salt content of described reverse osmosis concentrated saline is 1%��6%, CODCrConcentration is 100��1000mg/L, and ammonia nitrogen concentration is that 1��10mg/L, B/C ratio is lower than 0.2, it is characterised in that comprise the following steps:
Measure the pH value of reverse osmosis concentrated saline; 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; Add composite synergistic component, after continuing Air Exposure 20��60h, collect water outlet;
Or
Measure the pH value of reverse osmosis concentrated saline; When the pH value of reverse osmosis concentrated saline is 5��11, adds immobilization height salt tolerant COD degradation bacterium, be simultaneously introduced composite synergistic component, carry out continuous aeration, after processing 5��80h, collect water outlet;
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;
Described composite synergistic component includes: at least one in minor metallic element needed for COD degradation bacterium, alcohols, carbohydrate, phosphate, carbamide, ammonia spirit, ammonium salt.
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, 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, 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, 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 the minor metallic element needed for described COD degradation bacterium includes: at least one in aluminum, calcium, cobalt, chromium, nickel, molybdenum, vanadium, stannum, strontium, rubidium, copper, ferrum, lead, magnesium, manganese, zinc.
The bioremediation of a kind of reverse osmosis concentrated saline provided by the invention, adopt immobilization height salt tolerant COD degradation bacterium and add composite synergistic component reverse osmosis concentrated saline is carried out enhanced biological process, 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 waste water; Composite synergistic component provides required nutrient substance can under the insufficient condition of nutrient substance immobilization height salt tolerant COD degradation bacterium. Method provided by the invention belongs to bioanalysis, less costly relative to advanced oxidation processes.
Detailed description of the invention
The invention provides the bioremediation of a kind of reverse osmosis concentrated saline, the salt content of described reverse osmosis concentrated saline is 1%��6%, CODCrConcentration is 100��1000mg/L, ammonia nitrogen concentration be 1��10mg/L, B/C ratio lower than 0.2, comprise the following steps:
Measure the pH value of reverse osmosis concentrated saline; 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; Add composite synergistic component, continue Air Exposure 20��60h (hour) and collect water outlet afterwards;
Or
Measure the pH value of reverse osmosis concentrated saline; When the pH value of reverse osmosis concentrated saline is 5��11, adds immobilization height salt tolerant COD degradation bacterium, be simultaneously introduced composite synergistic component, carry out continuous aeration, after processing 5��80h, collect 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 under high saliferous (salt content >=2%) condition. 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. It will be appreciated by persons skilled in the art that COD degradation bacterium refers to a class bacterium, the antibacterial of the COD in all energy degrading waste waters all can be described as COD degradation bacterium. High salt tolerant COD degradation bacterium in technical solution of the present invention can be obtained by single certain COD degradation bacterium domestication, it is also possible to being obtained by the domestication of multiple COD degradation bacterium, this is not defined by the present invention.
The inventors have also found that, being concentrated by the high salt tolerant COD degradation bacterium of domestication gained, after making 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. Because strain concentration is higher in immobilization height salt tolerant COD degradation bacterium, reverse osmosis concentrated saline had intensive biooxidation effect, it is possible to the material that degraded conventional microbiological can not be degraded. The dosage of described immobilization height salt tolerant COD degradation bacterium is 10��100g/L. Wherein, 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, is fixed in the carrier by high salt tolerant COD degradation bacterium; Wherein, described carrier is be not decomposed by the microorganisms and the carrier material of not polluted water, it is possible to be the natural macromolecular materials such as sodium alginate, it is also possible to be the synthesis macromolecular materials such as polyvinyl alcohol, can also is that the material such as zeolite, activated carbon, this is not construed as limiting by the present invention. Such as by after high salt tolerant COD degradation bacterium and polymerization medicament mixing, being then added dropwise in firming agent and make immobilization height salt tolerant COD degradation bacterium, the polymerization medicament in the method can be sodium alginate, it is also possible to be polyvinyl alcohol etc. For example with sodium alginate or carrageenan or agar or chitosan, and high salt tolerant COD degradation bacterium mixes, and under the effect of cross-linking agent, is fixed by high salt tolerant COD degradation bacterium, thus the high salt tolerant COD degradation bacterium of being fixed. For example with activated carbon or polyurethane cellular material, adsorb high salt tolerant COD degradation bacterium and prepare immobilization height salt tolerant COD degradation bacterium.
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, along with immobilization height salt tolerant COD degradation bacterium to reverse osmosis concentrated saline process the time increase, nutrient substance in reverse osmosis concentrated saline is more and more poorer, after being typically in process 5��20h, nutrient substance in reverse osmosis concentrated saline can not meet the needs of immobilization height salt tolerant COD degradation bacterium, it is to say, processing after 5��20h, immobilization height salt tolerant COD degradation bacterium cannot degradable organic pollutant again. Now, in reverse osmosis concentrated saline, add composite synergistic component, increase the nutrient substance in reverse osmosis concentrated saline so that immobilization height salt tolerant COD degradation bacterium can continue degradable organic pollutant. Described composite synergistic component includes: at least one in minor metallic element needed for COD degradation bacterium, alcohols, carbohydrate, phosphate, carbamide, ammonia spirit, ammonium salt. Wherein, described alcohols and described carbohydrate are used to provide carbon to immobilization height salt tolerant COD degradation bacterium, and described phosphate is used to provide P elements to immobilization height salt tolerant COD degradation bacterium; Described carbamide, described ammonia spirit, described ammonium salt are used to provide nitrogen element to immobilization height salt tolerant COD degradation bacterium. 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; Described ammonium salt includes: at least one in ammonium nitrate, ammonium sulfate, ammonium chloride, diammonium phosphate; Minor metallic element needed for described COD degradation bacterium includes: at least one in aluminum, calcium, cobalt, chromium, nickel, molybdenum, vanadium, stannum, strontium, rubidium, copper, ferrum, lead, magnesium, manganese, zinc.
In practical application, those skilled in the art can by least one in the minor metallic element needed for COD degradation bacterium, alcohols, carbohydrate, phosphate, carbamide, ammonia spirit, ammonium salt, it is added to the water, prepares and there is certain density composite synergistic component aqueous solution. Those skilled in the art can add composite synergistic component by the mode of addition composite synergistic component aqueous solution in reverse osmosis concentrated saline. In practical operation, those skilled in the art can prepare composite synergistic component according to the concrete condition of reverse osmosis concentrated saline and control the addition of composite synergistic component. Such as: the phosphorus content in reverse osmosis concentrated saline is less, the needs of immobilization height salt tolerant COD degradation bacterium cannot be met, those skilled in the art can join in reverse osmosis concentrated saline by including phosphatic composite synergistic component, and phosphorus content and the addition of composite synergistic component in composite synergistic component can control according to the phosphorus content in reverse osmosis concentrated saline.
Described composite synergistic component can be added after immobilization height salt tolerant COD degradation bacterium is to reverse osmosis concentrated saline treatment 5��20h again, it is also possible to is added simultaneously in reverse osmosis concentrated saline with immobilization height salt tolerant COD degradation bacterium.
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.
Research and development centre of high salt tolerant COD degradation Jun Shi Poten Environment Group Co., Ltd. in embodiment obtains after being placed in Halite water sample by COD degradation bacterium domestication step by step; 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.
The composite synergistic component used in embodiment is adopted and is prepared with the following method:
By 0.5gK2HPO4��0.1gFeSO4��7H2O��0.2g(NH4)2SO4��0.25gMgSO4��7H2O�� 0.32gCuSO4��5H2O and 0.2g carbamide joins in the water of 1L, prepares composite synergistic component.
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 10h;Then adding 5mL composite synergistic component again in reverse osmosis concentrated saline, continue to pass into air and carry out continuous aeration, the flow of air is 30L/min, collects water outlet after continuing Air Exposure 40h.
Effluent index: CODCrConcentration is 25.8mg/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 12, with sulfur acid for adjusting pH value to 5, adds 300g 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 15h; Then adding 10mL composite synergistic component again in reverse osmosis concentrated saline, continue to pass into air and carry out continuous aeration, the flow of air is 30L/min, collects water outlet after continuing Air Exposure 60h.
Effluent index: CODCrConcentration is 28.9mg/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 8.9, adds 200g immobilization height salt tolerant COD degradation bacterium, is simultaneously introduced 8mL composite synergistic component, passes into air and carry out continuous aeration, and the flow of air is 30L/min, collects water outlet after Air Exposure 20h.
Effluent index: CODCrConcentration is 27.2mg/L.
From above-described embodiment, the bioremediation of a kind of reverse osmosis concentrated saline provided by the invention, adopt immobilization height salt tolerant COD degradation bacterium and add composite synergistic component reverse osmosis concentrated saline is carried out enhanced biological process, 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 waste water; Composite synergistic component provides required nutrient substance can under the insufficient condition of nutrient substance immobilization height salt tolerant COD degradation bacterium. The COD of the reverse osmosis concentrated saline obtained after adopting method provided by the invention processCrConcentration, lower than 30mg/L, can be made directly evaporative crystallization. Method provided by the invention belongs to bioanalysis, less costly relative to advanced oxidation processes.
Above the bioremediation of a kind of reverse osmosis concentrated saline 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 (9)
1. a bioremediation for reverse osmosis concentrated saline, the salt content of described reverse osmosis concentrated saline is 1%��6%, CODCrConcentration is 100��1000mg/L, and ammonia nitrogen concentration is that 1��10mg/L, B/C ratio is lower than 0.2, it is characterised in that comprise the following steps:
Measure the pH value of reverse osmosis concentrated saline; 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; Add composite synergistic component, after continuing Air Exposure 20��60h, collect water outlet;
Or
Measure the pH value of reverse osmosis concentrated saline; When the pH value of reverse osmosis concentrated saline is 5��11, adds immobilization height salt tolerant COD degradation bacterium, be simultaneously introduced composite synergistic component, carry out continuous aeration, after processing 5��80h, collect water outlet;
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;
Described composite synergistic component includes: at least one in minor metallic element needed for COD degradation bacterium, alcohols, carbohydrate, phosphate, carbamide, ammonia spirit, ammonium salt.
2. bioremediation 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. bioremediation 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.
4. bioremediation as claimed in claim 3, 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%.
5. bioremediation 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��
6. bioremediation as claimed in claim 1 or 2, it is characterised in that described carbohydrate includes: at least one in monosaccharide, polysaccharide.
7. bioremediation as claimed in claim 1 or 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.
8. bioremediation as claimed in claim 1 or 2, it is characterised in that described ammonium salt includes: at least one in ammonium nitrate, ammonium sulfate, ammonium chloride, diammonium phosphate.
9. bioremediation as claimed in claim 1, it is characterised in that the minor metallic element needed for described COD degradation bacterium includes: at least one in aluminum, calcium, cobalt, chromium, nickel, molybdenum, vanadium, stannum, strontium, rubidium, copper, ferrum, lead, magnesium, manganese, zinc.
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| CN108117220A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of integrated conduct method of high slat-containing wastewater |
| CN108117225A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of processing method of high slat-containing wastewater |
| CN110372094A (en) * | 2019-07-17 | 2019-10-25 | 浙江卓锦环保科技股份有限公司 | A kind of high-salt wastewater integrated biochemical processing method |
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| CN103613190A (en) * | 2013-11-28 | 2014-03-05 | 广东联泰环保股份有限公司 | Salt-containing sewage treatment method |
| CN104150608A (en) * | 2014-07-31 | 2014-11-19 | 湖南永清水务有限公司 | Biochemical treatment process for high salinity wastewater |
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| JP2008100151A (en) * | 2006-10-18 | 2008-05-01 | Kobelco Eco-Solutions Co Ltd | Organic wastewater treatment method and organic waste water treatment device |
| CN103613190A (en) * | 2013-11-28 | 2014-03-05 | 广东联泰环保股份有限公司 | Salt-containing sewage treatment method |
| CN104150608A (en) * | 2014-07-31 | 2014-11-19 | 湖南永清水务有限公司 | Biochemical treatment process for high salinity wastewater |
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| CN108117225A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of processing method of high slat-containing wastewater |
| CN110372094A (en) * | 2019-07-17 | 2019-10-25 | 浙江卓锦环保科技股份有限公司 | A kind of high-salt wastewater integrated biochemical processing method |
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Denomination of invention: Biological treatment method for reverse osmosis strong brine Effective date of registration: 20200511 Granted publication date: 20181116 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 |