CN101318731A - Method for removing industrial wastewater with magnetic biological adsorption agent - Google Patents
Method for removing industrial wastewater with magnetic biological adsorption agent Download PDFInfo
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- CN101318731A CN101318731A CNA2008100318023A CN200810031802A CN101318731A CN 101318731 A CN101318731 A CN 101318731A CN A2008100318023 A CNA2008100318023 A CN A2008100318023A CN 200810031802 A CN200810031802 A CN 200810031802A CN 101318731 A CN101318731 A CN 101318731A
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- biological adsorption
- phanerochaete chrysosporium
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Abstract
The invention discloses a method for removing lead in industrial waste water by means of a magnetic biologic adsorbent. The method comprises the following steps that: firstly, the pH value of industrial waste water to be treated is adjusted to between 3.5 and 7; then, no less than 45g of magnetic biologic adsorbent is added in every stere of lead-containing waste water, and the temperature of the waste water is controlled between 20 and 40 DEG C; oscillation adsorption is carried out for 24 to 48 hours and then the adsorbent is filtered out; the filtered water is adjusted to neutrality and then is discharged, thereby completing the treatment of industrial waste water; and the magnetic biologic adsorbent is an immobilized magnetic nano particle-phanerochaete chrysosporium biologic adsorbent. The method has high adsorption efficiency, good adsorption effect, wide application range, simple treatment process, convenient operation and low cost, and can effectively remove lead in industrial waste water.
Description
Technical field
The present invention relates to a kind of bioremediation of trade effluent, relate in particular to bioremediation plumbous in a kind of trade effluent.
Background technology
The harm of heavy metal is more and more paid attention to by human in the environment, wherein lead is a kind of serious environmental poison and neural poison, to all toxic effects of system such as the nerve of human body, blood, digestion, uropoiesis, reproduction, internal secretion, immunity, will cause in various degree murder by poisoning to each system of human body whole body in case poison, especially influence brain functions such as infant, children's intelligence growth and learning and memory.Therefore, the processing to plumbous in the environment not only is related to growing up healthy and sound of children, also has influence on the long-range competitive power of Chinese follow-on intellectual level, population quality and country.
Lead waste water is mainly from battery production factory, Electroplate Factory and smeltery.Improvement for lead waste water, traditional method has chemiadsorption, ion exchange method, reverse osmosis, redox, solvent extraction, membrane sepn and electrodip process etc., but traditional method all more or less exists, and processing efficiency is not high, the bad defectives such as (it are following to make metal concentration drop to emission standard) of treatment effect, often needs that several different methods is united use and just can reach reasonable effect.
Biological adsorption technology is the new technology of the processing industrial pollution waste water that develops rapidly in recent years of environmental area, and it is with the heavy metal ion in various organisms (natural organism or its dead body) the absorption waste water.Compare with traditional method, biological method has advantages such as loading capacity is big, selectivity is strong, efficient is high, energy consumption is low, simple to operate, viable economically, can handle effectively and purification contains low-concentration heavy metal ionic waste water.Yet the biological adsorption agent of existing report mostly is the free state microorganism, because problems such as its long action time, reaction efficiency are low, solid-liquid separation difficulty make its application be subjected to very big restriction again.Immobilized microorganism technique is a kind of new bio technology of rising the eighties in 20th century, it utilizes the polymer material of biological or chemical that the microorganism embedding is got up not only to increase substantially the microorganism concn of participating in reaction, make microorganism be difficult for running off and polluting, and action time is longer, antitoxin and tolerance is obviously strengthened, solid-liquid separation is easy, and secondary pollution is few, thereby demonstrates good prospects for application.How immobilized microorganism technique is applied in the lead waste water processing, just becomes the new problem that those skilled in the art face.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide a kind of adsorption efficiency height, advantages of good adsorption effect, applied widely, treatment process is simple, the magnetic biological adsorption agent that utilizes easy to operate, that cost is low is removed method plumbous in the trade effluent.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is that a kind of magnetic biological adsorption agent that utilizes is removed method plumbous in the trade effluent, it is characterized in that: pH value to 3.5～7 of regulating pending trade effluent earlier, in every cubic metre lead waste water, add the magnetic biological adsorption agent of 45～50g then, temperature is controlled at 20 ℃～40 ℃, the absorption of vibrating again, filtering sorbent material after 24～48 hours, filtrate is adjusted to the discharging of neutral back, finishes processing trade effluent; Described magnetic biological adsorption agent is immobilized magnetic nano-particle-Phanerochaete chrysosporium biological adsorption agent.
Above-mentioned vibration adsorption process is to adopt shaking table to carry out, and the revolution of shaking table is 150～200rpm.
The magnetic nano-particle of said fixingization-Phanerochaete chrysosporium biological adsorption agent is to be carrier with the alginate calcium, and being embedded with Phanerochaete chrysosporium bacterium powder and magnetic nano-particle, the mass ratio of described Phanerochaete chrysosporium bacterium powder, magnetic nano-particle and alginate calcium is 1: (0.5～1.25): (8～10).This magnetic biological adsorption agent is to prepare by the following method: liquid cultivation Phanerochaete chrysosporium (Phanerochaete chrysosporium, CCTCC AF96007), collect the bacterium ball with its lyophilize, and grind to form the bacterium powder; Prepare magnetic nano-particle and sodium alginate soln simultaneously, it is in 1%～2% the sodium alginate soln that magnetic nano-particle and Phanerochaete chrysosporium bacterium powder mixture are joined mass concentration, add 0.125～0.225g magnetic nano-particle and Phanerochaete chrysosporium bacterium powder mixture in every milliliter of sodium alginate soln, stir; Getting the sodium alginate soln that 1～2 volume has been added with magnetic nano-particle and Phanerochaete chrysosporium bacterium powder mixture, is the CaCl of 0.2mol/L～0.3mol/L with syringe with its concentration that dropwise changes 10 volumes over to
2In the solution, left standstill under room temperature 18～24 hours, with sterilized water and the washing of sodium succinate damping fluid, drying prepares magnetic biological adsorption agent again.
Described magnetic nano-particle and Phanerochaete chrysosporium bacterium powder mixture are prepared as follows and are obtained: will cultivate the Phanerochaete chrysosporium bacterium ball lyophilize after (30～37 ℃ of culture temperature) in 4～6 days, be ground into 120～200 purpose bacterium powder again, bacterium powder and magnetic nano-particle are pressed mass ratio 1: (0.5～1.25) is evenly mixed.
PH value in the technical solution of the present invention, temperature control and adsorption time are to determine by following adsorption test to laboratory simulation waste water.
1, pH value scope determines.Get 1m
3100mg/L contain Pb
2+Waste water by adding NaOH solution or salt acid for adjusting pH value, is made into the serial solution of pH value 2～7, add the magnetic biological adsorption agent that the 48g method for preparing obtains, temperature is 35 ℃, stir 24h on the vibrator after, filter, measure the lead ion content (measurement result sees Table 1) in the water of absorption back.Be higher than at 3.5 o'clock in the pH value, the Pb more than 99% is arranged
2+Be removed.Consider under alkaline condition Pb
2+Can form the lead hydroxide precipitation, so the pH scope of the suitable absorption of this magnetic biological adsorption agent is: 3.5～7.0, optimal adsorption pH value is 4.5.
Table 1 sorbent material under different pH condition to Pb
2+Removal
| The pH value | 2 | 2.5 | 3 | 3.5 | 4 | 4.5 | 5 | 5.5 | 6 | 7 |
| Clearance (%) | 87.4 | 95.0 | 98.5 | 99.2 | 99.6 | 99.5 | 99.4 | 99.4 | 99.3 | 99.2 |
2, the optimal adsorption temperature determines.By under condition of different temperatures, mixed adsorbent is added to 100mg/L, the pH value is in 4.5 the laboratory simulation waste water, under the rotating speed 150rpm condition, respectively under 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ temperature, vibration absorption 24h.Waste water after the processing leaves standstill, and sorbent material directly precipitates rapidly, filters, and absorbs Pb in the solution of spectrophotometric determination absorption back with NITRATE BY FLAME ATOMIC
2+Concentration, the record result, as shown in table 2, the suitable adsorption temp that magnetic biological adsorption agent of the present invention is handled lead waste water is 20 ℃～40 ℃, the optimal adsorption temperature is 35 ℃.
Table 2 sorbent material in condition of different temperatures to Pb
2+Removal
| Adsorption temp (℃) | 20.0 | 25.0 | 30.0 | 35.0 | 40.0 |
| Clearance (%) | 98.23 | 98.48 | 99.42 | 99.61 | 99.55 |
3, the optimal adsorption time determines.The magnetic biological adsorption agent that adds above-mentioned preparation respectively is to Pb
2+Concentration is 100mg/L, and the pH value is in 4.5 the laboratory simulation waste water.At 35 ℃ of constant temperature, under the rotating speed 150rpm condition, vibration absorption, adsorption time is respectively 0.5h, 1h, 2h, 4h, 6h, 8h, 16h, 24h, 36h, 48h.Take out sample at above adsorption time, filter, and collect filtrate in the 25mL volumetric flask, absorb Pb in the solution of spectrophotometric determination absorption back in NITRATE BY FLAME ATOMIC
2+Concentration, the result is as shown in table 3 for record, and the optimal adsorption time that it is suitable that magnetic biological adsorption agent of the present invention is handled lead-containing industrial wastewater is 24h～48h, because 36h, 48h and 24h treatment effect difference are little, so the aspect considers that the optimal adsorption time is 24h from saving time.
Table 3 sorbent material at different adsorption times to Pb
2+Removal
| Adsorption time (h) | 0.5 | 1.0 | 2.0 | 4.0 | 6.0 | 8.0 | 16.0 | 24.0 | 36.0 | 48.0 |
| Clearance (%) | 58.62 | 71.25 | 76.78 | 79.25 | 82.48 | 85.08 | 94.73 | 99.46 | 99.53 | 99.54 |
Therefore, utilize method of the present invention to handle the processing efficiency height of lead waste water, clearance is more than 98%.Be 4.5 in the pH value, temperature is that 35 ℃, adsorption time are under the top condition of 24h, the clearance of the inventive method can reach 99.5%.Method of the present invention has improved ability to bear and the stability of magnetic biological adsorption agent to toxic substance, improved the processing load and the processing efficiency of pollutent, and technology is simple, and it is lower to pollute investment cost and working cost.
Description of drawings
Fig. 1 is that the inventive method is to containing different concns Pb
2+The adsorption effect comparison diagram of waste water.
Embodiment
Embodiment:
1, the preparation of Phanerochaete chrysosporium bacterium powder
The Phanerochaete chrysosporium (CCTCC AF96007) of buying scraped from the slant medium of preservation get, and be seeded to the potato dextrose culture-medium, dress liquid nutrient medium 200mL in every 500mL Erlenmeyer flask, 30～37 ℃ of culture temperature,, after 5 days the bacterium ball is leached in shaking culture under 150～180rpm rotating speed, use the deionized water repetitive scrubbing, after collecting the lyophilize of bacterium ball, ground 180 mesh sieves and obtained the bacterium powder.Described potato dextrose culture-medium consists of: potato 40g, glucose 4g, water 200mL.
2, the preparation of magnetic nano-particle
(1) the hydrochloric acid 50mL of preparation 0.4mol/L gets 38mL in beaker, inflated with nitrogen 10min; Take by weighing the FeCl of 8.5g
36H
2The FeCl of O and 3g
24H
2O is dissolved in the hydrochloric acid of the 0.4mol/L that filled nitrogen;
(2) the ammoniacal liquor 375mL of preparation 0.7mol/L, inflated with nitrogen 10min before the preparation; Intense mechanical stirs down, with above-mentioned FeCl
3, FeCl
2Pour in the ammoniacal liquor with the mixed solution of hydrochloric acid, generate Fe
3O
4Gelatinous precipitate 3.48g; Mechanical stirring 30min, natural subsidence is also followed magneticseparation (24 hours), removes supernatant liquor;
(3) with Fe
3O
4With ultrapure water washing 3 times, natural subsidence is followed magneticseparation (24 hours), is scattered in then in the ultrapure water of 150mL (23.2mg/mL);
(4) get the Fe that obtains after the above-mentioned dispersion
3O
4Suspension 20mL joins in the n-propyl alcohol of 200mL ultrasonic 20min; Mechanical stirring adds polyglycol (PEG) 5.36g (1.34mmol, molecular weight 4000), 20mL ultrapure water, 10mL ammoniacal liquor successively; Stirring at room 24h;
(5) centrifugation: under the rotating speed of 8000rpm, centrifugal 5min; Use ethanol, water ultrasonic cleaning 2 times respectively; Separate, lyophilize makes magnetic nano-particle.
3, the immobilization of magnetic nano-particle and Phanerochaete chrysosporium bacterium powder
With in the above-mentioned steps 1 preparation Phanerochaete chrysosporium bacterium powder and step 2 in the preparation magnetic nano-particle mix, the mass ratio of Phanerochaete chrysosporium bacterium powder and magnetic nano-particle is 1: 0.5, with 5g magnetic nano-particle and Phanerochaete chrysosporium bacterium powder mixture, join the 40mL mass concentration and be in 2% the sodium alginate soln, stir; Dropwise change it CaCl of 200mL 0.2mol/L over to syringe
2In the solution, under room temperature, placed 18 hours, wash repeatedly with sterilized water and 0.05mol/L sodium succinate damping fluid (pH 4.5) again, finish immobilization process, make the spherical magnetic biological adsorption agent of even rule.
4, the lead in the trade effluent is handled
Get waste water 1m
3, analyze the Pb of this waste water
2+Content is about 100mg/L, after waste water regulated pH value to 4.5 by the acid-alkali accommodation pond, in reactive tank, add the above-mentioned magnetic biological adsorption agent for preparing of 48g, in temperature is 35 ℃, and rotating speed is under the 150rpm condition, vibration absorption, behind the question response 24h, leave standstill, direct filtration is separated water outlet and used magnetic biological adsorption agent.Measuring the lead content that is not adsorbed with atomic absorption spectrophotometry is 0.276mg/L, and (total lead＜1.0mg/L), plumbous clearance reaches 99.7% to be lower than the highest permission emission standard of national first kind pollutent.Because the pH value of processed waste water is subacidity, adds and can directly discharge after a little alkali is adjusted to 6～9.Magnetic biological adsorption agent after the use can be recycled by parsing.
The immobilization magnetic biological adsorption agent that again method for preparing is obtained adds to respectively in the lead-containing industrial wastewater of different concns, and it is to Pb
2+Adsorption effect see Table 4 and Fig. 1.Clearance to the lead waste water of 50mg/L reaches 99.9%, absorption back Pb
2+Residual volume is 0.014mg/L, reaches national standard (total lead＜1.0mg/L) of the highest permission emission concentration of first kind pollutent; The clearance of trade effluent that to lead concentration is 300mg/L～500mg/L is all more than 99%, but remaining lead concentration surpasses 1.0mg/L, does not reach emission standard, therefore, when using immobilized magnetic nano-particle-Phanerochaete chrysosporium biological adsorption agent, if Pb in the trade effluent
2+Concentration surpass 200mg/L, can handle by increasing this magnetic biological adsorption agent usage quantity.As seen, utilize method of the present invention to handle the trade effluent that contains lead concentration≤500mg/L, effect is best.
Table 4 magnetic biological adsorption agent is to removal effect plumbous in the trade effluent
| Lead concentration (mg/L) before handling | 50.00 | 100.00 | 200.00 | 300.00 | 500.00 |
| Residual lead concentration (mg/L) | 0.014 | 0.276 | 0.679 | 1.609 | 2.055 |
Claims (5)
1, a kind of magnetic biological adsorption agent that utilizes is removed method plumbous in the trade effluent, it is characterized in that: pH value to 3.5～7 of regulating pending trade effluent earlier, in every cubic metre lead waste water, add the magnetic biological adsorption agent that is no less than 45g then, temperature is controlled at 20 ℃～40 ℃, the absorption of vibrating again, filtering sorbent material after 24～48 hours is adjusted to the discharging of neutral back with filtrate, finishes the processing to trade effluent; Described magnetic biological adsorption agent is immobilized magnetic nano-particle-Phanerochaete chrysosporium (Phanerochaete chrysosporium) biological adsorption agent.
2, method according to claim 1, it is characterized in that described immobilized magnetic nano-particle-Phanerochaete chrysosporium biological adsorption agent is to be carrier with the alginate calcium, and being embedded with Phanerochaete chrysosporium bacterium powder and magnetic nano-particle, the mass ratio of described Phanerochaete chrysosporium bacterium powder, magnetic nano-particle and alginate calcium is 1: (0.5～1.25): (8～10).
3, method according to claim 1 is characterized in that described vibration adsorption process is to adopt shaking table to carry out, and the revolution of shaking table is 150～200rpm.
4, method according to claim 1 is characterized in that the processing parameter in adsorption process satisfies:
The pH value is 4.5;
Temperature is 35 ℃;
Adsorption time is 24h.
5, according to each described method in the claim 1～4, it is characterized in that: when containing lead concentration when 500mg/L is following in the pending trade effluent, the addition of described magnetic biological adsorption agent is to add 45～50g in every cubic metre the lead waste water.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816920A (en) * | 2010-03-25 | 2010-09-01 | 湖南大学 | Modified phanerochaete chrysosporium adsorbent as well as preparation and application thereof |
| CN102531194A (en) * | 2010-12-24 | 2012-07-04 | 中国科学院过程工程研究所 | Biological dechromizing medium, preparation method thereof and biological dechromizing method |
| CN103168619A (en) * | 2013-03-04 | 2013-06-26 | 武汉理工大学 | Cultural method for improving degradation performance of phanerochaete chrysosporium |
| CN104138738A (en) * | 2014-07-18 | 2014-11-12 | 常州大学 | Method for removing nitrite in drinking water grade polymeric aluminum chloride prepared from waste acid |
| CN104941592A (en) * | 2015-05-26 | 2015-09-30 | 东华理工大学 | Magnetic biological material capable of adsorbing uranium (VI) in aqueous solution and preparation method of magnetic biological material |
-
2008
- 2008-07-17 CN CN200810031802A patent/CN100582023C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816920A (en) * | 2010-03-25 | 2010-09-01 | 湖南大学 | Modified phanerochaete chrysosporium adsorbent as well as preparation and application thereof |
| CN101816920B (en) * | 2010-03-25 | 2012-07-04 | 湖南大学 | Modified phanerochaete chrysosporium adsorbent as well as preparation and application thereof |
| CN102531194A (en) * | 2010-12-24 | 2012-07-04 | 中国科学院过程工程研究所 | Biological dechromizing medium, preparation method thereof and biological dechromizing method |
| CN103168619A (en) * | 2013-03-04 | 2013-06-26 | 武汉理工大学 | Cultural method for improving degradation performance of phanerochaete chrysosporium |
| CN103168619B (en) * | 2013-03-04 | 2016-01-06 | 武汉理工大学 | A kind of cultural method improving Phanerochaete chrysosporium degradation property |
| CN104138738A (en) * | 2014-07-18 | 2014-11-12 | 常州大学 | Method for removing nitrite in drinking water grade polymeric aluminum chloride prepared from waste acid |
| CN104138738B (en) * | 2014-07-18 | 2016-06-15 | 常州大学 | A kind of minimizing technology utilizing spent acid to prepare drinking water level aluminium polychlorid nitrite |
| CN104941592A (en) * | 2015-05-26 | 2015-09-30 | 东华理工大学 | Magnetic biological material capable of adsorbing uranium (VI) in aqueous solution and preparation method of magnetic biological material |
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|---|---|
| CN100582023C (en) | 2010-01-20 |
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