CN103041777A - Fe3O4/CS magnetic material adsorbent, preparation method of Fe3O4/CS magnetic material adsorbent, and sewage treatment method - Google Patents
Fe3O4/CS magnetic material adsorbent, preparation method of Fe3O4/CS magnetic material adsorbent, and sewage treatment method Download PDFInfo
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- CN103041777A CN103041777A CN201310031463XA CN201310031463A CN103041777A CN 103041777 A CN103041777 A CN 103041777A CN 201310031463X A CN201310031463X A CN 201310031463XA CN 201310031463 A CN201310031463 A CN 201310031463A CN 103041777 A CN103041777 A CN 103041777A
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Abstract
The invention relates to a Fe3O4/CS magnetic material adsorbent, a preparation method of the Fe3O4/CS magnetic material adsorbent, and a sewage treatment method. According to the preparation method, the Fe3O4/CS magnetic material adsorbent is compounded by using a one-step solvothermal method, the shape of the Fe3O4/CS magnetic material adsorbent shows up as a monodispersed fuzz ball body and is nearly free from an agglomerate phenomenon, the diameter of the Fe3O4/CS magnetic material adsorbent is 100-200nm, the specific surface area is 32.18 m<2>/g, the adsorption equilibrium can be fast realized within 30min in the adsorption process for adsorbing and removing sodium pentachlorophenate (PCP-Na) by Fe3O4/CS, and the largest removing rate (91.5%) of the sodium pentachlorophenate (PCP-Na) is obtained under a condition approaching the normal temperature (25 DEG C) and a neutral slightly-acidic condition that the pH value approaches the common water body, so that the high efficiency for realizing the adsorption equilibrium of the Fe3O4/CS in water adsorbing and removing and the high efficiency for adsorbing and removing the PCP-Na by the Fe3O4/CS are embodied, and the Fe3O4/CS has feasibility and superiority in the practical application, not only is the repeated use of the adsorbent realized, but also the waste and the secondary pollution caused by inconvenient recycling of an adsorption catalyst are avoided.
Description
Technical field
The present invention relates to a kind of sewage disposal, relate in particular to a kind of Fe
3O
4/ CS magnetic material adsorbent and preparation method and sewage water treatment method.
Background technology
Pentachlorophenol (PCP) and salt compounds, especially penta sodium pentachlorophenate (PCP-Na) worldwide once were widely used in preventing the pesticide of arboreal growth fungi, prevention and cure of schistosomiasis etc.Because its toxicity, mutagenicity, carcinogenicity, endocrine interference and bioconcentration, pentachlorophenol and its esters have been known as priority pollutant and persistence organic pollutant.Pentachlorophenol in disposing of sewage pollutes and mostly adopts the adsorbents such as resin, active carbon, carbon black, float stone, zeolite, but, exist the problem of cost costliness.
At present, seek the effectively adsorbent of adsorbing and removing organic pollutants, also good dispersion, the rate of adsorption are fast round seeking simultaneously, advantages of good adsorption effect and reclaim and be easy to adsorbent.
Summary of the invention
Main purpose of the present invention is to solve the problem of above-mentioned dispose of sewage middle pentachlorophenol and saline pollution thereof, and a kind of Fe is provided
3O
4/ CS magnetic material adsorbent and preparation method and sewage water treatment method.
It is documented that absorption method needs to improve aspect two: 1, absorption method mainly is the heavy metal pollution etc. that is applied in the adsorbing and removing water, also is weak and be directed to the adsorbing and removing organic pollutants; 2, mostly to exist adsorption capacity less for current adsorbent, bad dispersibility, reclaims difficulty, even cause the shortcoming such as secondary pollution, and simultaneously, also there is expensive problem in adsorbent (such as active carbon etc.).
The technical solution adopted for the present invention to solve the technical problems is:
Fe
3O
4/ CS magnetic material adsorbent is synthetic by a step solvent-thermal method, and its pattern shows as monodispersed bobbles body, and almost without agglomeration, between the 200nm, specific area is 32.18m to diameter between 100nm
2/ g, Fe
3O
4The adsorption process of penta sodium pentachlorophenate (PCP-Na) has just realized rapidly adsorption equilibrium at 30min with interior in the/CS adsorbing and removing water, and descends to obtain maximum penta sodium pentachlorophenate (PCP-Na) removal efficiency (91.5%) near ambient temperature (25 ℃) and acid-base value near the neutral slant acidity condition (pH=6.5) of general water body.
Fe of the present invention
3O
4/ CS magnetic Nano material adsorbent is synthetic by a step solvent-thermal method, possesses novel pattern, shows as monodispersed bobbles body, almost without agglomeration, its diameter be at 100nm between the 200nm, specific area is 32.18m
2/ g.Fe
3O
4The adsorption process of penta sodium pentachlorophenate (PCP-Na) has just realized rapidly adsorption equilibrium at 30min with interior in the/CS adsorbing and removing water, and descend to obtain maximum PCP-Na removal efficiency (91.5%) near the neutral slant acidity condition (pH=6.5) of general water body near ambient temperature (25 ℃) and acid-base value, shown Fe
3O
4Feasibility and the superiority of/CS adsorbent adsorbing and removing PCP-Na.
Among the present invention without chitosan-modified Fe
3O
4Nano material shows as the round and smooth orbicule in surface, has more serious agglomeration, the about 200 ~ 350nm of average diameter, and specific area is 6.35m2/g.Fe of the present invention is described
3O
4/ CS magnetic Nano material adsorbent particle diameter has reduced, and dispersiveness has strengthened, and specific area has also increased thereupon.Preparation initial p CP concentration is 100mg/L, and initial pH is 6.5, and the temperature that shaking bath is set is 25 ℃, and oscillation rate is 250rpm.Fe
3O
4The adsorption process of/CS adsorbing and removing PCP-Na has just realized adsorption equilibrium having shown Fe rapidly with interior at 30min
3O
4The high efficiency of/CS adsorbing and removing PCP-Na.Fe
3O
4The amount of/CS adsorbent is very large on the impact of adsorbing and removing PCP-Na.As the Fe that uses 0.15g
3O
4During/CS nano material, the amount of removing of PCP-Na is 70.0%, and when the amount of adsorbent was increased to 0.28g, the amount of removing of PCP-Na increased to 91.5%.
In the 100L mixer, add the anhydrous FeCl of 200g ~ 1.6kg
3With 40L ethylene glycol, after mixer fully stirred, solution was the red tan solution of homogeneous transparent.In transparent red tan solution, add people 0.9kg ~ 7.2kg sodium acetate and 0.2 ~ 5.0kg shitosan, continue to stir 30min, form the outstanding turbid homogenate of rufous.
The present invention adds the anhydrous FeCl of 200g ~ 1.6kg in the mixer of 100L
3With 40L ethylene glycol, open the stirring power supply, after fully stirring, formed the red tan solution of homogeneous transparent.In this clear solution, add 0.9kg ~ 7.2kg sodium acetate and 0.2 ~ 5.0kg shitosan, continue to stir 30min, form the outstanding turbid homogenate of rufous.
The present invention continues to increase the amount of adsorbent, and (0.30 ~ 0.40g) does not remove generation facilitation, Fe to PCP-Na
3O
4The optimal dose of/CS adsorbing and removing PCP-Na is 2.8g/L.Simultaneously, according to Fe
3O
4/ CS and Fe
3O
4Can find as adsorbent respectively, under identical experiment condition, utilize Fe
3O
4During as adsorbent, the maximum amount of removing of PCP-Na is 69.2%, and adsorption process could realize adsorption equilibrium at about 2h.Obviously, Fe
3O
4The rate of adsorption of/CS magnetic Nano material and adsorbance have all shown remarkable adsorption effect, prove that it is as feasibility and the superiority of adsorbent adsorbing and removing PCP-Na.
In with teflon-lined stainless steel autoclave, import outstanding turbid homogenate, the temperature of conditioned reaction still is 200 ℃, off-response still after the reaction 12h, the question response still naturally cools to room temperature, obtains black suspension, isolate black solid by magnetic field, black solid is imported in the washing system, with absolute ethanol washing number time, at last black solid is placed 60 ℃ of drying boxes to dry to constant weight, obtain black powder, black powder is put into drier store for future use.
The present invention should be hanged turbid homogenate and be imported in the 50L band teflon-lined stainless steel autoclave, and the temperature of conditioned reaction still is 200 ℃, the temperature control power supply of off-response still after the reaction 12h.After the question response still naturally cools to room temperature, obtain black suspension.Isolate black solid by magnetic field, this black solid is imported in washing system, with absolute ethanol washing number time, at last black solid is placed 60 ℃ of drying boxes to dry to constant weight, obtain black powder, put into drier and store for future use.The transmission electron microscope photo of this powder is seen Fig. 1, and X-ray diffractogram and Fourier's infrared spectrogram are seen Fig. 2, and hysteresis graph is seen Fig. 3.
B-H loop of the present invention shows a kind of Fe that the present invention is prepared
3O
4/ CS magnetic Nano material adsorbent has superparamagnetism, its saturation magnetization with without chitosan-modified Fe
3O
4Nano material is not compared and is reduced, and this means that beautify chitosan does not change the saturation magnetization of material.After finishing adsorption experiment, can from the absorption solute, isolate Fe rapidly by using a permanent magnet
3O
4/ CS magnetic Nano material, and then effective separation and the recycling of realization adsorbent have shown that magnetic adsorbent is applied to the superiority of sewage disposal, as shown in Figure 3.
Wash-out regenerative system by magnetic material absorption processing system and saturable magnetic materials adsorbent forms, absorption processing system is by water inlet pipe, retort, the electric stirring slurry, at the bottom of the open-close type tank, adsorbent adds pipe, control device, saturable magnetic materials adsorbent collection bucket, outlet pipe, suction pump and sealing hinge form, retort integral body is tubbiness, be hollow in the bucket, capacity is 200L at least, reaction liquid enters retort by water inlet pipe, the retort top ends is installed adsorbent and is added pipe and control device, control device control adsorbent adds the amount that pipe drops into adsorbent, install the electric stirring slurry in the retort, the electric stirring slurry stirs and drops into retort internal reaction liquid.
The present invention is divided into the wash-out regenerative system of magnetic material absorption processing system and saturable magnetic materials adsorbent, by the magnetic material absorption processing system sewage is implemented adsorption treatment first, again the saturable magnetic materials adsorbent that produces in the adsorption treatment process is implemented wash-out regeneration, magnetic material adsorbent after the wash-out regeneration changes the magnetic material absorption processing system over to again and reuses the reciprocation cycle of going round and beginning again.
Outlet pipe and suction pump are installed in the top of retort, insert in the retort one end of outlet pipe, the other end of outlet pipe is connected with suction pump, by after treatment reaction liquid in outlet pipe and the suction pump extraction tank, water inlet pipe is installed in the bottom of retort, inputs need sewage to be processed by water inlet pipe in retort.
The top of retort of the present invention arranges adsorbent and adds pipe, control device and electric stirring oar, and adjustment control device control adsorbent adds pipe and input the amount that needs in retort, starts the interior reaction liquid of the abundant stirred tank of electric stirring oar.
Install at the bottom of the open-close type tank bottom of retort, be tightly connected by sealing hinge and retort at the bottom of the open-close type tank, install the sucked type electromagnet at the bottom of the open-close type tank, on the saturable magnetic materials adsorbent is adsorbed onto at the bottom of the open-close type tank behind the plugged, saturable magnetic materials adsorbent collection bucket is installed in the following and retort corresponding section of retort, saturable magnetic materials adsorbent collection bucket is collected the saturable magnetic materials adsorbent, opens to emit the saturated adsorption agent at the bottom of the open-close type tank of retort and enter saturable magnetic materials adsorbent collection bucket.
Arranging at the bottom of the open-close type tank of retort of the present invention, the sucked type electromagnet is set at the bottom of the open-close type tank, adsorb the saturable magnetic materials adsorbent in the anti-retort, saturable magnetic materials adsorbent collection bucket is set below the retort, collect the saturable magnetic materials adsorbent in the retort.
The wash-out regenerative system of saturable magnetic materials adsorbent is comprised of adsorbent feed pipe, adsorbent control device, wash-out exchange column, eluent water inlet pipe, peristaltic pump, eluent outlet pipe, sample tap, eluent circulation pipe and eluent drainpipe, wash-out exchange column integral body is tubbiness, be hollow in the bucket, wash-out exchange column top ends is installed adsorbent feed pipe and adsorbent control device, adsorbent control device control adsorbent feed pipe injected volume in the wash-out exchange column.
Eluent outlet pipe, sample tap and eluent drainpipe are installed in the top of wash-out exchange column, and an end of eluent outlet pipe is connected with the wash-out exchange column, and the other end of eluent outlet pipe is connected with sample tap, and sample tap is connected with the eluent drainpipe.
The top of the wash-out exchange column of the wash-out regenerative system of saturable magnetic materials adsorbent of the present invention arranges the adsorbent feed pipe, the adsorbent control device is set, the input amount of adsorbent control device control adsorbent feed pipe input wash-out exchange column on the adsorbent feed pipe.The top of wash-out exchange column arranges the eluent outlet pipe, and the eluent outlet pipe is connected with the eluent drainpipe, between eluent outlet pipe and the eluent drainpipe sample tap is set, and extracts eluent sample liquid from sample tap, and examinations.
The eluent water inlet pipe is installed in the bottom of wash-out exchange column, one end of eluent water inlet pipe is connected with the bottom of wash-out exchange column, the other end of eluent water inlet pipe is connected with the eluent circulation pipe, install peristaltic pump on the eluent water inlet pipe, the eluent circulation pipe is connected with the eluent drainpipe, drive peristaltic pump the eluent in the eluent circulation pipe is carried in the wash-out exchange column, wash-out exchange column inner bottom part arranges supporting layer, and supporting layer adopts the bead of particle diameter 6 ~ 7mm.
The bottom of wash-out exchange column of the present invention arranges the eluent water inlet pipe, the eluent water inlet pipe is connected with the eluent circulation pipe, the eluent circulation pipe is connected with the eluent drainpipe, eluent water inlet pipe, eluent circulation pipe and eluent drainpipe consist of the circulation road, on the eluent water inlet pipe peristaltic pump is set, drives the eluent circulation.Eluent exchange column inner bottom part arranges supporting layer, and supporting layer is evenly arranged eluent in the eluent exchange column.
Then the processing of at first sewage being adsorbed magnetic material in the magnetic material absorption processing system is carried out wash-out regeneration to the saturable magnetic materials adsorbent and is processed the Fe that wash-out bears again in the wash-out regenerative system of saturable magnetic materials adsorbent
3O
4/ CS magnetic material adsorbent is reused in the magnetic material absorption processing system again, be the PCP-Na solution of 50g ~ 200mg/L by water inlet pipe input initial concentration in the retort, add hydrochloric acid and sodium hydroxide solution in the retort, after the pH value of PCP-Na solution reaches 6.0 ~ 11.0 in the conditioned reaction tank, open control device, add pipe by adsorbent and in retort, add 150g ~ 400g Fe
3O
4/ CS adsorbent.Start the electric stirring slurry, the liquid in the abundant stirred tank, the stir speed (S.S.) of electric stirring slurry is 250rpm, the temperature of retort is respectively 25 ℃, 35 ℃ and 45 ℃.
The present invention is that to add initial concentration in the retort of 200L be the PCP-Na solution 100L of 50 ~ 200mg/L toward volume, regulate the pH to 6.0 of PCP-Na solution ~ 11.0 with hydrochloric acid and sodium hydroxide solution after, in retort, add 150 ~ 400g Fe
3O
4/ CS adsorbent.Open the electric stirring slurry power supply in the retort tank body, the adjusting stir speed (S.S.) is 250rpm, and the temperature of conditioned reaction tank is respectively 25 ℃, 35 ℃ and 45 ℃.
After liquid adsorption reaction in the retort finishes, close the electric stirring slurry, sucked type electromagnet at the bottom of the startup open-close type tank, according to the electromagnetic conversion principle, sucked type electromagnet at the bottom of the open-close type tank produces powerful electromagnetic attraction under "on" position, treat at the bottom of the open-close type tank at the bottom of the saturable magnetic materials adsorbent is drawn onto rapidly the tank of retort on.
Start suction pump, the solution after adsorption reaction transfers out retort by outlet pipe, and the sucked type electromagnet power supply in closing at the bottom of the open-close type tank stops adsorption operation.The opening encapsulation hinge, the pot bottom of retort is opened, and the saturable magnetic materials adsorbent imports in the saturable magnetic materials adsorbent collection bucket below the retort.
After adsorption reaction finishes, close electric stirring slurry power supply, open the power supply of the sucked type electromagnet at the bottom of the sucked type open-close type tank at the bottom of the retort tank, according to the electromagnetic conversion principle, sucked type electromagnet at the bottom of the sucked type open-close type tank produces powerful electromagnetic attraction under "on" position, be drawn onto rapidly at the bottom of the tank of retort until the saturated adsorption agent after, open suction pump, the solution after adsorption reaction is taken away by suction pump.The power supply of the sucked type electromagnet in then closing at the bottom of the open-close type tank is opened the tank body of coupled reaction tank and the sealing hinge at the bottom of the tank, is opened at the bottom of the tank of retort, and the saturable magnetic materials adsorbent arrives saturable magnetic materials adsorbent collection bucket and obtains collection.
The saturable magnetic materials adsorbent is imported the wash-out regenerative system of saturable magnetic materials adsorbent, implementing wash-out regeneration processes, bottom in the wash-out exchange column arranges supporting layer, supporting layer adopts the bead of particle diameter 6 ~ 7mm, open the adsorbent control device, saturable magnetic materials adsorbent in the saturable magnetic materials adsorbent collection bucket is input in the wash-out exchange column by the adsorbent feed pipe, the NaOH solution of methyl alcohol and 0.5 ~ 1.5mol/L by volume 1:1 be mixed into eluent, flowing through from bottom to top in the wash-out exchange column through the eluent water inlet pipe by peristaltic pump is filled with the saturable magnetic materials adsorbent, and the flow velocity of eluent is 5 ~ 40mL/h;
The wash-out regenerative system of the saturable magnetic materials adsorbent input saturable magnetic materials adsorbent that the present invention discharges in the retort of magnetic material absorption processing system is implemented the wash-out regeneration of saturable magnetic materials adsorbent and is processed.
The present invention fills up internal diameter toward wash-out exchange column bottom be that the bead of 6 ~ 7mm is as supporting layer, then toward wherein adding the saturated adsorption agent of collecting after the adsorption experiment end.By the NaOH solution of methyl alcohol and the 0.5 ~ 1.5mol/L eluent that mixes of the 1:1 wash-out exchange column of flowing through from bottom to top and being filled with the saturable magnetic materials adsorbent by the eluent water inlet pipe by volume.The flow velocity of regulating eluent by the speed-regulating type peristaltic pump is 5 ~ 40mL/h.
Regularly from the sample tap of eluent outlet pipe eluent is taken a sample, and the concentration of PCP-Na in the mensuration eluent, when the concentration of PCP-Na is lower than 50mg/L, eluent enters in the wash-out exchange column by the bottom of eluent circulation pipe by the wash-out exchange column from the top of wash-out exchange column, iterative cycles, when the concentration of PCP-Na in the eluent reached a peak, saturated eluent was discharged from the eluent drainpipe, successively the reciprocation cycle wash-out.
The present invention's timing is at the sample tap quantitative collection eluent at the eluent outlet pipe place of saturated adsorption agent wash-out regenerative system, measure the concentration of PCP-Na in the eluent, when the concentration of PCP-Na is lower than 50mg/L, eluent returns the wash-out regenerative system by the eluent circulation pipe, when the concentration of PCP-Na in the eluent reached a peak, saturated eluent was discharged by the eluent drainpipe.
When the concentration of PCP-Na is lower than 5mg/L, finish the wash-out regenerative response of saturable magnetic materials adsorbent, collect the magnetic material adsorbent, and oven dry preserves, send into the recycling of magnetic material absorption processing system.
The concentration that the present invention measures PCP-Na is lower than the wash-out regenerative response that 5mg/L stops the saturable magnetic materials adsorbent, the eluent that a new round is fresh enters the wash-out exchange column by the eluent water inlet pipe, still regularly measure the concentration of PCP-Na in the eluent, recycling elution successively, when the concentration of PCP-Na is lower than 5mg/L, finish the wash-out regenerative response of saturable magnetic materials adsorbent, collect adsorbent and oven dry preservation, import the magnetic material absorption processing system and reuse.
The present invention is Fe
3O
4/ CS magnetic material adsorbent and preparation method and sewage water treatment method.Prepared Fe
3O
4/ CS magnetic material adsorbent shows as novel single bobbles bodily form looks of disperseing, almost without agglomeration.Fe
3O
4The adsorption process of PCP-Na has just realized rapidly adsorption equilibrium at 30min with interior in the/CS adsorbing and removing water, and according to data, a lot of adsorbents in use need 2h even 24h could realize adsorption equilibrium, have shown Fe
3O
4The high efficiency of/CS adsorbent adsorbing and removing PCP-Na.Fe
3O
4The adsorption process of PCP-Na is descended to obtain maximum PCP-Na removal efficiency (91.5%) near the neutral slant acidity condition (pH=6.5) of general water body near ambient temperature (25 ℃) and acid-base value in/the CS adsorbing and removing water, shows Fe
3O
4/ CS magnetic Nano material adsorbent has feasibility and the superiority of practical application.Fe
3O
4Can realize the purpose of rapid efficient adsorbent by utilizing magnetic field behind the PCP-Na in the/CS adsorbing and removing water, both realize the recycling of adsorbent, be not easy to reclaim waste and the secondary pollution that causes thereby also effectively improved adsoption catalyst.
Description of drawings
Below in conjunction with drawings and Examples to the detailed description of the invention.
Fig. 1 Fe
3O
4Single schematic diagram that disperses bobbles bodily form looks of/CS magnetic material adsorbent.
Fig. 2 Fe
3O
4(A) X-ray diffraction (XRD) of/CS magnetic material adsorbent and (B) Fourier's infrared spectrum analysis (FTIR).
Fig. 3 Fe
3O
4The result that the B-H loop of/CS magnetic material adsorbent is measured.
Fig. 4 Fe
3O
4/ CS magnetic material adsorbent places PCP-Na solution to carry out the schematic diagram of adsorption treatment.
Fig. 5 Fe
3O
4/ CS magnetic material adsorbent places PCP-Na solution to carry out the schematic diagram of adsorption treatment.
Fig. 6 Fe
3O
4The schematic diagram of the absorption processing system of/CS magnetic material adsorbent.
Fig. 7 Fe
3O
4The wash-out regenerative system schematic diagram of the saturated adsorption agent of/CS magnetic material adsorbent.
1 water inlet pipe, 2 retort, 3 electric stirrings slurry is at the bottom of the 4 open-close type tanks, 5 adsorbents add pipe, 6 control device, 7 saturable magnetic materials adsorbent collection buckets, 8 outlet pipes, 9 suction pumps, 10 sealing hinges, 11 adsorbent feed pipes, 12 adsorbent control device, 13 wash-out exchange columns, 14 eluent water inlet pipes, 15 peristaltic pumps, 16 eluent outlet pipes, 17 sample taps, 18 eluent circulation pipes, 19 eluent drainpipes.
The specific embodiment
Fe
3O
4/ CS magnetic material adsorbent is synthetic by a step solvent-thermal method, and its pattern shows as monodispersed bobbles body, and almost without agglomeration, between the 200nm, specific area is 32.18m to diameter between 100nm
2/ g, Fe
3O
4The adsorption process of penta sodium pentachlorophenate (PCP-Na) has just realized rapidly adsorption equilibrium at 30min with interior in the/CS adsorbing and removing water, and descend to obtain maximum penta sodium pentachlorophenate (PCP-Na) removal efficiency (91.5%) near the neutral slant acidity condition (pH=6.5) of general water body near ambient temperature (25 ℃) and acid-base value, such as Fig. 1, Fig. 2, Fig. 4, shown in Figure 5.
In the 100L mixer, add the anhydrous FeCl of 200g ~ 1.6kg
3With 40L ethylene glycol, after mixer fully stirred, solution was the red tan solution of homogeneous transparent.In transparent red tan solution, add people 0.9kg ~ 7.2kg sodium acetate and 0.2 ~ 5.0kg shitosan, continue to stir 30min, form the outstanding turbid homogenate of rufous.
In with teflon-lined stainless steel autoclave, import outstanding turbid homogenate, the temperature of conditioned reaction still is 200 ℃, the power supply of off-response still after the reaction 12h, the question response still naturally cools to room temperature, obtain black suspension, isolate black solid by magnetic field, black solid is imported in the washing system, with absolute ethanol washing number time, at last black solid is placed 60 ℃ of drying boxes to dry to constant weight, obtain black powder, black powder is put into drier store for future use, such as Fig. 1, Fig. 2, Fig. 3, Fig. 4, shown in Figure 5.
Wash-out regenerative system by magnetic material absorption processing system and saturable magnetic materials adsorbent forms, absorption processing system is by water inlet pipe (1), retort (2), electric stirring slurry (3), at the bottom of the open-close type tank (4), adsorbent adds pipe (5), control device (6), saturable magnetic materials adsorbent collection bucket (7), outlet pipe (8), suction pump (9) and sealing hinge (10) form, retort (2) integral body is tubbiness, be hollow in the bucket, capacity is 200L at least, reaction liquid enters retort (2) by water inlet pipe (1), retort (2) top ends is installed adsorbent and is added pipe (5) and control device (6), control device (6) control adsorbent adds pipe (5) input amount, install electric stirring slurry (3) in the retort (2), electric stirring slurry (3) stirs and drops into retort (2) internal reaction liquid.
Outlet pipe (8) and suction pump (9) are installed in the top of retort (2), insert in the retort (2) one end of outlet pipe (8), the other end of outlet pipe (8) is connected with suction pump (9), by after treatment reaction liquid in outlet pipe (8) and suction pump (9) the extraction tank (2), water inlet pipe (1) is installed in the bottom of retort (2), inputs need sewage to be processed by water inlet pipe (1) in retort.
(4) at the bottom of the open-close type tank are installed in the bottom of retort (2), (4) are tightly connected by sealing hinge (10) and retort (2) at the bottom of the open-close type tank, install the sucked type electromagnet at the bottom of the open-close type tank in (4), the saturable magnetic materials adsorbent is adsorbed onto at the bottom of the open-close type tank on (4) behind the plugged, saturable magnetic materials adsorbent collection bucket (7) is installed in following and retort (2) corresponding section of retort (2), saturable magnetic materials adsorbent collection bucket (7) is collected the saturable magnetic materials adsorbent, open at the bottom of the open-close type tank of retort (2) (4) and emit the saturated adsorption agent and enter saturable magnetic materials adsorbent collection bucket (7), as shown in Figure 6.
The wash-out regenerative system of saturable magnetic materials adsorbent is by adsorbent feed pipe (11), adsorbent control device (12), wash-out exchange column (13), eluent water inlet pipe (14), peristaltic pump (15), eluent outlet pipe (16), sample tap (17), eluent circulation pipe (18) and eluent drainpipe (19) form, wash-out exchange column (13) integral body is tubbiness, be hollow in the bucket, wash-out exchange column (13) top ends is installed adsorbent feed pipe (11) and adsorbent control device (12), and adsorbent control device (12) control adsorbent feed pipe (11) is to the interior amount of throwing in adsorbent of wash-out exchange column (13).
Eluent outlet pipe (16), sample tap (17) and eluent drainpipe (19) are installed in the top of wash-out exchange column (13), one end of eluent outlet pipe (16) is connected with wash-out exchange column (13), the other end of eluent outlet pipe (16) is connected with sample tap (17), and sample tap (17) is connected with eluent drainpipe (19).
Eluent water inlet pipe (14) is installed in the bottom of wash-out exchange column (13), one end of eluent water inlet pipe (14) is connected with the bottom of wash-out exchange column (13), the other end of eluent water inlet pipe (14) is connected with eluent circulation pipe (18), install peristaltic pump (15) on the eluent water inlet pipe (14), eluent circulation pipe (18) is connected with eluent drainpipe (19), driving peristaltic pump (15) carries the eluent in the eluent circulation pipe (18) in wash-out exchange column (13), wash-out exchange column (13) inner bottom part arranges supporting layer, supporting layer adopts the bead of particle diameter 6 ~ 7mm, as shown in Figure 7.
Then the processing of at first sewage being adsorbed magnetic material in the magnetic material absorption processing system is carried out wash-out regeneration to the saturable magnetic materials adsorbent and is processed the Fe that wash-out bears again in the wash-out regenerative system of saturable magnetic materials adsorbent
3O
4/ CS magnetic material adsorbent is reused in the magnetic material absorption processing system again, be the PCP-Na solution of 50g ~ 200mg/L by water inlet pipe (1) input initial concentration in the retort (2), add hydrochloric acid and sodium hydroxide solution in the retort (2), after the pH value of the interior PCP-Na solution of conditioned reaction tank (2) reaches 6.0 ~ 11.0, open control device (6), add pipe (5) by adsorbent and in retort (2), add 150g ~ 400g Fe
3O
4/ CS adsorbent.Start electric stirring slurry (3), the liquid in the abundant stirred tank (2), the stir speed (S.S.) of electric stirring slurry (3) is 250rpm, the temperature of retort (2) is respectively 25 ℃, 35 ℃ and 45 ℃.
After liquid adsorption reaction in the retort (2) finishes, close electric stirring slurry (3), sucked type electromagnet at the bottom of the startup open-close type tank in (4), according to the electromagnetic conversion principle, sucked type electromagnet at the bottom of the open-close type tank in (4) produces powerful electromagnetic attraction under "on" position, treat at the bottom of the open-close type tank at the bottom of the saturable magnetic materials adsorbent is drawn onto rapidly the tank of retort (2) on (4).
Start suction pump (9), the solution after adsorption reaction transfers out retort (2) by outlet pipe (8), closes (4) interior sucked type electromagnet power supply at the bottom of the open-close type tank, stops adsorption operation.Opening encapsulation hinge (10), the pot bottom of retort (2) is opened, and the saturable magnetic materials adsorbent imports in the following saturable magnetic materials adsorbent collection bucket (7) of retort (2), such as Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, shown in Figure 6.
The saturable magnetic materials adsorbent is imported the wash-out regenerative system of saturable magnetic materials adsorbent, implementing wash-out regeneration processes, bottom in wash-out exchange column (13) arranges supporting layer, supporting layer adopts the bead of particle diameter 6 ~ 7mm, open adsorbent control device (12), saturable magnetic materials adsorbent in the saturable magnetic materials adsorbent collection bucket (7) is input in the wash-out exchange column (13) by adsorbent feed pipe (11), the NaOH solution of methyl alcohol and 0.5 ~ 1.5mol/L by volume 1:1 be mixed into eluent, flowing through from bottom to top in wash-out exchange column (13) through eluent water inlet pipe (14) by peristaltic pump (15) is filled with the saturable magnetic materials adsorbent, and the flow velocity of eluent is 5 ~ 40mL/h.
Regularly from the sample tap (17) of eluent outlet pipe (16) eluent is taken a sample, and the concentration of PCP-Na in the mensuration eluent, when the concentration of PCP-Na is lower than 50mg/L, eluent enters in the wash-out exchange column (13) by the bottom of eluent circulation pipe (18) by wash-out exchange column (13) from the top of wash-out exchange column (13), iterative cycles, when the concentration of PCP-Na in the eluent reaches a peak, saturated eluent is discharged from eluent drainpipe (19), successively the reciprocation cycle wash-out.
When the concentration of PCP-Na is lower than 5mg/L, finish the wash-out regenerative response of saturable magnetic materials adsorbent, collect the magnetic material adsorbent, and oven dry is preserved, send into the recycling of magnetic material absorption processing system, such as Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, shown in Figure 7.
Claims (3)
1. Fe
3O
4/ CS magnetic material adsorbent is characterized in that Fe
3O
4/ CS magnetic material adsorbent is synthetic by a step solvent-thermal method, and its pattern shows as monodispersed bobbles body, and almost without agglomeration, between the 200nm, specific area is 32.18m to diameter between 100nm
2/ g, Fe
3O
4The adsorption process of penta sodium pentachlorophenate (PCP-Na) has just realized rapidly adsorption equilibrium at 30min with interior in the/CS adsorbing and removing water, and descends to obtain maximum penta sodium pentachlorophenate (PCP-Na) removal efficiency (91.5%) near ambient temperature (25 ℃) and acid-base value near the neutral slant acidity condition (pH=6.5) of general water body.
2. make Fe claimed in claim 1 for one kind
3O
4The preparation method of/CS magnetic material adsorbent is characterized in that adding the anhydrous FeCl of 200g ~ 1.6kg in the 100L mixer
3With 40L ethylene glycol, after mixer fully stirred, solution was the red tan solution of homogeneous transparent; In transparent red tan solution, add 0.9kg ~ 7.2kg sodium acetate and 0.2 ~ 5.0kg shitosan, continue to stir 30min, form the outstanding turbid homogenate of rufous;
Outstanding turbid homogenate is imported 50L with in the teflon-lined stainless steel autoclave, the temperature of conditioned reaction still is 200 ℃, off-response still power supply after the reaction 12h, the question response still naturally cools to room temperature, obtains black suspension, isolate black solid by magnetic field, black solid is imported in the washing system, with absolute ethanol washing number time, at last black solid is placed 60 ℃ of drying boxes to dry to constant weight, obtain black powder, black powder is put into drier store for future use.
3. one kind is utilized Fe claimed in claim 1
3O
4The sewage water treatment method of/CS magnetic material adsorbent, it is characterized in that being formed by the wash-out regenerative system of magnetic material absorption processing system and saturable magnetic materials adsorbent, absorption processing system is by water inlet pipe (1), retort (2), electric stirring slurry (3), at the bottom of the open-close type tank (4), adsorbent adds pipe (5), control device (6), saturable magnetic materials adsorbent collection bucket (7), outlet pipe (8), suction pump (9) and sealing hinge (10) form, retort (2) integral body is tubbiness, be hollow in the bucket, capacity is 200L at least, reaction liquid enters retort (2) by water inlet pipe (1), retort (2) top ends is installed adsorbent and is added pipe (5) and control device (6), control device (6) control adsorbent adds pipe (5) input amount, install electric stirring slurry (3) in the retort (2), electric stirring slurry (3) stirs and drops into retort (2) internal reaction liquid; Outlet pipe (8) and suction pump (9) are installed in the top of retort (2), insert in the retort (2) one end of outlet pipe (8), the other end of outlet pipe (8) is connected with suction pump (9), by after treatment reaction liquid in outlet pipe (8) and suction pump (9) the extraction tank (2), water inlet pipe (1) is installed in the bottom of retort (2), inputs need sewage to be processed by water inlet pipe (1) in retort; (4) at the bottom of the open-close type tank are installed in the bottom of retort (2), (4) are tightly connected by sealing hinge (10) and retort (2) at the bottom of the open-close type tank, install sucked type sucked type electromagnet at the bottom of the open-close type tank in (4), the saturable magnetic materials adsorbent is adsorbed onto at the bottom of the open-close type tank on (4) behind the plugged, saturable magnetic materials adsorbent collection bucket (7) is installed in following and retort (2) corresponding section of retort (2), saturable magnetic materials adsorbent collection bucket (7) is collected the saturable magnetic materials adsorbent, opens at the bottom of the open-close type tank of retort (2) (4) and emits the saturated adsorption agent and enter saturable magnetic materials adsorbent collection bucket (7);
The wash-out regenerative system of saturable magnetic materials adsorbent is by adsorbent feed pipe (11), adsorbent control device (12), wash-out exchange column (13), eluent water inlet pipe (14), peristaltic pump (15), eluent outlet pipe (16), sample tap (17), eluent circulation pipe (18) and eluent drainpipe (19) form, wash-out exchange column (13) integral body is tubbiness, be hollow in the bucket, wash-out exchange column (13) top ends is installed adsorbent feed pipe (11) and adsorbent control device (12), and adsorbent control device (12) control adsorbent feed pipe (11) is to the interior amount of throwing in adsorbent of wash-out exchange column (13); Eluent outlet pipe (16), sample tap (17) and eluent drainpipe (19) are installed in the top of wash-out exchange column (13), one end of eluent outlet pipe (16) is connected with wash-out exchange column (13), the other end of eluent outlet pipe (16) is connected with sample tap (17), and sample tap (17) is connected with eluent drainpipe (19); Eluent water inlet pipe (14) is installed in the bottom of wash-out exchange column (13), one end of eluent water inlet pipe (14) is connected with the bottom of wash-out exchange column (13), the other end of eluent water inlet pipe (14) is connected with eluent circulation pipe (18), install peristaltic pump (15) on the eluent water inlet pipe (14), eluent circulation pipe (18) is connected with eluent drainpipe (19), driving peristaltic pump (15) carries the eluent in the eluent circulation pipe (18) in wash-out exchange column (13), wash-out exchange column (13) inner bottom part arranges supporting layer, and supporting layer adopts the bead of particle diameter 6 ~ 7mm;
Then the processing of at first sewage being adsorbed magnetic material in the magnetic material absorption processing system is carried out wash-out regeneration to the saturable magnetic materials adsorbent and is processed the Fe that wash-out bears again in the wash-out regenerative system of saturable magnetic materials adsorbent
3O
4/ CS magnetic material adsorbent is reused in the magnetic material absorption processing system again, be the PCP-Na solution of 50 ~ 200mg/L by water inlet pipe (1) input initial concentration in the retort (2), add hydrochloric acid and sodium hydroxide solution in the retort (2), after the pH value of the interior PCP-Na solution of conditioned reaction tank (2) reaches 6.0 ~ 11.0, open control device (6), add pipe (5) by adsorbent and in retort (2), add 150g ~ 400g Fe
3O
4/ CS adsorbent;
Start electric stirring slurry (3), the liquid in the abundant stirred tank (2), the stir speed (S.S.) of electric stirring slurry (3) is 250rpm, the temperature of retort (2) is respectively 25 ℃, 35 ℃ and 45 ℃;
After liquid adsorption reaction in the retort (2) finishes, close electric stirring slurry (3), sucked type electromagnet at the bottom of the startup open-close type tank in (4), according to the electromagnetic conversion principle, sucked type electromagnet at the bottom of the open-close type tank in (4) produces powerful electromagnetic attraction under "on" position, treat that the saturable magnetic materials adsorbent is drawn onto rapidly at the bottom of the open-close type tank of pot bottom of retort (2) on (4); Start suction pump (9), the solution after adsorption reaction transfers out retort (2) by outlet pipe (8), closes (4) interior sucked type electromagnet power supply at the bottom of the open-close type tank, stops adsorption operation; Opening encapsulation hinge (10), open (4) at the bottom of the open-close type tank of retort (2), and the saturable magnetic materials adsorbent imports in the following saturable magnetic materials adsorbent collection bucket (7) of retort (2);
The saturable magnetic materials adsorbent is imported the wash-out regenerative system of saturable magnetic materials adsorbent, implementing wash-out regeneration processes, bottom in wash-out exchange column (13) arranges supporting layer, supporting layer adopts the bead of particle diameter 6 ~ 7mm, open adsorbent control device (12), saturable magnetic materials adsorbent in the saturable magnetic materials adsorbent collection bucket (7) is input in the wash-out exchange column (13) by adsorbent feed pipe (11), the NaOH solution of methyl alcohol and 0.5 ~ 1.5mol/L by volume 1:1 be mixed into eluent, by the wash-out exchange column (13) that peristaltic pump (15) is flowed through from bottom to top and is filled with the saturable magnetic materials adsorbent through eluent water inlet pipe (14), the flow velocity of eluent is 5 ~ 40mL/h;
Regularly from the sample tap (17) of eluent outlet pipe (16) eluent is taken a sample, and the concentration of PCP-Na in the mensuration eluent, when the concentration of PCP-Na is lower than 50mg/L, eluent enters in the wash-out exchange column (13) by the bottom of eluent circulation pipe (18) by wash-out exchange column (13) from the eluent outlet pipe (16) on the top of wash-out exchange column (13), iterative cycles, when the concentration of PCP-Na in the eluent reaches a peak, saturated eluent is discharged from eluent drainpipe (19), successively the reciprocation cycle wash-out; Take turns through several that concentration as PCP-Na is lower than 5mg/L behind the recycling elution, finish the wash-out regenerative response of saturable magnetic materials adsorbent, collect the magnetic material adsorbent, and oven dry preserves, send into the recycling of magnetic material absorption processing system.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105080522A (en) * | 2015-09-21 | 2015-11-25 | 威士邦（厦门）环境科技有限公司 | Continuous cyclic regeneration fluidized bed for adsorbing materials |
| CN105536721A (en) * | 2016-01-04 | 2016-05-04 | 南京理工大学 | Application of magnetic chitosan microspheres in adsorption of trifluoroacetic acid |
| CN106215880A (en) * | 2016-08-31 | 2016-12-14 | 南京大学 | The preparation method of chitosan magnetic bead |
| CN106914219A (en) * | 2017-04-07 | 2017-07-04 | 安徽工业大学 | A kind of application of magnetic carbosphere Cr VI in waste water is removed |
| CN115367974A (en) * | 2022-07-25 | 2022-11-22 | 浙江大学 | Phosphorus-containing mud water recovery device and method based on magnetic adsorbent |
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2013
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| JIANZHI WANG ET AL.: "Reversible immobilization of glucoamylase onto magnetic chitosan nanocarriers", 《APPL MICROBIOL BIOTECHNOL》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105080522A (en) * | 2015-09-21 | 2015-11-25 | 威士邦（厦门）环境科技有限公司 | Continuous cyclic regeneration fluidized bed for adsorbing materials |
| CN105080522B (en) * | 2015-09-21 | 2023-12-19 | 威士邦（厦门）环境科技有限公司 | Adsorption material continuous circulation regeneration fluidized bed |
| CN105536721A (en) * | 2016-01-04 | 2016-05-04 | 南京理工大学 | Application of magnetic chitosan microspheres in adsorption of trifluoroacetic acid |
| CN106215880A (en) * | 2016-08-31 | 2016-12-14 | 南京大学 | The preparation method of chitosan magnetic bead |
| CN106914219A (en) * | 2017-04-07 | 2017-07-04 | 安徽工业大学 | A kind of application of magnetic carbosphere Cr VI in waste water is removed |
| CN115367974A (en) * | 2022-07-25 | 2022-11-22 | 浙江大学 | Phosphorus-containing mud water recovery device and method based on magnetic adsorbent |
| CN115367974B (en) * | 2022-07-25 | 2024-04-16 | 浙江大学 | Device and method for recycling phosphorus-containing muddy water based on magnetic adsorbent |
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