CN103495399A - Preparation method and application of sludge activated carbon - Google Patents
Preparation method and application of sludge activated carbon Download PDFInfo
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- CN103495399A CN103495399A CN201310499480.6A CN201310499480A CN103495399A CN 103495399 A CN103495399 A CN 103495399A CN 201310499480 A CN201310499480 A CN 201310499480A CN 103495399 A CN103495399 A CN 103495399A
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Abstract
The invention discloses a preparation method of sludge activated carbon. The preparation method of the sludge activated carbon comprises the following steps that surplus sludge taken from a sewage treatment plant is dried, smashed and screened, and then the sludge activated carbon is obtained through pyrolysis treatment, oxidation treatment, ammonification treatment and methylation treatment. The invention further relates to the application of the sludge activated carbon obtained through the preparation method for treating low-concentration perchlorate waste water. The preparation method is simple, easy to implement and low in cost, the prepared sludge activated carbon is high in adsorption capacity, recyclable and capable of effectively treating low-concentration perchlorate solutions, and secondary pollution cannot be caused in the adsorption process.
Description
Technical field
The present invention relates to sewage treatment area, be specifically related to a kind of preparation method of active sludge carbon and the application of processing low concentration perchlorate waste water.
Background technology
For many years, perchlorate is widely used in the fields such as propellant, pyrotechnics manufacture, munitions industry, automobile airbag, expressway safety Flash board, also morely as additive is used to lubricating oil, fabric fixative, electroplate liquid, leather retanning agent, rubber, fuel coating, smelts in the production of the products such as aluminium and magnesium cell.Take in the chemical fertilizer that sodium nitrate is raw material of using in agricultural production also contains certain density perchlorate, and a large amount of uses of material, make a large amount of perchlorate enter into natural water, so that polluted drinking water.Because perchlorate is a kind of novel persistent pollutant matter, diffusion velocity is fast, stability is high, difficult degradation, after perchlorate enters natural water, it can enter human body by drinking water and animals and plants and also finally act on the thyroid gland of human body, disturbs its normal function.Perchlorate will be combined with iodine after entering human body in thyroid gland, hinder the absorption of thyroid gland to iodine, cause the minimizing of thyroid hormone synthetic quantity, affect the particularly growth of cerebral tissue of human body.In addition, excessive perchlorate can cause the thyroid hormone secretion deficiency in human body, thereby affects the generation of hemoglobin, the growth of cardio-pulmonary function and bone, the maintaining of immunity, hearing organ's normal function etc.
American Academy of Sciences's research shows, when perchlorate, when people's in-vivo content surpasses the 0.0007mg/kg body weight, when Perchlorate in Drinking Water concentration is 24.5 μ g/L, will impact health.Therefore Environmental Protection Agency (EPA) to have announced the safety standard of perchlorate in drinking water be 18 μ g/L, and lower safety standard value has been formulated in more serious area to some damage ratios.
Due to non-volatile, the highly dissoluble of perchlorate, present the characteristics of chemical kinetics inertia in the aqueous solution, when concentration<10% (w/w), with most of reproducibility ions, do not react, particularly more difficult to the removal of the low concentration perchlorate of 20 μ g/L～200 μ g/L, therefore, there is very large difficulty in the development process technology.And conventional treatment technology as coagulation, filter, add reducing agent ion etc. and all can not effectively remove perchlorate (ClO
4 -).Present stage, the more pollution control technology of research and application mainly comprises ion-exchange, biodegradation and reparation, chemical/electrochemical reduction, electrodialysis and counter-infiltration.The ion-exchange principle is simple, but most of ion exchange resin is selectively not strong, regenerates very difficult, and cost is higher, therefore is difficult to obtain large-scale application.Membrane filtration comprises reverse osmosis and receives pore membrane and filter, and there is the problem that pellicle easily damages, concentrate subsequent treatment difficulty is large in the method; Electroosmose process is to ClO
4 -clearance very low, operating cost is very high, the subsequent treatment of concentrate is very difficult; Electrochemical reduction is directly on negative electrode, to apply a high potential perchlorate is reduced to chlorion, the subject matter that the method exists at present is electrode corrosion, electrode passivation and fouling of the electrode, and the characteristics of electronation and electrochemical reducing have determined that its cost may be higher.Active carbon adsorption is as the adsorption method of dissolubility pollutant in common water, have be widely used, successful, characteristics simple to operate, but common active carbon is general to the adsorption effect of perchlorate, particularly to the perchlorate of low concentration, can not effectively adsorb.Can improve the adsorption capacity to perchlorate by selecting the materials such as cationic surfactant to carry out modification to active carbon, but increase greatly like this preparation cost of active carbon, therefore be difficult to be widely used.The active sludge carbon effect that utilizes sewage treatment plant residual mud to prepare and business active carbon approach is even having better effect aspect some, be subject to people and more and more paid close attention to, also more and more deep to the research of its preparation process.At present about the research of perchlorate in the active sludge carbon adsorbed water also in the exploratory stage, also do not find the active sludge carbon preparation method of perchlorate in effective adsorbed water.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides a kind of and prepares simplely, with low cost, can effectively process low concentration perchlorate waste water, can not cause the preparation method and application of the active sludge carbon of secondary pollution.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of preparation method of active sludge carbon comprises the following steps:
(1) pyrolysis processing: will after drying sludge, pulverize and sieve, carry out pyrolytic reaction in ammonia atmosphere, dry after washing, obtain active sludge carbon powdered carbon raw material;
(2) oxidation processes: active sludge carbon powdered carbon raw material is added in hydrogen peroxide solution, and after the vibration oxidation reaction, washing is dry, obtains sludge activity char combustion powdered carbon raw material;
(3) ammonification is processed: by sludge activity char combustion powdered carbon raw material as in heater, pass into the air in nitrogen emptying heater, carry out aminating reaction to passing into ammonification gas in heater again, finally be cooled to room temperature to passing into nitrogen in heater again, after washing, vacuum drying, obtain active sludge carbon ammonification powdered carbon raw material;
(4) processing that methylates: active sludge carbon ammonification powdered carbon raw material is immersed in to methylating reagent, and the airtight standing methylation reaction that carries out, clean with sodium chloride solution after methylation reaction, then, by deionized water washing final vacuum drying, obtain active sludge carbon.
As a further improvement on the present invention,
The excess sludge that in described step (1), mud is sewage treatment plant, the temperature of drying sludge is 105 ℃～110 ℃, be 24h～48h drying time, sieves and be of a size of 200 orders～300 orders; In described step (1), the flow velocity of ammonia is 50mL/min～100mL/min; The step of pyrolytic reaction is in described step (1), and first the speed with 20 ℃/min～30 ℃/min is warming up to 110 ℃, stops 5min, then is warming up to 400 ℃～600 ℃ of end reaction temperature with the speed of 10 ℃/min～30 ℃/min, stops 60min～120min; In described step (1), the rear dry temperature of washing is 105 ℃～110 ℃, and the time is 12h～24h.
In described step (2), the mass concentration of hydrogen peroxide solution is 5%～20%, and the quality of active sludge carbon powdered carbon raw material and the volume ratio of hydrogen peroxide solution are 1: 5g/ml～1: 20g/ml; In described step (2), the temperature of vibration oxidation reaction is 40 ℃～70 ℃, and rotating speed is 120r/min～150r/min, and the time is 5h～10h; Temperature dry in described step (2) is 105 ℃～110 ℃, and the time is 5h～10h.
The step of the air in described step (3) in the emptying heater is, with the flow velocity of 100mL/min, passes into nitrogen 10min; In described step (3), the step of aminating reaction is, stop passing into described nitrogen while with 20 ℃/min speed, being warming up to 400 ℃, flow velocity with 10mL/min～30mL/min passes into ammonification gas, speed with 20 ℃/min～30 ℃/min is warming up to 650 ℃～850 ℃ of aminating reaction temperature, and stops 60min～120min; In described step (3), vacuum drying temperature is 105 ℃～110 ℃, and the time is 8h～15h.
In described step (4), methylating reagent is methyl iodide; In described step (4), the mass ratio of active sludge carbon ammonification powdered carbon raw material and methylating reagent is 1.5～2: 10～20; In described step (4), the standing time is 48h～120h; In described step (4), the molar concentration of sodium chloride solution is 2mol/L～4mol/L; In described step (4), vacuum drying temperature is 50 ℃～120 ℃, and the time is 12h～24h.
Described ammonification gas is ammonia, or ammonia-carbon dioxide gas mixture, and in described An Qi – carbon dioxide gas mixture, the volume ratio of ammonia and carbon dioxide is 10～30: 1～20.
As a total technical conceive, the present invention also provides a kind of above-mentioned active sludge carbon to process the application of low concentration perchlorate waste water, comprise the following steps: active sludge carbon is packed in adsorption system, the low concentration perchlorate waste water of 20 μ g/L～200 μ g/L is sent into to described adsorption system and carry out adsorption reaction, the volume ratio of the quality of described active sludge carbon and perchlorate waste water is 1: 7.48g/ L～1: 15.04g/ L.
Described perchlorate waste water is the sodium perchlorate aqueous solution or the potassium hyperchlorate aqueous solution.
Described adsorption system comprises an adsorption column, and the adsorption column two ends are connected with respectively water inlet pipe and outlet pipe, is connected to peristaltic pump on water inlet pipe, and water inlet pipe passes in former liquid pool away from an end of adsorption column.
In addition, the active sludge carbon of processing perchlorate waste water can pass through micro wave regeneration, again processes perchlorate waste water.Micro wave regeneration comprises the following steps: will process the active sludge carbon of perchlorate waste water after 105 ℃～110 ℃ dry 24h～48h, be placed in micro-wave oven, in 800 ℃～1000 ℃ heating 30min～120min, obtain the regeneration sludge active carbon under the condition of steam and carbon dioxide existence.The regeneration sludge active carbon can be processed under the condition that perchlorate waste water is identical and process low concentration perchlorate waste water with active sludge carbon.
Active sludge carbon powdered carbon raw material is the material that mud obtains after pyrolysis processing, sludge activity char combustion powdered carbon raw material is the material that active sludge carbon powdered carbon raw material obtains after by oxidation processes, and active sludge carbon ammonification powdered carbon raw material is the material obtained after sludge activity char combustion powdered carbon raw material is processed by ammonification.
Compared with prior art, beneficial effect of the present invention is:
1, preparation method of the present invention is simple, with low cost, adopt hydrogen peroxide to process and can increase surface oxygen functional group, recycling ammonification gas carries out the ammonification processing, finally utilize methylating reagent to be methylated to process to form the alkylation pyridine, prepare the strong close perchlorate sorbing material with quaternary ammonium salt and pyridine structure.
2, the active sludge carbon that prepared by the present invention is to take the excess sludge of sewage treatment plant as prepared by raw material, after excess sludge is carried out to a series of processing, has obtained active sludge carbon, realizes the recycling to mud.
3, sludge activity carbon surface of the present invention exists a large amount of quaternary ammonium salts and pyridine structure, comprises in addition the structures such as amine substance, oxynitrides and pyrroles, and quaternary ammonium salt and pyridine structure can be in conjunction with the ClO in water
4 -, the low concentration perchlorate waste water that effectively adsorption of Low Concentration perchlorate waste water, particularly concentration are 20 μ g/L～200 μ g/L.The application that the present invention processes perchlorate waste water can not cause secondary pollution, the active sludge carbon of processing perchlorate waste water also can pass through micro wave regeneration, again process low concentration perchlorate waste water, active sludge carbon after having avoided using becomes solid refuse and pollutes, and can reduce processing cost.
The accompanying drawing explanation
Fig. 1 be in the present embodiment 1 XPS to each results of elemental analyses of activated carbon surface figure.
Fig. 2 is the peak spectrogram of N in XPS analysis in the present embodiment 1.
The XPS peak spectrum fitted figure that Fig. 3 is sludge activity carbon surface nitrogen substance in the present embodiment 1.
Fig. 4 is adsorption system structural representation in the present embodiment 2.
The breakthrough curve figure that Fig. 5 is different adsorbent absorption perchlorate waste water.
In figure: 1-outlet pipe, 2-adsorption column, 3-mineral wool, 4-packed column, 5-water inlet pipe, 6-peristaltic pump, the former liquid pool of 7-.
The specific embodiment
Below in conjunction with Figure of description, with concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
The preparation method of the active sludge carbon of the present embodiment comprises the following steps:
(1) will take from the excess sludge of sewage treatment plant after 105 ℃ of dry 48h, pulverize and successively cross 200 orders and 300 mesh sieves, mud after getting 10g and sieving is put into tube type resistance furnace, flow velocity with 80mL/min passes into ammonia, be warming up to 110 ℃ with 25 ℃/min speed and stop 5min, be warming up to 500 ℃ of end reaction temperature with 25 ℃/min speed again, stop 90min, be cooled to room temperature, again with deionized water rinsing to pH=6.8, finally freeze-day with constant temperature 24h at 105 ℃ of temperature, obtain active sludge carbon powdered carbon raw material;
(2) 10g active sludge carbon powdered carbon raw material is added in the hydrogen peroxide solution that the 200mL mass concentration is 10%, again in 60 ℃, the 150r/min Water Under is bathed vibration 10h, reacted rear with deionized water rinsing to pH=7.2, finally dry 10h under 105 ℃, obtain sludge activity char combustion powdered carbon raw material;
(3) 4g sludge activity char combustion powdered carbon raw material is positioned in tube type resistance furnace, flow velocity with 100mL/min passes into nitrogen 10min with the air in drain, stop passing into nitrogen while being warming up to 400 ℃ with 20 ℃/min speed again, flow velocity with 20mL/min passes into ammonia, and be warming up to 750 ℃ and stop 90min with the speed of 20 ℃/min, stop passing into ammonia, then the speed with 50mL/min passes into nitrogen, be cooled to room temperature, reacted rear with deionized water rinsing to pH=7.0, finally in 105 ℃ of lower vacuum drying 15h, obtain active sludge carbon ammonification powdered carbon raw material,
(4) 2g active sludge carbon ammonification powdered carbon raw material is added in the brown conical flask of ground, add the CH of 20g
3i makes its submergence, and the standing 72h of jam-pack bottle stopper cleans with the sodium chloride solution of 2mol/L after reaction, then with deionized water rinsing to pH=6.9, finally, in 80 ℃ of lower vacuum drying 24h, obtain active sludge carbon.
Surface mass with x-ray photoelectron spectroscopy (XPS) to active sludge carbon is characterized, and result as shown in Figure 1.Result shows, the active sludge carbon surface nitrogen content is 4.17%.Carry out the high power analysis by near the peak to 400eV and obtained the open score about N, result as shown in Figure 2.The peak spectrogram that by Fig. 2, can obtain N is not the peak spectrum of simple a kind of nitrogen substance, but is mixed and formed by the peak spectrum of multiple nitrogen substance.
Due to pyridine structure (N-6), pyrrole structure (N-5), amine substance (Amines), oxynitrides (N-O
x) and quaternary ammonium salt structure (N-Q) in conjunction with can be respectively: 398.7 ± 0.3eV, 400.3 ± 0.3eV, 399.4eV, 402 eV～405eV and 401.4eV, and pyridine structure and quaternary ammonium salt can with the aqueous solution in ClO
4 -in conjunction with.Peak spectrum to the nitrogen element is carried out the matching of above-mentioned nitrogen substance, and result as shown in Figure 3.As shown in Figure 3, the nitrogen substance of the sludge activity carbon surface that the present invention is prepared mainly contains: pyridine structure, pyrrole structure, quaternary ammonium salt structure, amine substance and oxynitrides, and the perchlorate of active sludge carbon of the present invention in can adsorbed water.
The active sludge carbon of the present embodiment is processed low concentration perchlorate aqueous solution's application, comprises the following steps:
The adsorption system that the present embodiment adopts, as shown in Figure 4.Described adsorption system comprises an adsorption column 2, and adsorption column 2 two ends are connected with respectively water inlet pipe 5 and outlet pipe 1, are connected to peristaltic pump 6 on water inlet pipe 5, and water inlet pipe 5 passes in former liquid pool 7 away from an end of adsorption column 2.
Specifically be implemented as follows: by a length, be 10cm, the lucite post that diameter is 6cm is as adsorption column 2, offer along its length the packed column run through 4 that a diameter is 3mm, respectively widening a length at packed column 4 two ends is 8mm, the screwed hole that diameter is 6mm, respectively load onto the metal sleeve that an internal diameter is 3mm, by two internal diameters, is 3.0mm, the emulsion tube that external diameter is 5.0mm is connected on metal sleeve, as outlet pipe 1 and water inlet pipe 5.
To in packed column 4, fill up active sludge carbon, the active sludge carbon quality is 0.35g, and volume is about 0.7cm
3, be decided to be 1BV, filled after active sludge carbon with mineral wool 3 sealings, in case active sludge carbon flows out with current and blocks pipeline.Take 400 μ L/min speed by peristaltic pump 6 initial concentration in former liquid pool 7 is sent into to packed column 4 as the sodium perchlorate aqueous solution of 80 μ g/L, carry out adsorption treatment.At outlet pipe, the 1 every 30min in place gets sample one time, detects the concentration of perchlorate with ion chromatograph, until active sludge carbon penetrates fully, goes out the initial concentration that water concentration reaches or approach the sodium perchlorate aqueous solution in former liquid pool 7.Adopt untreated mud in contrast sample under similarity condition, adsorbed.
Result shows, the volume of water sample of processing when control sample is penetrated fully is 626BV, and while using active sludge carbon, the volume of water sample by adsorption column does not all detect perchlorate while being less than 2362BV, the volume of water sample that active sludge carbon passes through while penetrating fully is 4870BV.By calculating above-mentioned active sludge carbon, to the adsorption capacity of sodium perchlorate, be 0.52mg/g.
embodiment 3
The regeneration of the active sludge carbon of the present embodiment and application thereof comprise the following steps:
By the dry 24h under 105 ℃ of the active sludge carbon after penetrating fully, then be heated to 500 ℃ under nitrogen protection in micro-wave oven, constant temperature 10min, finally at steam and CO
2environment under be heated to 800 ℃ and process 60min, obtain the regeneration sludge active carbon; The regeneration sludge active carbon is continued to put back in packed column 4, is that the 80 μ g/L sodium perchlorate aqueous solution are adsorbed to concentration under the adsorption conditions identical with embodiment 2.
Result shows, processes when the water yield is 2000BV and do not detect perchlorate, and when the regeneration sludge active carbon penetrates fully, by volume of water sample, be 4020BV.Process calculating regeneration sludge active carbon is 0.44mg/g to the adsorption capacity of sodium perchlorate.Through micro wave regeneration, make active sludge carbon obtain very large recovery to the adsorption capacity of sodium perchlorate, recovery rate is 84.6%.
The preparation method of the active sludge carbon of the present embodiment and application comprise the following steps:
Preparation process and embodiment 1 are basically identical, and difference is: in step (1), in the step of pyrolytic reaction, the end reaction temperature is 550 ℃, stops 60min; In step (2), the mass concentration of hydrogen peroxide is 15%; In step (3), the temperature of aminating reaction is 650 ℃; In step (4), 2g active sludge carbon ammonification powdered carbon raw material is immersed in the 15g methyl iodide.By the active sludge carbon that obtains according to being that the 80 μ g/L sodium perchlorate aqueous solution are adsorbed to concentration under the condition identical with embodiment 2.
Result shows, the volume of water sample that active sludge carbon passes through while penetrating fully is 6680BV, and active sludge carbon is 0.68mg/g to the adsorption capacity of sodium perchlorate.
The preparation method of the active sludge carbon of the present embodiment and application comprise the following steps:
Preparation process and embodiment 1 are basically identical, and difference is: in step (1), the ammonia flow velocity is 50mL/min, and in the step of pyrolytic reaction, the end reaction temperature is 550 ℃; In step (2), 10g active sludge carbon ammonification powdered carbon raw material is added in the 150mL hydrogen peroxide solution, and the time of vibration oxidation reaction is 5h; In step (3), the temperature of aminating reaction is 850 ℃; In step (4), 2g active sludge carbon ammonification powdered carbon raw material is immersed in the 12g methyl iodide, and time of repose is 96h.By the active sludge carbon that obtains according to being that the 80 μ g/L sodium perchlorate aqueous solution are adsorbed to concentration under the condition identical with embodiment 2.
Result shows, the volume of water sample that active sludge carbon passes through while penetrating fully is 3845BV, and active sludge carbon is 0.45mg/g to the adsorption capacity of sodium perchlorate.
The preparation method of the active sludge carbon of the present embodiment and application comprise the following steps:
Preparation process and embodiment 1 are basically identical, and difference is: in step (1), in the step of pyrolytic reaction, the end reaction temperature is 600 ℃, and the time of staying is 60min; In step (2), the mass concentration of hydrogen peroxide is that 15%, 10g active sludge carbon powdered carbon raw material is added in the 120mL hydrogen peroxide solution; In step (3), the temperature of aminating reaction is 750 ℃, and the time is 120min, and ammonification gas is ammonia-carbon dioxide gas mixture, and in mist, ammonia flow is 30mL/min, and the flow of carbon dioxide gas amount is 20 mL/min; In step (4), 2g active sludge carbon ammonification powdered carbon raw material is immersed in the 10g methyl iodide, and time of repose is 120h.By the active sludge carbon that obtains according to being that the 80 μ g/L sodium perchlorate aqueous solution are adsorbed to concentration under the condition identical with embodiment 2.
Result shows, the volume of water sample that active sludge carbon passes through while penetrating fully is 4920BV, and active sludge carbon is 0.54mg/g to the adsorption capacity of sodium perchlorate.
The preparation method of the active sludge carbon of the present embodiment and application comprise the following steps:
Preparation process and embodiment 1 are basically identical, and difference is: in step (1), in the step of pyrolytic reaction, after first being warming up to 110 ℃, then be warming up to 550 ℃ of end reaction temperature with 20 ℃/min speed; In step (2), the mass concentration of hydrogen peroxide is 18%, and volume is 100mL, and the temperature of vibration oxidation reaction is 55 ℃, and the time is 8h; In step (3), the temperature of aminating reaction is 750 ℃, and the time is 120min, the mist that ammonification gas is ammonia-carbon dioxide, and in mist, ammonia flow is 30mL/min, the flow of carbon dioxide gas amount is 10 mL/min; In step (4), the 2g active sludge carbon is immersed in the 16g methyl iodide, and time of repose is 60h.By the active sludge carbon that obtains according to being that the 80 μ g/L sodium perchlorate aqueous solution are adsorbed to concentration under the condition identical with embodiment 2.
Result shows, the volume of water sample that active sludge carbon passes through while penetrating fully is 5740BV, and active sludge carbon is 0.59mg/g to the adsorption capacity of sodium perchlorate.
To the breakthrough curve of the sodium perchlorate aqueous solution as shown in Figure 5, adsorbent is respectively active sludge carbon powdered carbon raw material to different adsorbents, prepared active sludge carbon and the regeneration sludge active carbon of embodiment 3 gained in embodiment 2,4,5,6,7.Known according to Fig. 5, active sludge carbon is compared active sludge carbon powdered carbon raw material the sodium perchlorate aqueous solution of low concentration is had to stronger adsorption capacity, and after regeneration is processed, active sludge carbon obtains good recovery to the adsorption capacity of the sodium perchlorate aqueous solution of low concentration.
The preparation method of the active sludge carbon of the present embodiment and application comprise the following steps:
Preparation process and embodiment 1 are basically identical, and difference is: in step (1), in the step of pyrolytic reaction, temperature first reaches 110 ℃, then is warming up to 500 ℃ of end reaction temperature with the speed of 20 ℃/min; In step (2), the mass concentration of hydrogen peroxide is 15%, and volume is 150mL, and the temperature of vibration oxidation reaction is 55 ℃, and the time is 8h; In step (3), the temperature of aminating reaction is 750 ℃, and the time is 120min, the mist that ammonification gas is ammonia-carbon dioxide, and in mist, ammonia flow is 30mL/min, the flow of carbon dioxide gas amount is 10mL/min; In step (4), 2g active sludge carbon ammonification carbon dust raw material is immersed in the 16g methyl iodide, and time of repose is 50h.By the active sludge carbon that obtains according to being that the 20 μ g/L sodium perchlorate aqueous solution are adsorbed to concentration under the condition identical with embodiment 2.
Result shows, the volume of water sample that active sludge carbon passes through while penetrating fully is 7520BV, and active sludge carbon is 0.28mg/g to the adsorption capacity of sodium perchlorate.
embodiment 9
The preparation method of the active sludge carbon of the present embodiment and application comprise the following steps:
Preparation process and embodiment 1 are basically identical, and difference is: in step (1), in the step of pyrolytic reaction, after temperature first reaches 110 ℃, then be warming up to 500 ℃ of end reaction temperature with the speed of 25 ℃/min; In step (2), the mass concentration of hydrogen peroxide is 18%, and volume is 50mL, and the temperature of vibration oxidation reaction is 55 ℃, and the time is 10h; In step (3), the temperature of aminating reaction is 750 ℃, and the time is 90min, the mist that ammonification gas is ammonia-carbon dioxide, and in mist, ammonia flow is 20mL/min, the flow of carbon dioxide gas amount is 10mL/min; In step (4), 2g active sludge carbon ammonification powdered carbon raw material is immersed in the 12g methyl iodide, and time of repose is 60h.By the active sludge carbon that obtains according to being that the 200 μ g/L sodium perchlorate aqueous solution are adsorbed to concentration under the condition identical with embodiment 2.
Result shows, the volume of water sample that active sludge carbon passes through while penetrating fully is 3740BV, and active sludge carbon is 0.71mg/g to the adsorption capacity of sodium perchlorate.
In above embodiment, 1BV=0.7ml, from the embodiment result, the volume ratio of the quality of active sludge carbon and perchlorate waste water is 1: 7.48g/ L～1: 15.04g/ L.
In above embodiment, the given sodium perchlorate aqueous solution, active sludge carbon also can be processed the low concentration potassium hyperchlorate aqueous solution.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention also not only is confined to above-described embodiment.All technical schemes belonged under thinking of the present invention all belong to protection scope of the present invention.Be noted that for those skilled in the art, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of an active sludge carbon is characterized in that comprising the following steps:
(1) pyrolysis processing: will after drying sludge, pulverize and sieve, carry out pyrolytic reaction in ammonia atmosphere, dry after washing, obtain active sludge carbon powdered carbon raw material;
(2) oxidation processes: active sludge carbon powdered carbon raw material is added in hydrogen peroxide solution, and after the vibration oxidation reaction, washing is dry, obtains sludge activity char combustion powdered carbon raw material;
(3) ammonification is processed: by sludge activity char combustion powdered carbon raw material as in heater, pass into the air in nitrogen emptying heater, carry out aminating reaction to passing into ammonification gas in heater again, finally be cooled to room temperature to passing into nitrogen in heater again, after washing, vacuum drying, obtain active sludge carbon ammonification powdered carbon raw material;
(4) processing that methylates: active sludge carbon ammonification powdered carbon raw material is immersed in to methylating reagent, and the airtight standing methylation reaction that carries out, clean with sodium chloride solution after methylation reaction, then, by deionized water washing final vacuum drying, obtain active sludge carbon.
2. the preparation method of active sludge carbon according to claim 1, it is characterized in that: the excess sludge that in described step (1), mud is sewage treatment plant, the temperature of drying sludge is 105 ℃～110 ℃, and be 24h～48h drying time, sieves and is of a size of 200 orders～300 orders; In described step (1), the flow velocity of ammonia is 50mL/min～100mL/min; The step of pyrolytic reaction is in described step (1), and first the speed with 20 ℃/min～30 ℃/min is warming up to 110 ℃, stops 5min, then is warming up to 400 ℃～600 ℃ of end reaction temperature with the speed of 10 ℃/min～30 ℃/min, stops 60min～120min; In described step (1), the rear dry temperature of washing is 105 ℃～110 ℃, and the time is 12h～24h.
3. the preparation method of active sludge carbon according to claim 2, it is characterized in that: in described step (2), the mass concentration of hydrogen peroxide solution is 5%～20%, and the quality of active sludge carbon powdered carbon raw material and the volume ratio of hydrogen peroxide solution are 1: 5g/ml～1: 20g/ml; In described step (2), the temperature of vibration oxidation reaction is 40 ℃～70 ℃, and rotating speed is 120r/min～150r/min, and the time is 5h～10h; Temperature dry in described step (2) is 105 ℃～110 ℃, and the time is 5h～10h.
4. the preparation method of active sludge carbon according to claim 3 is characterized in that: the step of the air in described step (3) in the emptying heater is, with the flow velocity of 100mL/min, passes into nitrogen 10min; In described step (3), the step of aminating reaction is, stop passing into described nitrogen while with 20 ℃/min speed, being warming up to 400 ℃, flow velocity with 10mL/min～30mL/min passes into ammonification gas, speed with 20 ℃/min～30 ℃/min is warming up to 650 ℃～850 ℃ of aminating reaction temperature, and stops 60min～120min; In described step (3), vacuum drying temperature is 105 ℃～110 ℃, and the time is 8h～15h.
5. the preparation method of active sludge carbon according to claim 4 is characterized in that: in described step (4), methylating reagent is methyl iodide; In described step (4), the mass ratio of active sludge carbon ammonification powdered carbon raw material and methylating reagent is 1.5～2: 10～20; In described step (4), the standing time is 48h～120h; In described step (4), the molar concentration of sodium chloride solution is 2mol/L～4mol/L; In described step (4), vacuum drying temperature is 50 ℃～120 ℃, and the time is 12h～24h.
6. according to the preparation method of the described active sludge carbon of claim 1～5 any one, it is characterized in that: described ammonification gas is ammonia, or ammonia-carbon dioxide gas mixture, in described An Qi – carbon dioxide gas mixture, the volume ratio of ammonia and carbon dioxide is 10～30: 1～20.
One kind as arbitrary as claim 1～6 as described in the active sludge carbon for preparing of method be applied to process low concentration perchlorate waste water.
8. the application of active sludge carbon according to claim 7, it is characterized in that comprising the following steps: active sludge carbon is packed in adsorption system, the low concentration perchlorate waste water of 20 μ g/L～200 μ g/L is sent into to described adsorption system and carry out adsorption reaction, the volume ratio of the quality of described active sludge carbon and perchlorate waste water is 1: 7.48g/ L～1: 15.04g/ L.
9. the application of active sludge carbon according to claim 8 is characterized in that: described perchlorate waste water is the sodium perchlorate aqueous solution or the potassium hyperchlorate aqueous solution.
10. the application of active sludge carbon according to claim 8 or claim 9, it is characterized in that: described adsorption system comprises an adsorption column (2), adsorption column (2) two ends are connected with respectively water inlet pipe (5) and outlet pipe (1), be connected to peristaltic pump (6) on water inlet pipe (5), and water inlet pipe (5) passes in former liquid pool (7) away from an end of adsorption column (2).
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