CN103613232A - Method of treating traditional Chinese medicine wastewater by utilizing modified fly ashes and photocatalyst - Google Patents
Method of treating traditional Chinese medicine wastewater by utilizing modified fly ashes and photocatalyst Download PDFInfo
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Abstract
The invention relates to a method of treating traditional Chinese medicine wastewater by utilizing modified fly ashes and a photocatalyst. The method specifically comprises the following steps of: modifying fly ashes by utilizing an activator, roasting, and the like, wherein each modified fly ash is used for carrying out original fluid pre-treatment onto the traditional Chinese medicine wastewater in sequence; carrying out photocatalytic degradation onto the pre-treated traditional Chinese medicine wastewater under radiation of sunlight, wherein the used photocatalyst is obtained by loading TiO2/Cu2O with the fly ashes; finally, carrying out flocculating settling onto the catalyzed water by a flocculating agent prepared by fly ashes. Fly ashes, waste scrap iron, industrial waste acid, and the like, are used as main materials, so that treatment cost of the traditional Chinese medicine wastewater can be effectively lowered, and secondary pollution can also be avoided; during treatment, the composite photocatalyst with efficient catalytic degradation ability in the sun is used, so that decomposition time of organic pollutants is effectively shortened, and the photocatalyst can be recycled for repeated catalysis by loading the photocatalyst with the fly ashes; wastewater treatment scale can be large and small, and ferric aluminum polysilicate can be prepared on the scene according to actually generated wastewater amount and characteristics of the wastewater.
Description
Technical field
The present invention relates to a kind of pharmaceutical wastewater treatment process, particularly a kind of method of utilizing modified coal ash and photocatalyst treatment traditional Chinese medicine wastewater.
Background technology
Traditional Chinese medicine wastewater, mainly from production plant ,Ge great institute of traditional Chinese medicine and Chinese medicine pharmacy, produces in washing the processes such as bubble boiling medicinal material, flushing, preparation.Traditional Chinese medicine wastewater comprises the former medicine washing water in production process, in the sewage producing in the unit operations such as medicine original juice raffinate, filtration, distillation, extraction, production unit washing, floor wash water, steam condensate and ion exchange resin acid-base solution and water etc.
In traditional Chinese medicine wastewater, pollutent is roughly divided into two large classes: a class is water miscible, and another kind of is insoluble.Water miscible pollutent main component is carbohydrate (polysaccharide is main), protein, xylogen, organic acid, resin, mucus fat, alkaloid, amino acid, steroidal, phenols, alcohol compound etc. and the nontoxic pigment introduced by film-making operation; The subparticle that insoluble pollutent main composition thing is silt, vegetable fibre, inorganic salt and other suspended substances etc.
Traditional Chinese medicine wastewater is because drug kinds is many, production technique difference is large, and the waste water of discharge has complicated component conventionally, and organic pollutant category is many, saltiness is high, NH
3-N concentration is high, itrogenous organic substance toxicity is large, colourity is dark, suspended substance is many, hard-degraded substance is many, COD value high, and the directly discharge if waste water is not treated, will have a strong impact on ecotope around.A few days ago, the treatment process of pharmacy waste water mainly contains: Physical, chemical method, physico-chemical processes, biochemical process etc., what by Chinese medicine manufacturing enterprise, extensively adopted now is biochemical process.
Application number is that a kind of traditional Chinese medicine wastewater treatment process has been announced in an application for a patent for invention of 201210494723.2, and the traditional Chinese medicine wastewater treatment process that this application is announced is to utilize the microorganism in active sludge aerobic pond and catalytic oxidation Aerobic Pond to consume the organism in traditional Chinese medicine wastewater.When described application is processed for traditional Chinese medicine wastewater, although this technique can be carried out the separation disposal of pollutent and the conversion of objectionable impurities is decomposed, but need to being exposed to for a long time, this technique in air, carries out microorganism decomposition, large, the consuming time length of floor space, waste water treatment efficiency is low, and large amount of organic long-term exposure, in air, even also can produce the secondary pollution to surrounding environment.Conventionally after organic acid enters waste water in Chinese medicine processing, can make waste water present acid buffer system, be unfavorable for the flora existence in biological degradation, even can cause microorganism mortality, cause water treatment effect unsatisfactory.
Summary of the invention
The object of the invention is to overcome the deficiency that existing method exists, a kind of method of utilizing modified coal ash and photocatalyst treatment traditional Chinese medicine wastewater is provided, the method can effectively shorten the sewage disposal time, avoid secondary pollution, make traditional Chinese medicine wastewater treatment process can adapt to the processing of different scales, different concns traditional Chinese medicine wastewater, effectively improved processing efficiency and the adaptive faculty of traditional Chinese medicine wastewater treatment system.
In order to realize foregoing invention object, the invention provides following technical scheme:
A method of utilizing modified coal ash and photocatalyst treatment traditional Chinese medicine wastewater, comprises stoste pre-treatment, photocatalytic degradation, flocculating settling.
(1) stoste pre-treatment: flyash has been carried out to three different modifications, traditional Chinese medicine wastewater utilizes activation ash, sodium hydroxide modification ash and three different modification ashes of high-temperature roasting ash piece to carry out pre-treatment successively, thereby realize the pre-treatment to traditional Chinese medicine wastewater, make it meet the requirement of carrying out photocatalytic degradation, the main chemical compositions of flyash used has SiO
2, Al
2o
3, Fe
2o
3, CaO, MgO, NaO and unburnt carbon etc., wherein the massfraction of effective constituent is respectively SiO
2(40%～60%), Al
2o
3(17%～35%) and Fe
2o
3(2%～15%) (1) activation ash: will add activator M in flyash, add mass ratio to control as M:SiO
2=1:4 is placed in High Temperature Furnaces Heating Apparatus, under the condition of 900 ℃, roasting 1 hour, room temperature to be returned to is taken out, and grinds a little, obtains activation ash, activation ash is controlled at 1:10-1:15 with the mass ratio of traditional Chinese medicine wastewater, stir standing centrifugation after 10 minutes, obtain filtrate A, wherein: the ratio of activator M composition quality is Na
2cO
3: NaCl:CaO=10:2.5:1; (2) sodium hydroxide modification ash: utilize volumetric molar concentration flyash to be carried out to modification for 2mol/LNaOH solution, mass ratio is controlled at NaOH:SiO
2=1:15, while being heated to 130 ℃, constant temperature stirs 5 minutes post-dryings and obtains sodium hydroxide modification ash, according to sodium hydroxide modification ash and traditional Chinese medicine wastewater mass ratio 1:10-1:15, filtrate A is added in sodium hydroxide modification ash and carries out second step pre-treatment, stir the B that filters to get filtrate after 10 minutes; (3) high-temperature roasting ash piece: flyash is directly placed in to High Temperature Furnaces Heating Apparatus, after taking out for 4 hours, 800 ℃ of-850 ℃ of roastings adopt the pressure of powder compressing machine 20t to be pressed into the high-temperature roasting ash piece that 1cm is thick, liquor B is filtered by high-temperature roasting ash piece, obtains liquor C;
(2) photocatalytic degradation: this one-phase comprises the preparation of activation ash loading photocatalyst and utilize self-made photocatalyst catalyzed degradation traditional Chinese medicine wastewater under daylight.(1) activation ash loading photocatalyst TiO
2/ Cu
2the preparation of O: the activation ash in stoste pre-treatment step is fully ground, cross the postactivated ash of 50 mesh sieve and commercially available P25 type TiO
2after 2:1 mixes in mass ratio, will activate ash and commercially available P25 type TiO
2miscellany joins 0.35mol/L Cu (NO
3)
2in solution, control TiO
2with Cu (NO
3)
2amount of substance than for 1:6, again by amount of substance than cupric nitrate: quadrol=1:3 adds quadrol, after fully stirring, add sodium hydroxide, control amount of substance than cupric nitrate: sodium hydroxide=1:2, after fully dissolving, by amount of substance, than cupric nitrate: glucose=1:0.54, add glucose to obtain reaction solution F again, the beaker that fills reaction solution F is put in oil bath pan, 75 ℃ of temperature constant magnetic stirrings 30 minutes, to obtain product precipitation, filter, with deionized water and ethanol, respectively clean 5 times, in loft drier, 60 ℃ obtain product photocatalyst TiO for dry 3 hours
2/ Cu
2o; (2) day photocatalytic degradation traditional Chinese medicine wastewater: will activate ash loading photocatalyst TiO
2/ Cu
2the photocatalyst TiO preparing in the preparation process of O
2/ Cu
2o joins in liquor C, and controlling photocatalyst and liquor C mass ratio is 1:40-1:200, and lucifuge stirs 30 minutes after photocatalyst fully mixes with filtrate, adds H
2o
2pro-oxidant, add-on is controlled and is added 1mlH for every 100g liquor C
2o
2, mixed solution is placed in and under daylight, carries out photocatalytic degradation, during continue to pass into air in constantly stirring, it is 120L/h that air passes into flow control, catalyzed degradation is separated filtrate D after 120 minutes;
(3) flocculating settling: first this one-phase utilizes flyash to prepare poly-ferro-aluminum, poly-silicic acid, rear control felicity condition is prepared poly aluminium iron silicate, finally utilizes the flocculation agent of preparation to carry out flocculating settling processing to passing through the traditional Chinese medicine wastewater filtrate D of photocatalytic degradation.(1) preparation of poly-ferro-aluminum: by flyash and Na
2cO
3after mixing, put into High Temperature Furnaces Heating Apparatus, control mass ratio Na
2cO
3: SiO
2=1:3,900 ℃ of roastings obtain product α for 1 hour, product α is added in nitration mixture and stirs and leach at 65 ℃, control product α and nitration mixture mass ratio 1:4, leach filtering separation after 120 minutes, obtain filter residue I and filtrate I, in filtrate I, add waste iron filing and hydrochloric acid to adjust ferro-aluminum amount of substance, treat that ferro-aluminum amount of substance obtains product β than for 1:1, nitration mixture used is that mass percent concentration is 15%HCl and 25%H
2sO
41:1 is formulated in mass ratio; (2) preparation of poly-silicic acid: filter residue I is dried at 100-200 ℃ in loft drier, control filter residue I and sodium hydroxide mass ratio 1:3 and add mass percent concentration 20%NaOH solution to be heated to 80 ℃ of constant temperature immersions after 60 minutes, be diluted with water to SiO
3 2-mass percent concentration be 8%-10%, then use mass percent concentration 25%H
2sO
4regulate pH to 2-3, this liquid is labeled as product γ.(3) preparation of poly aluminium iron silicate: product β is mixed and carries out polymerization with product γ, and controlling ferro-aluminum total amount is 1:1 with the amount ratio of silicon matter, and under agitation controlling pH is 1.7-2, and room temperature obtains sorrel liquid poly silicate aluminium ferric flocculating agent for standing 4 hours; (4) flocculation treatment: poly silicate aluminium ferric flocculating agent is joined and carries out flocculation treatment through in the filtrate D of photocatalytic degradation, it is that poly aluminium iron silicate is 1:30 with quality ratio that additional proportion is controlled, after 60 minutes, water and flocculation agent are carried out to separated obtaining and finally process rear water, this water is carried out to analyzing and testing.
The present invention is owing to having selected flyash, waste iron filing, industrial waste acid etc. to process raw material as traditional Chinese medicine wastewater, and in each step, treatment agent used all can be realized reclaiming and re-use, and effectively reduces traditional Chinese medicine wastewater processing cost; For current conventional Chinese medicine waste water treatment process mesophytization method, process that waste water floor space is large, long processing period, be exposed in air and can cause the problems such as secondary environmental pollution for a long time, what the present invention adopted is to utilize photocatalysis to degrade organic matter under daylight within 120 minutes, can complete organic effective degraded, greatly shortens the treatment cycle of traditional Chinese medicine wastewater; Flyash also makes the photocatalyst can efficient recovery to the load of photocatalyst, realizes the regeneration of catalyzer and uses; The technique of processing mainly for large-scale waste water in pharmaceutical plants in other traditional Chinese medicine wastewater patented technologies, for Miniature Chinese medicine infusion waste water, cannot apply, wastewater treatment scale of the present invention is changeable, to various COD(chemical oxygen demands) and SS(suspended substance) traditional Chinese medicine wastewater of parameter all has good treatment effect, refers to table 1; Poly aluminium iron silicate be also will gather again while using at the scene silicic acid and polymeric ferric aluminum on request ratio mix, convenient storage and transportation, also can accomplish to produce the on-the-spot preparation of wastewater flow rate according to reality.
Table 1 the present invention processes different COD traditional Chinese medicine wastewater effects
In table: COD represents chemical oxygen demand;
SS represents suspended substance (particle)
Accompanying drawing explanation
Fig. 1 is a kind of process flow sheet that utilizes the method for modified coal ash and photocatalyst treatment traditional Chinese medicine wastewater of the present invention;
Embodiment
Below in conjunction with embodiment and embodiment, the present invention is further illustrated, and the present invention can form a plurality of embodiment according to different proportionings, is not limited to listed three below.
Embodiment 1:
Adopt the mixing factory effluent of Inner Mongol herbal pharmaceutical factory, this pharmaceutical factory is at Chinese medicine production period, mix factory effluent mainly by Chinese traditional medicine wastewater treatment, wash bottle, wash plug waste water, resin regeneration waste water, machine maintenance waste water, sanitary wastewater, quality inspection waste water, the seven class waste water compositions such as raffinate after ethanol distillation reclaims.Waste water presents tawny, COD
cr(recording chemical oxygen demand with potassium dichromate process) mean value 14200mg/L, SS(represents suspended particle) mean value 3620mg/L, pH mean value is 4.5, the absorbancy of waste water at 340nm place is 0.523.Flyash main chemical compositions used has SiO
2, Al
2o
3, Fe
2o
3, CaO, MgO, NaO and unburnt carbon etc., wherein the massfraction of effective constituent is respectively SiO
2be 60%, Al
2o
3be 35% and Fe
2o
3be 2%.
Utilize the inventive method to carry out successively stoste pre-treatment, photocatalytic degradation, flocculating settling processing to traditional Chinese medicine wastewater, detailed process is as follows:
(1) stoste pre-treatment: flyash has been carried out to three different modifications, traditional Chinese medicine wastewater utilizes activation ash, sodium hydroxide modification ash and three different modification ashes of high-temperature roasting ash piece to carry out pre-treatment successively, thereby makes it meet the requirement of carrying out photocatalytic degradation.(1) activation ash: (mass ratio is controlled as M:SiO to take 1.5kg activator M and 10kg flyash
2=1:4), the two is mixed, be placed under the condition of 900 ℃ of High Temperature Furnaces Heating Apparatuss, roasting 1 hour, room temperature to be returned to is taken out, and grinds a little, obtain activation ash, take 10kg activation ash and joined (activation ash is controlled as 1:10 with the mass ratio of traditional Chinese medicine wastewater) in 100kg traditional Chinese medicine wastewater and stir standing centrifugation after 10 minutes, obtain filtrate A, wherein: the ratio of activator M composition quality is Na
2cO
3: NaCl:CaO=10:2.5:1; (2) sodium hydroxide modification ash: get volumetric molar concentration and be 2mol/LNaOH solution 5L and join and carry out modification in 10kg flyash and (control pure NaOH:SiO
2mass ratio is 1:15), while being heated to 130 ℃, constant temperature stirs 5 minutes post-dryings and obtains sodium hydroxide modification ash, according to sodium hydroxide modification ash and traditional Chinese medicine wastewater mass ratio 1:10, sodium hydroxide modification ash is added in filtrate A and carries out second step pre-treatment, stir the B that filters to get filtrate after 10 minutes; (3) high-temperature roasting ash piece: 1kg flyash is directly placed in to High Temperature Furnaces Heating Apparatus, adopts the pressure of powder compressing machine 20t to be pressed into the high-temperature roasting ash piece that 1cm is thick after 800 ℃ of roastings are taken out for 4 hours, liquor B is filtered by high-temperature roasting ash piece, obtains liquor C;
(2) photocatalytic degradation: this one-phase comprises the preparation of activation ash loading composite photo-catalyst and utilize self-made photocatalyst catalyzed degradation traditional Chinese medicine wastewater under daylight.(1) activation ash loading photocatalyst TiO
2/ Cu
2the preparation of O: the activation ash in stoste pre-treatment step is fully ground, cross the postactivated ash of 50 mesh sieve and commercially available P25 type TiO
2after 2:1 mixes in mass ratio, will activate ash and commercially available P25 type TiO
2miscellany joins 0.35mol/L Cu (NO
3)
2in solution, control TiO
2with Cu (NO
3)
2amount of substance than for 1:6, again by amount of substance than cupric nitrate: quadrol=1:3 adds quadrol, after fully stirring, add sodium hydroxide, control amount of substance than cupric nitrate: sodium hydroxide=1:2, after fully dissolving, by amount of substance, than cupric nitrate: glucose=1:0.54, add glucose to obtain reaction solution F again, the beaker that fills reaction solution F is put in oil bath pan, 75 ℃ of temperature constant magnetic stirrings 30 minutes, to obtain product precipitation, filter, with deionized water and ethanol, respectively clean 5 times, in loft drier, 60 ℃ obtain photocatalyst product TiO for dry 3 hours
2/ Cu
2o; (2) day photocatalytic degradation traditional Chinese medicine wastewater: will activate ash loading photocatalyst TiO
2/ Cu
2the photocatalyst TiO preparing in the preparation process of O
2/ Cu
2o joins in liquor C, and controlling photocatalyst and liquor C mass ratio is 1:40, and lucifuge stirs 30 minutes after photocatalyst fully mixes with filtrate, adds H
2o
2pro-oxidant, add-on is controlled and is added 1mlH for every 100g liquor C
2o
2, mixed solution is placed in and under daylight, carries out photocatalytic degradation, during continue to pass into air in constantly stirring, it is 120L/h that air passes into flow control, catalyzed degradation is separated filtrate D after 120 minutes;
(3) flocculating settling: first this one-phase utilizes flyash to prepare poly-ferro-aluminum, poly-silicic acid, rear control felicity condition is prepared poly aluminium iron silicate, finally utilizes the poly silicate aluminium ferric flocculating agent of preparation to carry out flocculating settling processing to passing through the traditional Chinese medicine wastewater of photocatalytic degradation.(1) preparation of poly-ferro-aluminum: take 4kgNa
2cO
3(control mass ratio Na with 20kg flyash
2cO
3: SiO
2=1:3) after mixing, put into High Temperature Furnaces Heating Apparatus, 900 ℃ of roastings obtain product α for 1 hour, product α is added in nitration mixture and stirs and leach at 65 ℃, control product α and nitration mixture mass ratio 1:4, leach filtering separation after 120 minutes, obtain filter residue I and filtrate I, in filtrate I, add waste iron filing and hydrochloric acid to adjust ferro-aluminum amount of substance ratio, treat that ferro-aluminum amount of substance obtains product β than for 1:1, nitration mixture used is that mass percent concentration is 15%HCl and 25%H
2sO
41:1 is formulated in mass ratio; (2) preparation of poly-silicic acid: filter residue I is dried at 200 ℃ in loft drier, control filter residue I and sodium hydroxide mass ratio 1:3 and add mass percent concentration 20%NaOH solution to be heated to 80 ℃ of constant temperature immersions after 60 minutes, be diluted with water to SiO
3 2-mass percent concentration be 10%, then use mass percent concentration 25%H
2sO
4regulate pH to 3, this liquid is labeled as product γ.(3) preparation of poly aluminium iron silicate: product β is mixed and carries out polymerization with product γ, and controlling ferro-aluminum total amount is 1:1 with the amount ratio of silicon matter, and under agitation controlling pH is 2, and room temperature obtains sorrel liquid poly silicate aluminium ferric flocculating agent for standing 4 hours; (4) flocculation treatment: poly silicate aluminium ferric flocculating agent is joined and carries out flocculation treatment through in the filtrate D of photocatalytic degradation, it is that poly aluminium iron silicate is 1:30 with quality ratio that additional proportion is controlled, after 60 minutes to water and flocculation agent carry out centrifugation obtain finally process after water outlet, flocculation agent can reclaim and reuse.
Effluent quality is limpid, water outlet COD after processing after measured
cr(recording chemical oxygen demand with potassium dichromate process) mean value 102mg/L, SS(represents suspended particle) mean value 70mg/L, COD clearance reaches 99%, SS clearance and reaches 98%.
Embodiment 2:
The waste water that adopts Inner Mongol institute of traditional Chinese medicine to produce in Chinese medicine processing is mainly to wash filling waste water.Waste water presents tawny, COD
cr(recording chemical oxygen demand with potassium dichromate process) mean value 6800mg/L, SS(represents suspended particle) mean value 3250mg/L, pH mean value is 5.1, the absorbancy of waste water at 340nm place is that 0.535. flyash main chemical compositions used has SiO
2, Al
2o
3, Fe
2o
3, CaO, MgO, NaO and unburnt carbon etc., wherein the massfraction of effective constituent is respectively SiO
2be 40%, Al
2o
3be 17% and Fe
2o
3be 15%.
Utilize the inventive method to carry out successively stoste pre-treatment, photocatalytic degradation, flocculating settling processing to traditional Chinese medicine wastewater, detailed process is as follows:
(1) stoste pre-treatment: flyash has been carried out to three different modifications, traditional Chinese medicine wastewater utilizes activation ash, sodium hydroxide modification ash and three different modification ashes of high-temperature roasting ash piece to carry out pre-treatment successively, thereby makes it meet the requirement of carrying out photocatalytic degradation.(1) activation ash: (mass ratio is controlled as M:SiO to take 1kg activator M and 10kg flyash
2=1:4), the two is mixed, be placed under the condition of 900 ℃ of High Temperature Furnaces Heating Apparatuss, roasting 1 hour, room temperature to be returned to is taken out, and grinds a little, obtain activation ash, take 10kg activation ash and joined (activation ash is controlled as 1:12 with the mass ratio of traditional Chinese medicine wastewater) in 120kg traditional Chinese medicine wastewater and stir standing centrifugation after 10 minutes, obtain filtrate A, wherein: the ratio of activator M composition quality is Na
2cO
3: NaCl:CaO=10:2.5:1; (2) sodium hydroxide modification ash: get volumetric molar concentration and be 2mol/LNaOH solution 3.4L and join and carry out modification in 10kg flyash and (control pure NaOH:SiO
2mass ratio is 1:15), while being heated to 130 ℃, constant temperature stirs 5 minutes post-dryings and obtains sodium hydroxide modification ash, according to sodium hydroxide modification ash and traditional Chinese medicine wastewater mass ratio 1:12, sodium hydroxide modification ash is added in filtrate A and carries out second step pre-treatment, stir the B that filters to get filtrate after 10 minutes; (3) high-temperature roasting ash piece: 1kg flyash is directly placed in to High Temperature Furnaces Heating Apparatus, adopts the pressure of powder compressing machine 20t to be pressed into the high-temperature roasting ash piece that 1cm is thick after 850 ℃ of roastings are taken out for 4 hours, liquor B is filtered by high-temperature roasting ash piece, obtains liquor C;
(2) photocatalytic degradation: this one-phase comprises the preparation of activation ash loading photocatalyst and utilize self-made photocatalyst catalyzed degradation traditional Chinese medicine wastewater under daylight.(1) activation ash loading photocatalyst TiO
2/ Cu
2the preparation of O: the activation ash in stoste pre-treatment step is fully ground, cross the postactivated ash of 50 mesh sieve and commercially available P25 type TiO
2after 2:1 mixes in mass ratio, will activate ash and commercially available P25 type TiO
2miscellany joins 0.35mol/L Cu (NO
3)
2in solution, control TiO
2with Cu (NO
3)
2amount of substance than for 1:6, again by amount of substance than cupric nitrate: quadrol=1:3 adds quadrol, after fully stirring, add sodium hydroxide, control amount of substance than cupric nitrate: sodium hydroxide=1:2, after fully dissolving, by amount of substance, than cupric nitrate: glucose=1:0.54, add glucose to obtain reaction solution F again, the beaker that fills reaction solution F is put in oil bath pan, 75 ℃ of temperature constant magnetic stirrings 30 minutes, to obtain product precipitation, filter, with deionized water and ethanol, respectively clean 5 times, in loft drier, 60 ℃ obtain photocatalyst product TiO for dry 3 hours
2/ Cu
2o; (2) day photocatalytic degradation traditional Chinese medicine wastewater: will activate ash loading photocatalyst TiO
2/ Cu
2the photocatalyst TiO preparing in the preparation process of O
2/ Cu
2o joins in liquor C, and controlling photocatalyst and liquor C mass ratio is 1:100, and lucifuge stirs 30 minutes after photocatalyst fully mixes with filtrate, adds H
2o
2pro-oxidant, add-on is controlled and is added 1mlH for every 100g liquor C
2o
2, mixed solution is placed in and under daylight, carries out photocatalytic degradation, during continue to pass into air in constantly stirring, it is 120L/h that air passes into flow control, catalyzed degradation is separated filtrate D after 120 minutes;
(3) flocculating settling: first this one-phase utilizes flyash to prepare poly-ferro-aluminum, poly-silicic acid, rear control felicity condition is prepared poly aluminium iron silicate, finally utilizes the poly silicate aluminium ferric flocculating agent of preparation to carry out flocculating settling processing to passing through the traditional Chinese medicine wastewater of photocatalytic degradation.(1) preparation of poly-ferro-aluminum: take 2.67kgNa
2cO
3(control mass ratio Na with 20kg flyash
2cO
3: SiO
2=1:3) after mixing, put into High Temperature Furnaces Heating Apparatus, 900 ℃ of roastings obtain product α for 1 hour, product α is added in nitration mixture and stirs and leach at 65 ℃, control product α and nitration mixture mass ratio 1:4, leach filtering separation after 120 minutes, obtain filter residue I and filtrate I, in filtrate I, add waste iron filing and hydrochloric acid to adjust ferro-aluminum amount of substance ratio, treat that ferro-aluminum amount of substance obtains product β than for 1:1, nitration mixture used is that mass percent concentration is 15%HCl and 25%H
2sO
41:1 is formulated in mass ratio; (2) preparation of poly-silicic acid: filter residue I is dried at 100 ℃ in loft drier, control filter residue I and sodium hydroxide mass ratio 1:3 and add mass percent concentration 20%NaOH solution to be heated to 80 ℃ of constant temperature immersions after 60 minutes, be diluted with water to SiO
3 2-mass percent concentration be 8%, then use mass percent concentration 25%H
2sO
4regulate pH to 2, this liquid is labeled as product γ.(3) preparation of poly aluminium iron silicate: product β is mixed and carries out polymerization with product γ, and controlling ferro-aluminum total amount is 1:1 with the amount ratio of silicon matter, and under agitation controlling pH is 1.7, and room temperature obtains sorrel liquid poly silicate aluminium ferric flocculating agent for standing 4 hours; (4) flocculation treatment: poly silicate aluminium ferric flocculating agent is joined and carries out flocculation treatment through in the filtrate D of photocatalytic degradation, it is that poly aluminium iron silicate is 1:30 with quality ratio that additional proportion is controlled, after 60 minutes to water and flocculation agent carry out centrifugation obtain finally process after water outlet, flocculation agent can reclaim and reuse.
Effluent quality is limpid, water outlet COD after processing after measured
cr(recording chemical oxygen demand with potassium dichromate process) mean value 101mg/L, SS(represents suspended particle) mean value 70mg/L, COD clearance reaches 98.5%, SS clearance and reaches 97.8%.
Embodiment 3:
Adopt the waste water producing in the Chinese medicine processing of packet header, Inner Mongol pharmacy, comprise wash water and wash filling waste water.Waste water presents tawny, COD
cr(recording chemical oxygen demand with potassium dichromate process) mean value 2289mg/L, SS(represents suspended particle) mean value 528mg/L, pH mean value is 5, the absorbancy of waste water at 340nm place is that 0.559. flyash main chemical compositions used has SiO
2, Al
2o
3, Fe
2o
3, CaO, MgO, NaO and unburnt carbon etc., wherein the massfraction of effective constituent is respectively SiO
2be 55%, Al
2o
3be 30% and Fe
2o
3be 6%.
Utilize the inventive method to carry out successively stoste pre-treatment, photocatalytic degradation, flocculating settling processing to traditional Chinese medicine wastewater, detailed process is as follows:
(1) stoste pre-treatment: flyash has been carried out to three different modifications, traditional Chinese medicine wastewater utilizes activation ash, sodium hydroxide modification ash and three different modification ashes of high-temperature roasting ash piece to carry out pre-treatment successively, thereby makes it meet the requirement of carrying out photocatalytic degradation.(1) activation ash: (mass ratio is controlled as M:SiO to take 0.138kg activator M and 1kg flyash
2=1:4), the two is mixed, be placed under the condition of 900 ℃ of High Temperature Furnaces Heating Apparatuss, roasting 1 hour, room temperature to be returned to is taken out, and grinds a little, obtain activation ash, take 1kg activation ash and joined (activation ash is controlled as 1:15 with the mass ratio of traditional Chinese medicine wastewater) in 15kg traditional Chinese medicine wastewater and stir standing centrifugation after 10 minutes, obtain filtrate A, wherein: the ratio of activator M composition quality is Na
2cO
3: NaCl:CaO=10:2.5:1; (2) sodium hydroxide modification ash: get volumetric molar concentration and be 2mol/LNaOH solution 0.46L and join and carry out modification in 1kg flyash and (control pure NaOH:SiO
2mass ratio is 1:15), while being heated to 130 ℃, constant temperature stirs 5 minutes post-dryings and obtains sodium hydroxide modification ash, according to sodium hydroxide modification ash and traditional Chinese medicine wastewater mass ratio 1:15, sodium hydroxide modification ash is added in filtrate A and carries out second step pre-treatment, stir the B that filters to get filtrate after 10 minutes; (3) high-temperature roasting ash piece: 1kg flyash is directly placed in to High Temperature Furnaces Heating Apparatus, adopts the pressure of powder compressing machine 20t to be pressed into the high-temperature roasting ash piece that 1cm is thick after 820 ℃ of roastings are taken out for 4 hours, liquor B is filtered by high-temperature roasting ash piece, obtains liquor C;
(2) photocatalytic degradation: this one-phase comprises the preparation of activation ash loading photocatalyst and utilize self-made photocatalyst catalyzed degradation traditional Chinese medicine wastewater under daylight.(1) activation ash loading photocatalyst TiO
2/ Cu
2the preparation of O: the activation ash in stoste pre-treatment step is fully ground, cross the postactivated ash of 50 mesh sieve and commercially available P25 type TiO
2after 2:1 mixes in mass ratio, will activate ash and commercially available P25 type TiO
2miscellany joins 0.35mol/L Cu (NO
3)
2in solution, control TiO
2with Cu (NO
3)
2amount of substance than for 1:6, again by amount of substance than cupric nitrate: quadrol=1:3 adds quadrol, after fully stirring, add sodium hydroxide, control amount of substance than cupric nitrate: sodium hydroxide=1:2, after fully dissolving, by amount of substance, than cupric nitrate: glucose=1:0.54, add glucose to obtain reaction solution F again, the beaker that fills reaction solution F is put in oil bath pan, 75 ℃ of temperature constant magnetic stirrings 30 minutes, to obtain product precipitation, filter, with deionized water and ethanol, respectively clean 5 times, in loft drier, 60 ℃ obtain photocatalyst product TiO for dry 3 hours
2/ Cu
2o; (2) day photocatalytic degradation traditional Chinese medicine wastewater: will activate ash loading photocatalyst TiO
2/ Cu
2the photocatalyst TiO preparing in the preparation process of O
2/ Cu
2o joins in liquor C, and controlling photocatalyst and liquor C mass ratio is 1:200, and lucifuge stirs 30 minutes after photocatalyst fully mixes with filtrate, adds H
2o
2pro-oxidant, add-on is controlled and is added 1mlH for every 100g liquor C
2o
2, mixed solution is placed in and under daylight, carries out photocatalytic degradation, during continue to pass into air in constantly stirring, it is 120L/h that air passes into flow control, catalyzed degradation is separated filtrate D after 120 minutes;
(3) flocculating settling: first this one-phase utilizes flyash to prepare poly-ferro-aluminum, poly-silicic acid, rear control felicity condition is prepared poly aluminium iron silicate, finally utilizes the poly silicate aluminium ferric flocculating agent of preparation to carry out flocculating settling processing to passing through the traditional Chinese medicine wastewater of photocatalytic degradation.(1) preparation of poly-ferro-aluminum: take 0.43kgNa
2cO
3(control mass ratio Na with 2kg flyash
2cO
3: SiO
2=1:3) after mixing, put into High Temperature Furnaces Heating Apparatus, 900 ℃ of roastings obtain product α for 1 hour, product α is added in nitration mixture and stirs and leach at 65 ℃, control product α and nitration mixture mass ratio 1:4, leach filtering separation after 120 minutes, obtain filter residue I and filtrate I, in filtrate I, add waste iron filing and hydrochloric acid to adjust ferro-aluminum amount of substance ratio, treat that ferro-aluminum amount of substance obtains product β than for 1:1, nitration mixture used is that mass percent concentration is 15%HCl and 25%H
2sO
41:1 is formulated in mass ratio; (2) preparation of poly-silicic acid: filter residue I is dried at 150 ℃ in loft drier, control filter residue I and sodium hydroxide mass ratio 1:3 and add mass percent concentration 20%NaOH solution to be heated to 80 ℃ of constant temperature immersions after 60 minutes, be diluted with water to SiO
3 2-mass percent concentration be 9%, then use mass percent concentration 25%H
2sO
4regulate pH to 2.5, this liquid is labeled as product γ.(3) preparation of poly aluminium iron silicate: product β is mixed and carries out polymerization with product γ, and controlling ferro-aluminum total amount is 1:1 with the amount ratio of silicon matter, and under agitation controlling pH is 1.8, and room temperature obtains sorrel liquid poly silicate aluminium ferric flocculating agent for standing 4 hours; (4) flocculation treatment: poly silicate aluminium ferric flocculating agent is joined and carries out flocculation treatment through in the filtrate D of photocatalytic degradation, it is that poly aluminium iron silicate is 1:30 with quality ratio that additional proportion is controlled, after 60 minutes to water and flocculation agent carry out centrifugation obtain finally process after water outlet, flocculation agent can reclaim and reuse.
Effluent quality is limpid, water outlet COD after processing after measured
cr(recording chemical oxygen demand with potassium dichromate process) mean value 116mg/L, SS(represents suspended particle) mean value 36mg/L, COD clearance reaches 94.9%, SS clearance and reaches 93.1%.
Claims (1)
1. a method of utilizing modified coal ash and photocatalyst treatment traditional Chinese medicine wastewater, is characterized in that, method steps is as follows: the pre-treatment of (one) stoste: (1) activation ash: will in flyash, add activator M, add mass ratio to control as M:SiO
2=1:4 is placed in High Temperature Furnaces Heating Apparatus, under the condition of 900 ℃, roasting 1 hour, room temperature to be returned to is taken out, and grinds a little, obtains activation ash, activation ash is controlled at 1:10-1:15 with the mass ratio of traditional Chinese medicine wastewater, stir standing centrifugation after 10 minutes, obtain filtrate A, wherein: the ratio of activator M composition quality is Na
2cO
3: NaCl:CaO=10:2.5:1; (2) sodium hydroxide modification ash: utilize volumetric molar concentration flyash to be carried out to modification for 2mol/LNaOH solution, mass ratio is controlled at NaOH:SiO
2=1:15, while being heated to 130 ℃, constant temperature stirs 5 minutes post-dryings and obtains sodium hydroxide modification ash, according to sodium hydroxide modification ash and traditional Chinese medicine wastewater mass ratio 1:10-1:15, sodium hydroxide modification ash is added in filtrate A, stirs the B that filters to get filtrate after 10 minutes; (3) high-temperature roasting ash piece: flyash is directly placed in to High Temperature Furnaces Heating Apparatus, after taking out for 4 hours, 800 ℃ of-850 ℃ of roastings adopt the pressure of powder compressing machine 20t to be pressed into the high-temperature roasting ash piece that 1cm is thick, liquor B is filtered by high-temperature roasting ash piece, obtains liquor C; (2) photocatalytic degradation: (1) activation ash loading photocatalyst TiO
2/ Cu
2the preparation of O: the activation ash in stoste pre-treatment step is fully ground, cross the postactivated ash of 50 mesh sieve and P25 type TiO
2after 2:1 mixes in mass ratio, will activate ash and P25 type TiO
2it is 0.35mol/L Cu (NO that miscellany joins concentration
3)
2in solution, control TiO
2with Cu (NO
3)
2amount of substance than for 1:6, again by amount of substance than cupric nitrate: quadrol=1:3 adds quadrol, after fully stirring, add sodium hydroxide, control amount of substance than cupric nitrate: sodium hydroxide=1:2, after fully dissolving, by amount of substance, than cupric nitrate: glucose=1:0.54, add glucose to obtain reaction solution F again, the beaker that fills reaction solution F is put in oil bath pan, 75 ℃ of temperature constant magnetic stirrings 30 minutes, to obtain product precipitation, filter, with deionized water and ethanol, respectively clean 5 times, in loft drier, 60 ℃ obtain photocatalyst product for dry 3 hours; (2) day photocatalytic degradation traditional Chinese medicine wastewater: concrete grammar is as follows: will activate ash loading photocatalyst TiO
2/ Cu
2the photocatalyst of preparing in the preparation process of O joins in liquor C, and controlling photocatalyst is 1:40-1:200 with liquor C mass ratio, lucifuge stirring 30 minutes, after add H
2o
2pro-oxidant, add-on is controlled and is added 1mlH for every 100g liquor C
2o
2, mixed solution is placed in and under daylight, carries out photocatalytic degradation, during continue to pass into air in constantly stirring, it is 120L/h that air passes into flow control, catalyzed degradation is separated filtrate D after 120 minutes; (3) flocculating settling: the preparation of (1) poly-ferro-aluminum: by flyash and Na
2cO
3after mixing, put into High Temperature Furnaces Heating Apparatus, control mass ratio Na
2cO
3: SiO
2=1:3,900 ℃ of roastings obtain product α for 1 hour, product α is added in nitration mixture and stirs and leach at 65 ℃, control product α and nitration mixture mass ratio 1:4, leach filtering separation after 120 minutes, obtain filter residue I and filtrate I, add waste iron filing and hydrochloric acid to adjust ferro-aluminum amount of substance than obtaining product β for 1:1 in filtrate I, nitration mixture used is that mass percent concentration is 15%HCl and 25%H
2sO
41:1 is formulated in mass ratio; (2) preparation of poly-silicic acid: filter residue I is dried at 100-200 ℃ in loft drier, control filter residue I and sodium hydroxide mass ratio 1:3 and add mass percent concentration 20%NaOH solution to be heated to 80 ℃ of constant temperature immersions after 60 minutes, be diluted with water to SiO
3 2-mass percent concentration be 8%-10%, then use mass percent concentration 25%H
2sO
4regulate pH to 2-3, this liquid is labeled as product γ.(3) preparation of poly aluminium iron silicate: product β and product γ are carried out to polymerization, and controlling ferro-aluminum total amount is 1:1 with the amount ratio of silicon matter, and under agitation controlling pH is 1.7-2, and room temperature obtains sorrel liquid poly silicate aluminium ferric flocculating agent for standing 4 hours; (4) flocculation treatment: poly aluminium iron silicate is joined and carries out flocculation treatment in the process filtrate D of photocatalytic degradation, and it is that poly aluminium iron silicate is 1:30 with quality ratio that additional proportion is controlled, and after 60 minutes, obtain separated with flocculation agent of water finally processed rear water.
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Cited By (3)
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| CN104478029A (en) * | 2014-10-20 | 2015-04-01 | 中国矿业大学(北京) | A water treating agent and a preparing method thereof |
| CN105016526A (en) * | 2015-07-10 | 2015-11-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Photocatalysis-adsorption flocculation combining technique for organic waste water difficult to degrade |
| CN111468090A (en) * | 2019-01-23 | 2020-07-31 | 阜阳师范学院 | High efficiency TiO 22Preparation of photocatalyst and application of photocatalyst in degradation of water pollutants |
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| CN102847561A (en) * | 2012-09-19 | 2013-01-02 | 合肥工业大学 | Microporous glass supported TiO2 nano composite photocatalyst and preparation method thereof |
| CN103073265A (en) * | 2013-01-14 | 2013-05-01 | 杜亚丽 | Preparation method of coal ash based photocatalysis brick |
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| JPH1119642A (en) * | 1997-06-30 | 1999-01-26 | Shogo Nasu | Purifying material for water and air |
| CN101564685A (en) * | 2008-08-13 | 2009-10-28 | 厦门城市环境研究所 | Method for preparing photocatalytic material of titanium oxide immobilized on fly ash |
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| CN102847561A (en) * | 2012-09-19 | 2013-01-02 | 合肥工业大学 | Microporous glass supported TiO2 nano composite photocatalyst and preparation method thereof |
| CN103073265A (en) * | 2013-01-14 | 2013-05-01 | 杜亚丽 | Preparation method of coal ash based photocatalysis brick |
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| CN105016526A (en) * | 2015-07-10 | 2015-11-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Photocatalysis-adsorption flocculation combining technique for organic waste water difficult to degrade |
| CN111468090A (en) * | 2019-01-23 | 2020-07-31 | 阜阳师范学院 | High efficiency TiO 22Preparation of photocatalyst and application of photocatalyst in degradation of water pollutants |
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