CN104307529A - A coprecipitation catalyst used for catalyzing wet oxidation processes, a preparing method thereof and applications of the catalyst - Google Patents
A coprecipitation catalyst used for catalyzing wet oxidation processes, a preparing method thereof and applications of the catalyst Download PDFInfo
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Abstract
The invention mainly overcomes the problems in biochemical printing and dyeing wastewater treatment, namely complex processes, odour of systems, overhigh costs, generation of secondary pollution and a low treatment efficiency, and provides a wet oxidation method for the wastewater. A catalyst comprises following raw materials by weight: 4-8 parts of Co(NO3)2.6H2O, 6-10 parts of Fe(NO3)3.9H2O, 7-20 parts of Ce(NO3)3.6H20, 0-11 parts of La(NO3)3.6H2O and 100 parts of distilled water; or 4-8 parts of Co(NO3)2.6H2O, 6-10 parts of Fe(NO3)3.9H2O, 0-11 parts of Ce(NO3)3.6H20, 7-20 parts of La(NO3)3.6H2O and 100 parts of distilled water. The catalyst is prepared by a coprecipitation method, and by following steps of: preparing a metal salt solution, performing ultrasonic coprecipitation, ageing, washing and separating precipitates, performing suction filtration, drying and calcinating. The catalyst is high in activity, high in stability and cheap, and has a nanometer particle structure. The BET specific surface and pore volume of the catalyst are respectively 53 m2/g and 0.36 cm<3>/g. By adoption of the catalyst CFCL, the CODCr, the BOD5, chromaticity and pH of the printing and dyeing wastewater all meet the primary standards of the Integrated Wastewater Discharge Standard (GB8978-1996).
Description
Technical field
The present invention relates to a kind of catalytic wet oxidation catalyst, be specifically related to a kind of preparation method of co-precipitated catalyst for the process of dyeing waste water CWO and the application in treatment of dyeing wastewater thereof, belong to water-treatment technology field.
Background technology
The waste water that printing and dyeing industry is discharged is the mixing to the various waste water that natural and man-made fibre material are reprocessed and produced such as printing and dyeing mill, woollen mill, knitting mill, silk mill.Dyeing and printing process generally comprises four procedures such as pretreatment (destarch, refining, bleaching, mercerising), dyeing, stamp, arrangement.Pretreatment stage (comprise singe, destarch, boiling-off, bleaching, the operation such as mercerising) desized wastewater, boiled-off waste water, bleaching effluent and mercerizing waste water will be discharged, dyeing discharges dyeing waste-water, printing technology discharges printing waste water and soap lye waste water, and finishing technique is discharged and arranged waste water.Dyeing waste water is the mixing of above all kinds of waste water, but the topmost source of dyeing waste water is dyeing waste-water.Because dyeing engineering take all water as medium, and often need the washing of one or many, therefore water consumption is larger.The waste water quality that various operation is discharged has very large difference by the difference of kinds of fibers, dyestuff and slurry.
The common feature of dyeing waste water: pollutant levels are high, chemical oxygen demand COD
crhigh, colourity is large, toxic, biodegradability is poor.Along with the development of fine chemistry industry and printing technology, in dyeing waste water, the biorefractory organic such as PVA dyestuff, New-type adjuvant is increasing, causes its intractability increasing.And the routine of sanitary sewage, production waste process, economically viable method is " biochemical process ", most printing and dyeing enterprises also at use biochemical treatment process, but improves biochemical process with anaerobism, UF membrane, electrolysis etc.The pollutant levels of dyeing waste water are high, and some dyestuff has toxicity, the biodegradability index B/C (i.e. biochemical oxygen demand (BOD)/COD) of dyeing waste water is general between 0 ~ 0.2, obviously even well below the critical value 0.3 of B/C, some dyeing waste waters can not determine BOD even at all
5value, because microorganism can not grow therefore not have the consumption of biochemical oxygen in waste water.Organic wastewater can biochemical indicator B/C higher than 0.3, then waste water well can be processed by biochemical process; If B/C is lower than 0.3, then waste water directly can not process with biochemical process.
Chinese invention patent grant number CN103274524B adopt " anaerobic fermentation " technology dyeing waste water is processed, anaerobic processes need the time of several days even tens days reaction time, its reaction time long and reaction in foul smelling gas produce;
Chinese invention patent grant number CN103274524B adopts " electrolysis and multiple film " technical finesse dyeing waste water, and relate to electrolysis, membrane process, its processing cost is too high, and economic feasibility is poor;
Chinese invention patent grant number CN101391210B adopts " photocatalytic method " treatment of dyeing and printing, and its treatment effect is general and running cost is high;
For overcoming the defect of dyeing waste water biodegradability difference, except adopting above-mentioned " anaerobism, electrolysis, film, photocatalysis " method, Ye You printing and dyeing mill cost several ten thousand hundreds of thousands buys inert fillers such as " Ackermams ", expects the space of improving microorganism and waste water, improves treatment effect.But microorganism is under toxic condition, enlarge active surface effectively can not improve Biochemical Treatment;
Ye You enterprise takes secretly dilution discharge, the mode of even paying forfeit money is dealt with problems.
In fact, CWO technology (Catalytic Wet Air Oxidation, being called for short CWAO) technology can solve the problem of dyeing waste water biochemical difference, available " catalytic wet air oxidation " replacement " anaerobism, electrolysis, film, photocatalysis " method.
Catalytic wet air oxidation is as new and effective water treatment purification techniques, refer under catalyst action, with oxygen or air for oxidant, under the condition of uniform temperature (80 ~ 300 DEG C), gaseous pressure (0.5 ~ 6MPa) and reaction time (30 ~ 120min), by the organic pollution (chemical oxygen demand COD of higher concentration
crbe about 1 ~ 100,000mg/L) be oxidized to the intermediate product or CO that are easy to microbial degradation process
2, N
2and H
2o.Therefore, CWAO method is the effective ways of process high concentration hard-degraded organic waste water.
CWO technology is in the starting stage at home at present, and the large-scale application of this technology in wastewater treatment rarely has report.But CWAO technology is used for the process of waste water, is paid close attention to widely abroad, and obtains the application of industrially scalable.The life factory effluent of Osaka, Japan Gas Company, after low temperature CWAO technical finesse, can be back to flush the toilet, the aspect such as greening, the zero-emission of waste water has been accomplished by low temperature CWAO technology by Osaka Gas Company.
The key of CWAO technology is the research and development of catalyst.CWAO catalytic component has three types: noble metal, transition metal and rare earth metal.Wherein noble metal catalyst (Pt, Ru and Pd etc.) price comparison costliness, but their catalytic activity and stability are far above transition metal oxide, especially in the Oxidative Degradation Process of biodegradable organic compounds, this type of catalyst often shows excellent catalytic activity; Transition metal oxide mainly contains CuO, Co
3o
4with NiO etc., this type of catalyst is with low cost, but exists selective poor, and under the CWAO reaction condition of harshness, the loss of active component easily causes the shortcomings such as catalysqt deactivation; Rare earth metal itself is without catalytic performance, but because its special physicochemical property, its interpolation can strengthen stability and the activity of catalyst, therefore rare earth metal is widely used in catalyst aid.
Current studies in China person pays close attention to the immersion-type catalyst of noble-metal-supported mostly, and this kind of catalyst is expensive and need the catalyst carrier material providing high strength;
The present invention adopts coprecipitation to prepare CWAO catalyst, do not use noble metal and carrier material, but transition metal Co, Fe higher for catalytic activity is mixed with Ce, the La with special physico-chemical performance, preparation " active high, stability strong, cheap " multicomponent co-precipitated catalyst.
The application of CWAO technology in treatment of dyeing wastewater is feasible, all has feasibility economically technically with level.CWAO method treatment effeciency is high, can by the various organic matter simultaneous oxidation process in waste water, and the time of process waste water generally needs half an hour; CWAO technical energy saving, after reaction starts, system liberated heat can maintain the carrying out of reaction system, does not generally need extra heating; CWAO technology non-secondary pollution, because the pollutant in waste water is thoroughly decomposed into carbon dioxide, water or small-molecule substance.
The reason of CWAO technology environmental protection circle slower development at home, one is domesticly to pay little attention to environmental protection work; Two is that a lot of enterprise allows acyclic guarantor person supervise efforts at environmental protection, and the shortage of chemical knowledge makes the wastewater treatment mode of staff to this high temperature high temperature hang back; In fact, chemical reaction has 98% all to use catalyst, and the chemical plant overwhelming majority also exists pressure vessel.
Summary of the invention
One of technical problem to be solved by this invention: for the problem of " complex process, produce stench, high cost, generation secondary pollution, treatment effeciency are low " in the biochemical treatment of dyeing wastewater of difficulty, the CWO processing method of the biochemical dyeing waste water of a kind of difficulty is provided, dyeing waste water biodegradability is improved, and then enter biochemical treatment system, or raise CWAO reaction temperature to more than 260 DEG C, make the disposable process of dyeing waste water to qualified discharge;
Technical problem two to be solved by this invention: a kind of Catalysts and its preparation method corresponding with one of technical solution problem is provided.
1, Catalysts and its preparation method provided by the invention, comprises the following steps:
(1) with weight parts, 4 ~ 8 parts of Co (NO are 1. taken
3)
26H
2o, 6 ~ 10 parts of Fe (NO
3)
39H
2o, 7 ~ 20 parts of Ce (NO
3)
36H
2o, 0 ~ 11 part of La (NO
3)
36H
2o, 100 parts of distilled water; Or 2. take 4 ~ 8 parts of Co (NO
3)
26H
2o, 6 ~ 10 parts of Fe (NO
3)
39H
2o, 0 ~ 11 part of Ce (NO
3)
36H
2o, 7 ~ 20 parts of La (NO
3)
36H
2o, 100 parts of distilled water.
(2) under middling speed magnetic agitation condition, by 1.0 ~ 3.0mol/L NH
3oH solution, with in the speed of 6/min instillation metal salt solution, makes precipitating reagent NH
3oH mixes with salting liquid and generates sediment, keeps the pH value 9 ~ 10 of mixed liquor;
(3) sediment of step (2) and solution are placed in ultrasonic cleaning machine, ultrasonic disperse, Aging Temperature is 35 ~ 85 DEG C, and digestion time is 2 ~ 6h;
(4) drain the water solution, and the sediment distilled water after ageing is washed three times, then use absolute ethanol washing three times, and after making cleaning, pH value of solution is between 7 ~ 8, then uses vacuum filtration machine, and suction filtration is separated, and is precipitated thing;
(5) sediment that step (4) obtains is placed in 100 ~ 120 DEG C of electric drying oven with forced convections, drying time 8 ~ 14h; Then be placed in chamber type electric resistance furnace, be warmed up to 300 ~ 750 DEG C with the rate of heat addition of 6 DEG C/min, constant temperature calcining 1.5 ~ 14h.
(6) the roasting sample of step (5) is ground, sieve out 60 ~ 80 object powders, obtain finished catalyst.
2, the catalytic wet air oxidation process of stimulated dye wastewater in catalyst preparing, comprises the following steps:
(1) stimulated dye wastewater of methyl orange concentration 0.952mg/L is configured, its COD
crfor 2000mg/L, absorbance is 71.4;
(2) measure the stimulated dye wastewater 250mL that step 2 (1) configures, take catalyst prepared by step 1, with the catalyst amount of 2g/L, drop in 0.5LGS type autoclave (as Fig. 1) simultaneously.
(3) setting reaction temperature is 180 DEG C, when reactor heats to design temperature, passes into the partial pressure of oxygen 1.0MPa of oxygen to setting, starts timing and terminates to 90min reaction.
3, catalytic wet air oxidation process actual dying provided by the invention, comprises the following steps:
(1) COD of dyeing waste water
crbe 1000 ~ 20,000mg/L, add the aluminium polychloride of 100 ~ 800mg/L, mix and blend 20 ~ 60min, sedimentation 20 ~ 60min, supernatant is pretreated dyeing waste water;
(2) pretreated for 250mL actual dying is placed in 0.5LGS type reactor (see Fig. 1), drops into simultaneously and adopt CFCL catalyst of the present invention 2 ~ 12g/L catalyst, setting reaction temperature is 160 ~ 300 DEG C;
(3), when reactor heats to design temperature, pass into oxygen or the air partial pressure of oxygen 0.5 ~ 5.0MPa to setting, start timing, be reacted to setting-up time 60 ~ 150min.
The present invention adopts CWO method treatment of dyeing and printing, has following advantage:
Advantage 1: co-precipitated catalyst provided by the invention, does not relate to noble metal and catalyst carrier, inexpensive; Catalyst formulation comprises highly active Co, Fe and has Ce, La of special physico-chemical performance, and its activity is high, stability is strong; The Particle Distribution of Kaolinite Preparation of Catalyst is even, and have nanostructured, its BET specific surface and pore volume are respectively 53m
2/ g, 0.36cm
3/ g.
Advantage 2:CWAO method can overcome the defect of dyeing waste water biodegradability difference, is CO under catalyst, high temperature, condition of high voltage by difficult degradation, virose contaminant degradation
2, H
2o or other small molecule organic compounds, can improve the biodegradability of dyeing waste water, and then carry out biochemical treatment again under lower CWAO reaction temperature (180 ~ 240 DEG C); Can by treatment of dyeing wastewater to qualified discharge under (240 ~ 300 DEG C) under slightly high CWAO reaction temperature;
Advantage 3: the whole processing procedure of this method only needs a coagulant precipitation pond and an autoclave, compared with the anaerobism of routine, electrolysis, biochemistry and other group technologies, its technological process is simple;
Advantage 4: in the CWAO reaction of dyeing waste water, need electrical heating at the initial period of reaction; Can discharge a large amount of heats when system is normally run, this heat can maintain the condition of high temperature of reaction system substantially, therefore reaction system energy-conserving and environment-protective.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.
Fig. 1 is the reactor of dyeing waste water catalytic wet air oxidation process.
The scanning electron microscope (SEM) photograph of the CFCL catalyst that Fig. 2 (a) obtains for embodiment 4.
The scanning electron microscope (SEM) photograph of the CFCL catalyst that Fig. 2 (b) obtains for embodiment 18.
Fig. 3 is the transmission electron microscope picture of the CFCL catalyst that embodiment 18 obtains.
Fig. 4 is the XRD figure of the CFCL catalyst that embodiment 18 obtains.
Fig. 5 is the XPS figure of the CFCL catalyst that embodiment 18 obtains.
Detailed description of the invention
[embodiment 1]
The preparation of metal salt solution: the total concentration of setting slaine is about 0.8mol/L, with weight parts, takes distilled water 100.0 parts.In setting metal salt mixture, the mol ratio of Cu-Fe-Ce-La metallic element is 1: 1: 1: 1, then salting liquid is formed: 4.82 parts of Cu (NO
3)
26H
2o, 8.08 parts of Fe (NO
3)
39H
2o, 8.68 parts of Ce (NO
3)
36H
2o, 8.66 parts of La (NO
3)
36H
2o, is dissolved in 100.0 parts of distilled water, obtains metal salt solution;
Under middling speed magnetic agitation condition, by 6mol/L NaOH solution with in the speed of 6/min instillation metal salt solution, make precipitating reagent NaOH mix with salting liquid and generate sediment, when mixed liquor pH value reaches 11, stop the instillation of NaOH;
Sediment and solution are positioned in ultrasonic cleaning machine, ultrasonic disperse, at 60 DEG C, precipitate ageing 4h;
Drain the water solution, and the sediment distilled water after ageing is washed three times, then use absolute ethanol washing three times, and after making cleaning, pH value of solution is between 7 ~ 8, then uses vacuum filtration machine, and suction filtration is separated, and is precipitated thing;
Sediment is placed in electric drying oven with forced convection, at 102 DEG C, dries 10h, then put into chamber type electric resistance furnace, be warmed up to 450 DEG C with the rate of heat addition of 6 DEG C/min, constant temperature calcining 6h.
The roasting sample of step is ground, sieves out 60 ~ 80 object powders, obtain finished catalyst.
By 250mLCOD
crfor the stimulated dye wastewater of 2000mg/L, be placed in 0.5LGS type reactor, drop into catalyst 2g/L prepared by the present embodiment simultaneously, setting reaction temperature 180 DEG C, temperature rises to 180 DEG C and passes into oxygen to partial pressure of oxygen 1.0MPa, starts timing and terminates to 90min reaction.
[embodiment 2 ~ 3]
Reaction condition is with embodiment 1, but the molar ratio of slaine is different, and catalytic component formation and application result are in table 1.
[comparative example 1]
Reaction condition with embodiment 1, but does not add catalyst, treatment of simulated dyeing waste water the results are shown in Table 3.
[embodiment 4 ~ 6]
Reaction condition is with embodiment 1, but the constituent of slaine is different, and catalytic component formation and application result are in table 2.
By embodiment 1 ~ 3, the catalyst of Cu-Fe-Ce-La compound has good catalytic activity relative to Cu-Fe-Ce, Cu-Fe-La, after but catalyst adds use, in waste water, Cu stripping concentration is up to 6.22mg/L, higher than the discharge grade III Standard 2.0mg/L of Cu in " integrated wastewater discharge standard " (GB8978-1996); Cu is Equations of The Second Kind pollutant, therefore attempts being formed with the component that highly active transition metal Co configures catalyst according to table 2.
[embodiment 7]
Reaction condition and used catalyst component are formed with embodiment 4, but precipitating reagent is different, with the NH of 2.0mol/L
3h
2o, as precipitating reagent, maintains the pH value of salting liquid 9 ~ 10.The catalyst treatment stimulated dye wastewater prepared with this results are shown in Table 2.
Contrast table 2 and table 1, component is configured to the catalyst of Co-Fe-Ce-La=1: 1: 1: 1 (n/n/n/n), the catalyst activity being configured to Cu-Fe-Ce-La=1: 1: 1: 1 (n/n/n/n) relative to component about exceeds 1 ~ 2 percentage point, and the stripping concentration of metal Co, metal Fe obviously reduces.Visible, slaine Co-Fe-Ce-La is compounded with stronger synergy, and the activity of catalyst slightly improves, and stability obviously strengthens.And precipitating reagent is replaced by the NH of embodiment 7 by the NaOH of embodiment 4
3h
2o, the Activity and stabill stability of catalyst improves further.Visible, the precipitation atmosphere of weak base has better effect than highly basic, and uses NH
3h
2o does not introduce impurity Na as precipitating reagent
+.
The amount ranges of embodiment 4 ~ 6 slaine is expanded, forms configuration by following catalyst: configuration 1: in parts by weight part, 4 ~ 8 parts of Co, 6 ~ 10 parts of Fe, 7 ~ 20 parts of Ce, 0 ~ 11 part of La, 100 parts of distilled water; Configuration 2: with weight parts, 4 ~ 8 parts of Co, 6 ~ 10 parts of Fe, 0 ~ 11 part of Ce, 7 ~ 20 parts of La, 100 parts of distilled water.
The CFCL catalyst obtained to above-described embodiment 18 detects: utilize on the ASAP2400 type physical adsorption appearance of Merck & Co., Inc of the U.S. and carry out N
2adsorption-desorption is tested, and to measure the hole structural properties such as the pore-size distribution of catalyst, obtains the BET specific surface of catalyst, pore volume, average pore size be respectively 53m
2/ g, 0.36cm
3/ g, 40nm; Japanese Shimadzu SSX550 type SEM (SEM) is utilized to observe the surface topography of catalyst, find that the surface distributed of catalyst activity component at carrier is evenly (as Fig. 2, amplify 10,000 times), relative to the catalyst (Fig. 2 (a)) taking NaOH as precipitating reagent, with NH
3h
2o is that catalyst (Fig. 2 (the b)) component of precipitating reagent is distributed with better uniformity; Utilize U.S. FEI Tecnai G2 type transmission electron microscope (TEM), the particle diameter of observation catalyst activity component, discovery grain diameter is 10 ~ 50nm, average grain diameter 25nm (as Fig. 3, amplifying 150,000 times); Utilize Rigaku D/max RB type X-ray diffractometer (XRD, CuK alpha ray, 40kV, 100mA) detect the crystalline structure (as Fig. 4) of sample and utilize Japanese Shimadzu Kratos AXIS Ultra DLD type x-ray photoelectron power spectrum (XPS) instrument to measure combination energy (as Fig. 5) of catalyst surface element, finding that carrier and active component are mainly with γ-Al in the catalyst
2o
3, Co
3o
4, Fe
2o
3, CeO
2, La
2o
3form exist.
[embodiment 20]
The pretreatment of actual dying: actual dying takes from the regulating reservoir outlet of printing and dyeing mill, its COD
cr, BOD
5, colourity, pH be followed successively by 5041mg/L, 800mg/L, 2353 times and 9.2.Add the aluminium polychloride of 300mg/L, mix and blend 30min, sedimentation 60min, supernatant is pretreated dyeing waste water.Pretreated dyeing waste water parameter index: COD
crfor 3680mg/L, BOD
5for 560mg/L, colourity be 1600 times, pH is 9.2.
[embodiment 21 ~ 22]
To CFCL catalyst prepared by embodiment 18, set different reaction conditions, use pretreated dyeing waste water in catalytic wet air oxidation Processing Example 20.Reaction condition and application result are in table 5.
[comparative example 2]
Reaction condition with embodiment 22, but does not add catalyst, and what process actual dying the results are shown in Table 5.In embodiment 21, embodiment 22, use CFCL catalyst, reaction temperature be respectively 200,220 DEG C, partial pressure of oxygen 1.5MPa, catalyst amount 4g/L condition under, through the process of 30min, the COD of dyeing waste water
crclearance, BOD
5clearance reaches 84.5%, 69.0% respectively.Key is, at 200,220 DEG C, the biodegradability index B/C of waste water is all higher than the critical value 0.3 of B/C.That is, for the dyeing waste water being difficult to degrade, if factory adds one " processing unit-CWO device " in wastewater treatment equipment, pretreatment is carried out to waste water, after the mass degradation of difficult degradation in waste water, in reusing system, original biochemical device processes, and so wastewater treatment is easy to qualified discharge.
[embodiment 23 ~ 25]
Reaction temperature, with embodiment 22, is just risen to 240,260,280 DEG C by reaction condition respectively.Reaction condition and the application result of CFCL catalyst in the process of dyeing waste water CWAO method are in table 5.Visible, waste water by waste water after simple coagulant precipitation process, can be passed into CWO device, CFCL catalyst amount 4g/L, reacts 30min, the COD of dyeing waste water under reaction temperature 260 ~ 280 DEG C, partial pressure of oxygen 1.5MPa by printing and dyeing mill
cr, BOD
5, colourity, pH be reduced to respectively 95mg/L, 18mg/L, 20 times and 6.87, the primary standard of " integrated wastewater discharge standard " (GB8978-1996) that be all up to state standards.
Claims (5)
1., for a co-precipitated catalyst for catalysis wet-type oxidation technology, with weight parts, the component of catalyst is formed: 1. 4 ~ 8 parts of Co (NO
3)
26H
2o, 6 ~ 10 parts of Fe (NO
3)
39H
2o, 7 ~ 20 parts of Ce (NO
3)
36H
2o, 0 ~ 11 part of La (NO
3)
36H
2o, 100 parts of distilled water;
Or 2. 4 ~ 8 parts of Co (NO
3)
26H
2o, 6 ~ 10 parts of Fe (NO
3)
39H
2o, 0 ~ 11 part of Ce (NO
3)
36H
2o, 7 ~ 20 parts of La (NO
3)
36H
2o, 100 parts of distilled water.
2. component described in claim 1 forms the preparation method of catalyst, comprises the following steps:
(1) according to claim 1, catalytic component is taken, configuration metal salt solution;
(2) under middling speed magnetic agitation condition, by 1.0 ~ 3.0mol/L NH
3oH solution, with in the speed of 6/min instillation metal salt solution, makes precipitating reagent NH
3oH mixes with salting liquid and generates sediment, keeps the pH value 9 ~ 10 of mixed liquor;
(3) sediment of step (2) and solution are placed in ultrasonic cleaning machine, ultrasonic disperse, Aging Temperature is 35 ~ 85 DEG C, and digestion time is 2 ~ 6h;
(4) drain well, washs three times by the sediment distilled water after ageing, then uses absolute ethanol washing three times, then uses vacuum filtration machine, and suction filtration is separated, and is precipitated thing;
(5) sediment that step (4) obtains is placed in 100 ~ 120 DEG C of electric drying oven with forced convections, drying time 8 ~ 14h; Then be placed in chamber type electric resistance furnace, be warmed up to 300 ~ 750 DEG C with the rate of heat addition of 6 DEG C/min, constant temperature calcining 1.5 ~ 14h.
(6) sample of step (5) roasting is ground, sieve out 60 ~ 80 object powders, obtain finished catalyst.
3. the catalyst of claim 2 preparation, its application in the process of dyeing waste water CWO: adopt CFCL catalyst prepared by the present invention, consumption 2 ~ 12g/L, reaction temperature are 200 ~ 300 DEG C, partial pressure of oxygen 0.5 ~ 5.0MPa, reaction time 30min, the biodegradability of difficult biochemical dyeing waste water significantly improves, and biodegradability index brings up to critical value more than 0.3; After reaction temperature brings up to 260 DEG C, the COD of dyeing waste water
cr, BOD
5, colourity, pH all reach the primary standard of " integrated wastewater discharge standard " (GB8978-1996).
4., according to the precipitation of the described slaine of claim 2 (2), it is characterized in that the NH that the precipitating reagent used is 2.0mol/L
3oH.
5. the ageing process according to claim 2 (3), it is characterized in that using ultrasonic cleaning machine, ultrasonic disperse, Aging Temperature is 35 ~ 85 DEG C.
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| CN107698055A (en) * | 2017-03-28 | 2018-02-16 | 佛山科学技术学院 | The CWO processing method of percolate |
| CN107088416A (en) * | 2017-04-10 | 2017-08-25 | 佛山科学技术学院 | A kind of catalysis process of co-precipitation Ru Fe Co La Ti composite catalysts |
| CN108927163A (en) * | 2018-07-13 | 2018-12-04 | 浙江大学 | It is a kind of using cerium oxide as the preparation method of the supported copper oxide catalyst of carrier |
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