CN105712466A - Ozone catalytic wet oxidation method for phenol-containing waste water - Google Patents
Ozone catalytic wet oxidation method for phenol-containing waste water Download PDFInfo
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Abstract
The invention discloses an ozone catalytic wet oxidation method for phenol-containing waste water. The method comprises the following steps: taking ozone as an oxidation medium, the phenol-containing waste water is contacted with a catalytic wet oxidation catalyst under room temperature and normal pressure and are subjected to a reaction, The catalyst comprises the following core-shell structure components, the core-shell structure components take active carbon as a core, and take alumina containing precious metal and rare earth metal as a shell. The catalyst has good catalysis performance, strong wear resistance, and good usage stability, the clearance rate of an organic matter is high under room temperature and normal pressure, and usage period is long.
Description
Technical field
A kind of method that the present invention relates to CWO, especially for the method for the CWO of phenol wastewater.
Background technology
Phenolic compound (phenol and its derivatives) is mainly derived from Coal Chemical Industry, petrochemical industry, pharmaceutical factory, phenol production and phenolic resin factory etc., it it is a kind of protoplasm highly toxic substance, to all toxic effect of all living things individuality, can pass through in skin, mucosa, oral cavity entrance organism, cell is made to lose activity with forming insoluble protein after the protein contacts in cell oleo stock, especially nervous system is had bigger affinity, makes nervous system generation pathological changes.Phenol is high toxicity common in industrial wastewater, hardly degraded organic substance, and be not only detrimental to health safety, and heavy damage balance of nature, cause serious environmental pollution.When phenol content reaches 5 ~ 10mg/L in water, Fish mortality can be caused.Additionally, use phenol wastewater irrigated farmland, crop production reduction or withered also can be made.Phenol wastewater for high concentration can adopt physical-chemical process, bioanalysis, chemical oxidization method etc. to process.Physical-chemical process includes absorption method, extraction, liquid Membrane Separation Technique, air stripping and distillation gas lifting manipulation, rectification method, and wherein the most commonly used is absorption method.Absorption method is that the aldehydes matter in waste water is adsorbed by the stronger absorption property utilizing the specific surface area that some porous adsorbents are higher to show, and renewable use after adsorbent is saturated, aldehydes matter can also be recycled.Conventional adsorbent mainly has the adsorbent such as activated carbon, sulfonated coal.Although activated carbon adsorption adsorbance is big, but regeneration difficulty, thus it uses and does not have an optimistic view of for people gradually.The adsorption capacity of sulfonated coal is less, does not far reach discharge standard containing phenol amount in processed waste water, need to carry out two stage treatment.So activated carbon and sulfonated coal receive certain restriction when processing high-concentration phenolic wastewater.Aldehydes matter is simply carried out concentrating and part transfer by this type of method, it is impossible to be inherently eliminated the phenolic comp ' ds pollution in sewage.For the phenol wastewater of high concentration, the treatment effect of bioanalysis is not as, and anaerobe is had certain toxic action by the part phenols in waste water, therefore, uses Biochemical method phenols wastewater general COD clearance not high, processes the time longer.Chemical oxidization method be in waste water in the aldehydes matter of dissolved state when temperature-pressure, be oxidized to micro-poison or nontoxic material by chemical reaction, or be converted into the form being easily separated from water, thus reaching the purpose removed.
Traditional chemical oxidization method needs High Temperature High Pressure, not only energy consumption is high but also equipment material requirement is also high, therefore, the industrial conventional oxidation method that is typically in is when processing phenol wastewater, add catalyst, to reduce the activation energy of reaction, so that reaction can complete gentleer when and within the shorter time.At present, the catalyst that Wet Catalytic Oxidation Method adopts, according to the form that catalyst is different, it is possible to catalyst is divided into homogeneous and heterogeneous two kinds.
Homogeneous catalyst mainly includes producing the Fenton reagent of oxygen radical, Fe3+、Cu2+, the metal ion such as cobalt and manganese, effect by means of these homogeneous catalysts, organic component in waste water, sulfide, ammonia nitrogen etc. are oxidized into low molecular acid (low mass molecule alcohol or carbon dioxide), sulfate or thiosulfate, nitrogen etc. by oxide isolations such as air, oxygen, ozone, make waste water reach the processing intent of decarburization, desulfurization and denitrogenation.Homogeneous oxidation catalyst preparation and use procedure are relatively simple, generally can directly select the slaines such as ferrum, copper, cobalt, manganese be made into aqueous solution or be directly thrown in handled waste water, and by the water outlet after processing being discharged or regeneration Posterior circle use.Adopt homogeneous catalytic oxidation, owing to metal active constituent can fully dissolve and disperse in waste water, generally can reach relatively stable water treatment effect, but also exist that reagent consumption is big, operating cost is high, the serious problems such as metal loss and secondary pollution, cause its application to be subject to bigger restriction.
Heterogeneous catalysis is mainly with activated carbon, aluminium oxide etc. for carrier, using one or more catalyst constituted as active component in alkali metal, alkaline-earth metal, transition metal or Pt, Pd noble metal.Black, hole that activated carbon is made up of carbonaceous material are flourishing, specific surface area is big, a class microcrystalline carbon of high adsorption capacity.Activated carbon property is stable, acidproof, alkaline-resisting, heat-resisting, and water insoluble or organic solvent easily regenerates, is a kind of environmentally friendly adsorbent, is widely used in the fields such as Industrial " three Waste " improvement, food, medicine, carrier, quasiconductor, battery and power storage.The heterogeneous catalysis being currently used for wastewater treatment selects activated carbon as carrier mostly, but select catalyst anti-wear performance prepared by activated carbon supported metal poor, mechanical strength is not high, and the metal of load is easy to run off so that the application effect of activated-carbon catalyst is made a discount.Amorphous alumina is because having good chemical stability, pore volume is big, the advantage such as there is certain acidity, pore size distribution$ is concentrated, mechanical strength is big, corrosion-resistant, it is widely used at catalytic field, but amorphous alumina exists the shortcoming that specific surface is little, organic absorption and conversion capability is relatively small.
CN201310610997.8 discloses a kind of charcoal carried catalyst for ozone oxidation and preparation method thereof.This charcoal carried catalyst is made up of with cerium, lanthanum or potassium promoter activated carbon loaded iron, copper, nickel or manganese transition metal active component.Organic wastewater with difficult degradation thereby is had significantly high catalysis activity by this catalyst, and COD clearance reaches more than 55%, but the employing of this catalyst is absorbent charcoal carrier, however it remains catalytic mechanical intensity is low, and active metal easily runs off, the problem that catalyst life cycle is short.
CN200710087328.1 discloses a kind of catalyst for wastewater treatment and a kind of waste water wet oxidation processing method using this catalyst.This catalyst, with manganese, cobalt, nickel, cerium, tungsten, copper, silver, gold, platinum, palladium, rhodium, ruthenium and iridium at least one element or its compound for catalytic active component, includes ferrum, titanium, silicon, aluminum and zirconium at least one element or its compound for carrier components being selected from.The specific surface area of this catalyst is little, and organic absorption conversion capability is more weak.
CN201110326788.1 discloses a kind of for removing the preparation method of the catalyst of phenolic compound in water.The method is the physicochemical properties utilizing supercritical water, by the oxide of manganese nitrate or manganese sulfate solution and the silica precursor manganese of in-situ preparation nano-scale under subcritical or supercritical water heat condition and be dispersed on silica particles, obtain MnOx/SiO2Catalyst, wherein MnOxFor MnO2Or Mn2O3.When this catalyst is used for processing phenols wastewater, its activity and stability all await further raising.
CN201110326788.1 discloses the method for a kind of microwave catalyst degraded phenol wastewater.The method includes: (1) prepares microwave catalyst: carrying transition metal oxide on the activated carbon；(2) solidliquid mixture is formed: in phenol wastewater, put into microwave catalyst prepared by a certain amount of step (1)；(3) microwave exposure: described solidliquid mixture carries out microwave catalysis oxidation reaction degraded containing phenol Organic substance under microwave field irradiation.The method adopts the method for microwave exposure, the shortcomings such as though degradation efficiency can be improved, but its catalyst is with activated carbon for carrier, however it remains bad mechanical strength, active metal easily loss.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of ozone catalytic wet oxidation method of phenol wastewater.The catalyst that the method adopts has the advantages that catalytic performance is good, anti-wear performance is strong, stability in use is good, is conducive to improving the organic clearance in waste water, and life cycle is long.
The CWO method of the present invention, its process includes: using ozone as oxide isolation, being contacted at room temperature, at a normal with catalytic wet oxidation catalyst by phenol wastewater and react, this catalyst includes following nucleocapsid structure component, and this nucleocapsid structure component is with activated carbon for core, with the aluminium oxide containing transition metal and rare earth metal for shell, with the weight of activated carbon and aluminium oxide for benchmark, activated carbon accounts for 10% ~ 70%, it is preferred to 30% ~ 70%, aluminium oxide accounts for 30% ~ 90%, it is preferred to 30% ~ 70%.
In catalyst used by the inventive method, described transition metal is one or more in the base metal in the 4th and 5 cycles in the periodic table of elements, and the granularity of described activated carbon is 150 order ~ 300 orders.
In catalyst used by the inventive method, transition metal is selected from one or more in vanadium, chromium, manganese, ferrum, cobalt, copper and titanium.In catalyst of the present invention, described rare earth metal is one or more in lanthanum, cerium.
In catalyst used by the inventive method, with transition metal and rare earth metal for active metal component, with the weight of catalyst for benchmark, the content of transition metal oxide is 1% ~ 15%, being preferably 1% ~ 10%, the content of rare-earth oxide is 1% ~ 15%, it is preferred to 1% ~ 10%, the content of activated carbon and aluminium oxide is 70% ~ 98%, it is preferred to 80% ~ 98%.
Catalyst used by the inventive method can be the powder catalyst not needing molding, it is also possible to be preformed catalyst.The granularity of powder catalyst is generally 0.05 ~ 0.2mm.Preformed catalyst can determine the size of granularity as required, is generally 0.5 ~ 8.0mm.
The character of the preformed catalyst used by the inventive method is as follows: specific surface area is 200 ~ 1000m2/ g, pore volume is 0.3 ~ 1.8cm3/ g, < 3wt%, side pressure strength is 100 ~ 250N/cm to rate of wear.
The aluminium oxide of heretofore described transition metal and rare earth metal can contain auxiliary agent, the adjuvant component that described auxiliary agent can be commonly used for carrier, in such as titanium, zirconium, magnesium, zinc etc. one or more, in the weight content of element below 10%, it is preferred to 1% ~ 5%.
The preparation process of catalytic wet oxidation catalyst of the present invention, including:
(1) by 150 order ~ 300 order activated carbon making beating；
(2) coprecipitation is being adopted to prepare the activated carbon serosity that aluminium oxide obtains with introducing step (1) in the plastic process of transition metal and rare-earth metal complex；
(3) material after the plastic that step (2) obtains carry out aging, filter, washing, dry；
(4) material of step (3) gained is made catalyst, it is preferable that at least adopt one of following method:
A, by the material of step (3) gained, roasting under inert gas shielding, obtain catalyst；
B, by the material forming of step (3) gained, after drying, roasting under inert gas shielding, obtain catalyst；
C, by material roasting under inert gas shielding of step (3) gained, then then through molding, after drying, roasting under inert gas shielding, obtain catalyst.
Step of the present invention (1) described activated carbon can be selected for the Powdered Activated Carbon commodity of routine, such as all kinds of wood activated charcoals, active fruit shell carbon, active carbon from coal；Can also select with wooden material, mineral material, plastics and garbage, such as the various activated carbon products that timber, wood flour, Linesless charcoal, coconut husk, pit, shell, coal, gangue, petroleum coke, asphalt, polrvinyl chloride, polypropylene, organic resin, damaged tire, excess sludge etc. obtain through traditional preparation methods.The activated carbon used in the present invention is powdered active carbon, granularity 150 ~ 300 order, specific surface area 500 ~ 3000m2/ g, pore volume 0.5 ~ 1.8cm3/ g, average pore radius 1 ~ 10nm.
In the inventive method, the making beating of activated carbon described in step (1) adopts conventional method to carry out, be generally adopted add water, one or more in low-carbon alcohols are pulled an oar, wherein low-carbon alcohols is carbon number is one or more in the monohydric alcohol of 1 ~ 5.
In the inventive method, step (1) preferably activated carbon first adopts saccharide to process, and then pulls an oar.Described saccharide is one or more in monosaccharide and disaccharide, polysaccharide, preferred carbon number is the saccharide of 3 ~ 20, such as: one or more in triose, tetrose, pentose, hexose, maltose, glucose, sucrose, more preferably one or more in glucose, sucrose.Described saccharide consumption accounts for the 2% ~ 50% of activated carbon weight, it is preferred to 5% ~ 20%.Saccharide processes activated carbon and can directly be mixed with activated carbon by saccharide, it is also possible to being dissolved in solvent by saccharide and add activated carbon, solvent therein is one or more in water, low-carbon alcohols (namely carbon number is the monohydric alcohol of 1 ~ 5).When saccharide processes activated carbon, its liquid-solid volume ratio is below 10, it is preferable that 1 ~ 5.After saccharide processes activated carbon, excessive liquid phase is preferably filtered to remove, and then pulls an oar again.Making beating can adopt conventional method to carry out, be generally adopted add water, one or more in low-carbon alcohols are pulled an oar, wherein low-carbon alcohols is carbon number is one or more in the monohydric alcohol of 1 ~ 5.
In step of the present invention (2), adopt coprecipitation to prepare aluminium oxide and can be undertaken by process well known to those skilled in the art with transition metal and rare earth metal composite oxide.It is usually the neutralization plastic process of acid material and alkaline material.Plastic process can adopt the mode of the continuous acid-base titration of soda acid, it would however also be possible to employ two kinds of materials also flow the mode of neutralization.
In step of the present invention (2), adopting coprecipitation to prepare aluminium oxide with transition metal and rare earth metal composite oxide is in aluminum source, (transition metal source is preferably vanadium source for transition metal source and rare earth metal source, chromium source, manganese source, ferrum source, cobalt source, one or more in copper source and titanium source, rare earth metal source is selected from lanthanum source, one or more in cerium source) react with precipitant and to carry out plastic, aluminum source is aluminum chloride, aluminum sulfate, one or more in aluminum nitrate, precipitant used is usually sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, one or several in ammonia etc..Transition metal source wherein used and rare earth metal source are generally adopted soluble metallic salt (such as nitrate, chloride etc.), can according to the Acidity of Aikalinity of metal salt solution used, it is mixed for co-precipitation with corresponding acid material or alkaline material, plastic cans can also be initially charged, then acid material carries out plastic with alkaline material, and above content those skilled in the art are known by coprecipitation.
Described coprecipitation, plastic process is typically at room temperature ~ 85 DEG C to carry out, be relatively suitably for 40 ~ 80 DEG C, it is preferred to 50 ~ 70 DEG C.Described plastic process is typically under certain pH value condition to carry out, and typical pH is 6.0 ~ 10.0, is relatively suitably for 7.0 ~ 9.5, it is preferred to 7.5 ~ 9.0.Aging described in step (3), condition is as follows: pH is 6.0 ~ 10.0, it is preferred to 7.0 ~ 9.5, and ageing time 0.25 ~ 8 hour is relatively adapted at 0.5 ~ 5 hour, it is preferred to 1 ~ 3 hour, and aging temperature is room temperature ~ 85 DEG C, it is preferred to 40 ~ 80 DEG C.Temperature and pH when temperature time aging and pH and neutralization are preferably identical.
In the present invention, step (2) adopts coprecipitation to prepare in the process of aluminium oxide and transition metal and rare-earth metal complex, can also adding the adjuvant component that carrier is conventional, one or more in such as titanium, zirconium, magnesium, zinc etc., its addition can select according to actual needs.
In step of the present invention (2), the incorporation way of step (1) gained mixture adopts the one or more combination of following manner: this mixture, in coprecipitation reaction process, is continuously added in plastic cans by (1)；(2) this mixture is charged first in plastic cans, then carries out coprecipitation reaction；(3) this mixture is mixed with one or more of coprecipitation reaction material, then carry out coprecipitation reaction.
In step of the present invention (3), the mode of washing of described material is known in those skilled in the art, can selecting to add the mode such as water washing, lower alcohols washing when making beating washing, filtration, the temperature of washing should in the temperature range of room temperature ~ 90 DEG C, it is preferable that 50 ~ 70 DEG C.The washing of described material is typically in the scope that pH is 1.0 ~ 9.0 to carry out, it is preferable that pH is 4.0 ~ 8.5.Material described in step of the present invention (3) washing, filter after should without or containing minimal amount of heteroion, heteroion includes Na+、Cl-、SO4 2-、NO3 -、K+Deng in one or more.
In step of the present invention (3), described material is after washing, filtering, filter cake is dried, and drying mode can adopt natural drying, oven drying, spray drying, microwave drying or infrared drying, and the drying condition being generally adopted is as follows: dry 1 ~ 15 hour at 50 ~ 150 DEG C.
In step of the present invention (4), method A obtains powder catalyst without molding roasting direct.Roasting condition described in method A is as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
In step of the present invention (4), method B and the molding described in method C can carry out as required, are generally strip, cylindric, spherical, irregular strip, special-shaped ball etc., and granularity can be determined as required, is generally 0.5 ~ 8.0mm.In described forming process, it is possible to one or more in addition shaping assistant such as binding agent, peptization acid, extrusion aid etc. as required.
In step of the present invention (4), the drying condition described in method B is generally at 80 ~ 200 DEG C, and dry 1 ~ 15 hour, sintering temperature was generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
In step of the present invention (4), in method C, by material roasting under inert gas shielding of step (3) gained, described roasting condition is as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.Then then through molding, after drying, roasting under inert gas shielding, obtain catalyst, the drying condition after molding is as follows: at 80 ~ 200 DEG C, and dry 1 ~ 15 hour, roasting condition was as follows: sintering temperature is generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
In the present invention, carrying out roasting under inert gas shielding, selected noble gas is generally nitrogen or argon.
The phenol wastewater that the inventive method processes is produce the waste water produced in phenolic resin process, and its COD is often as high as 600 ~ 40000mg/L, and free phenol content is at 0.2wt% ~ 1.2wt%.
The processing method of phenol wastewater of the present invention, uses bubbling bed reactor or fixed bed reactors, adopts CWO method, uses the wet oxidizing catalyst of the present invention, with containing ozone-air for oxide isolation, reaction temperature is room temperature, and reaction pressure is normal pressure.Adopt operating condition during bubbling bed reactor as follows: the volume ratio of catalyst and waste water is 1:1 ~ 1:10, response time is 0.25 ~ 5.0h, ozone content is 10 ~ 100mg/L, preferred operating condition is: the volume ratio of catalyst and waste water is 1:1.5 ~ 1:5, response time is 0.3 ~ 2.0h, and ozone content is 20 ~ 70mg/L.Adopt operating condition during fixed bed reactors as follows: volume space velocity 0.3 ~ 3.0h during liquid-1, ozone content is 10 ~ 100mg/L, and the volume ratio of gas and waste water is 50 ~ 300, it is preferred that operating condition is: during liquid, volume space velocity is 0.5 ~ 2.0h-1, ozone content is 20 ~ 70mg/L, and the volume ratio of gas and waste water is 80 ~ 300.
In the inventive method, described room temperature and normal pressure need not heat when referring to employing the inventive method Phenol-Containing Wastewater Treatment, it is not necessary to pressurization, room temperature is generally 10 ~ 40 DEG C, and normal pressure is generally 1 atmospheric pressure.
In catalyst used by the inventive method, nucleocapsid structure component be by with activated carbon be core, with the aluminium oxide containing transition metal and rare earth metal for shell, make full use of that activated carbon specific surface area is big, high adsorption capacity and aluminium oxide aperture is big, pore volume is high feature, activated carbon is for the high adsorption capacity of organic molecule, Preferential adsorption organic molecule, by the diffusion of the outer surface inner surface of catalyst, so makes reactant first react with the oxide contact containing active metal as shell；On the other hand, aluminium oxide is strong compared with the adhesion of activated carbon Yu active metal with the adhesion of active metal, the loss of active metal is not be provided providing sufficiently active while, makes catalyst have higher reactivity and stability in use, improve the service life of catalyst.
In the preparation process of catalyst of the present invention, aluminium oxide and introducing activated carbon in the plastic process of transition metal and rare-earth metal complex is prepared in coprecipitation, so make the alumina gel coating active charcoal containing transition metal and rare earth metal, formed with activated carbon for core, the complex being shell with the aluminium oxide containing transition metal and rare earth metal, so fully utilize activated carbon specific surface area big, advantage and aluminium oxide mechanical strength that absorption affinity is strong are high, aperture is big, the advantage of pore distribution concentration, aluminium oxide coating active charcoal, activated carbon is made to be evenly distributed in aluminium oxide, aluminium oxide provides good mechanical support and intensity, catalyst is made to have good mechanical strength and anti-wear performance, raw material is diffused into the inner surface of activated carbon by the duct of shell aluminium oxide simultaneously, catalyst is provided powerful specific surface area by activated carbon, activated carbon fine dispersion in aluminium oxide makes the utilization rate of activated carbon be improved, the surface of activated carbon obtains and utilizes more fully, the serviceability and stability improving catalyst had good facilitation.
In the preparation process of catalyst of the present invention, pull an oar again after processing activated carbon in particular by saccharide, then introduce in preparing the plastic process containing transition metal and the aluminium oxide of rare earth metal, saccharide is adsorbed on the surfaces externally and internally of activated carbon uniformly, make to be mixed in the carbohydrate breakdown carbonization in the middle of aluminium oxide and activated carbon by follow-up roasting process, the activated carbon being newly formed connects aluminium oxide and activated carbon, the combination making activated carbon and aluminium oxide is tightr, the inner surface of the former activated carbon of new Activated Carbon Modification through being decomposed to form of the saccharide on activated carbon inner surface, add the adsorption activity position of activated carbon inner surface.Therefore, preferably increase saccharide and process activated carbon, it is possible to promote aluminium oxide closely coating active charcoal, be conducive to improving mechanical strength and the abrasion resisting performance of catalyst, and improve the utilization rate of the inner surface of activated carbon, be conducive to improving activity and the stability of catalyst.
Using the inventive method Phenol-Containing Wastewater Treatment, under gentle reaction condition, can effectively reduce COD, improve BOD/COD, and can accelerate response speed, reduction processes energy consumption, reduces equipment investment.In use, activity stability is high for catalyst of the present invention, and without efflorescence, argillization phenomenon, reactor water outlet is analyzed measurement result through ICP-MS and shown, the stripping quantity of metal ion is only small, and catalyst has good stability.The processing method of phenol wastewater of the present invention can adopt industrial commonly used continuous fixed-bed reactor, has wide practical use.
Detailed description of the invention
The specific surface area of product of the present invention and pore volume are to adopt low temperature liquid nitrogen physisorphtion to measure.Rate of wear is to adopt drum-type abrasion instrument to measure (to be specifically shown in " catalyst support preparation and application technology " (petroleum industry publishing house, in May, 2002, Zhu Hongfa writes, and 4.5.4 saves).Grained catalyst granularity adopts laser particle size analyzer to measure；Preformed catalyst granularity adopts sieve method to record.In the present invention, wt% is mass fraction.
Below in conjunction with the preparation method that specific embodiment further illustrates the present invention, but the scope of the present invention is not limited solely to the scope of these embodiments.
The character of commercially available powdery coconut husk charcoal used in the present invention is as follows: specific surface area 928m2/ g, pore volume 1.0cm3/ g, average pore radius 1.1nm, iodine sorption value 700mg/g, granularity 200 order.
Embodiment 1
Joining in distilled water by solid aluminum chloride, cerous nitrate, copper nitrate, heating simultaneously is also stirred to dissolving, and obtains solution (a).Strong aqua ammonia is added appropriate distilled water diluting into about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in D/W, and liquid-solid volume ratio is 3:1, and then add water making beating, obtains serosity (c).After plastic cans adding (a) and being heated with stirring to 60 DEG C, open the valve of the container having (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, now in tank, add (c), continue dropping (b), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0.Keeping temperature is 60 DEG C; pH=8.0; aging 1 hour; being filtered by material in tank, washing is to without chloride ion, filtering; filter cake is dried 10 hours at 110 DEG C; obtain catalyst material A-1, then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverize and sieve and obtain powder catalyst J-1.The amount of plastic agents useful for same is listed in table 1.
Take powder catalyst J-1100 gram, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then at 110 DEG C dry 10 hours, under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst A, its composition is in Table 2.
Embodiment 2
Joining in distilled water by Solid aluminum sulfate, cerous nitrate, copper nitrate, heating simultaneously is also stirred to dissolving, and obtains solution (a).Strong aqua ammonia is added appropriate distilled water diluting into about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in D/W, and liquid-solid volume ratio is 5:1, and then add water making beating, obtains activated carbon serosity (c).Take a plastic cans, after tank adding (a) and being heated with stirring to 60 DEG C, open the valve of the container having (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, open the valve of (c) container, continue dropping (b), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c), it is ensured that be now added dropwise to complete.Keeping temperature is 60 DEG C; pH=8.0; aging 1 hour; material in tank is filtered, washs to sulfate radical-free ion, filter; filter cake is dried 10 hours at 110 DEG C; obtain catalyst material A-2, then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverize and sieve and obtain powder catalyst J-2.The amount of plastic agents useful for same is listed in table 1.
Take catalyst material A-2100 gram, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then at 110 DEG C dry 10 hours, under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst B, its composition is in Table 2.
Embodiment 3
Joining in distilled water by solid aluminum chloride, cerous nitrate, manganese nitrate, heating simultaneously is also stirred to dissolving, and obtains solution (a).Strong aqua ammonia is added appropriate distilled water diluting into about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in D/W, and liquid-solid volume ratio is 3:1, and then add water making beating, obtains activated carbon serosity (c).After plastic cans adding (a) and being heated with stirring to 60 DEG C, open the valve of the container having (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, now in tank, add (c), continue dropping (b), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0.Keeping temperature is 60 DEG C; pH=8.0; aging 1 hour; being filtered by material in tank, washing is to without chloride ion, filtering; filter cake is dried 10 hours at 110 DEG C; obtain catalyst material A-3, then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverize and sieve and obtain powder catalyst J-3.The amount of plastic agents useful for same is listed in table 1.
Take catalyst material A-3100 gram, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then at 110 DEG C dry 10 hours, under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst C, its composition is in Table 2.
Embodiment 4
Joining in distilled water by Solid aluminum sulfate, Lanthanum (III) nitrate, copper nitrate, heating simultaneously is also stirred to dissolving, and obtains solution (a).Strong aqua ammonia is added appropriate distilled water diluting into about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in D/W, and liquid-solid volume ratio is 3:1, and then add water making beating, obtains activated carbon serosity (c).Take a plastic cans, after tank adding (a) and being heated with stirring to 60 DEG C, open the valve of the container having (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, open the valve of (c) container, continue dropping (b), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c), it is ensured that be now added dropwise to complete.Keeping temperature is 60 DEG C; pH=8.0; aging 1 hour; material in tank is filtered, washs to sulfate radical-free ion, filter; filter cake is dried 10 hours at 110 DEG C; obtain catalyst material A-4, then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverize and sieve and obtain powder catalyst J-4.The amount of plastic agents useful for same is listed in table 1.
Take catalyst material A-4100 gram, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then at 110 DEG C dry 10 hours, under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst D, its composition is in Table 2.
Embodiment 5
Repeat the synthesis of embodiment 2, without saccharide in plastic process, prepare catalyst material A-5 and powder catalyst J-5.
Preformed catalyst is prepared with embodiment 2, obtains catalyst E, and its composition is in Table 2.
Comparative example 1
Repeat the synthesis of embodiment 2, without activated carbon and saccharide in plastic process, prepare comparative catalyst material PA-1 and powder catalyst DF-1, its appearance white.
Preformed catalyst is prepared with embodiment 2, obtains catalyst DA, and its composition is in Table 2.
Comparative example 2
Activated carbon 100g used in embodiment 2 is contacted with the peptization liquid containing nitric acid and forms paste, extruded moulding, then at 110 DEG C dry 10 hours, under nitrogen protection under 550 DEG C of conditions after roasting 5 hours, obtain carrier, its outward appearance is black.Then adopting dipping method supported active metals component, obtain catalyst DB, its composition is in Table 2.
Comparative example 3
By activated carbon used in embodiment 2 with catalyst material PA-1 physical mixed; contact with the peptization liquid containing nitric acid and form paste; extruded moulding; then dry 10 hours at 110 DEG C; under nitrogen protection under 550 DEG C of conditions after roasting 5 hours; obtaining catalyst carrier DZ-C, wherein activated carbon is identical with embodiment 2 with alumina content, its outward appearance black.Then adopting dipping method supported active metals component, obtain catalyst DC, its composition is in Table 2.
Table 1 plastic reagent quality
| Bearer number | J-1 | J-2 | J-3 | J-4 | J-5 |
| Aluminium salt, g | 1007 | 1284 | 1556 | 632 | 1284 |
| Sugar, g | 9 | 48 | 13 | 81 | - |
| Activated carbon, g | 165 | 383 | 255 | 440 | 402 |
| Cerous nitrate, g | 61 | 108 | 98 | - | 108 |
| Copper nitrate, g | 71 | 120 | - | 72 | 120 |
| Ferric nitrate, g | - | - | - | - | - |
| Manganese nitrate, g | - | - | 130 | - | - |
| Lanthanum (III) nitrate, g | - | - | - | 61 | - |
The composition of table 2 catalyst and character
| Catalyst is numbered | A | B | C | D | E | DA | DB | DC |
| CeO2, wt% | 3.69 | 4.22 | 3.82 | - | 4.12 | 4.24 | 4.24 | 4.20 |
| CuO, wt% | 3.74 | 4.11 | - | 2.83 | 4.07 | 4.12 | 4.08 | 4.14 |
| Fe2O3, wt% | - | - | - | - | - | - | - | - |
| MnO2, wt% | - | - | 3.80 | - | - | - | - | - |
| La2O3, wt% | - | - | - | 2.75 | - | - | - | - |
| Specific surface area, m2/g | 385 | 425 | 384 | 384 | 404 | 247 | 788 | 377 |
| Pore volume, mL/g | 0.45 | 0.34 | 0.44 | 0.26 | 0.33 | 0.62 | 0.40 | 0.31 |
| Side pressure strength, N/cm | 229 | 183 | 249 | 177 | 174 | 225 | 47 | 163 |
| Abrasion, wt% | 0.56 | 0.63 | 0.63 | 0.75 | 0.78 | 0.28 | 5.80 | 0.94 |
By catalyst property in table 2 it can be seen that adopt the catalyst that saccharide obtains after processing activated carbon compared with the catalyst obtained without saccharide, bulk property is improved.
It is canescence by the outward appearance of the catalyst material of embodiment of the present invention gained and catalyst, without obvious black, illustrates that activated carbon becomes the core of catalyst material and catalyst.
In the present invention, adopt X-ray photoelectron spectroscopy (XPS) that the element of embodiment 2 and comparative example 1 gained catalyst material surface is analyzed.From analyzing result, the elementary composition and PA-1 composition on embodiment 2 gained catalyst material A-2 surface is essentially identical, all has the elemental carbon of trace.This further illustrates, and the catalyst of the present invention is with activated carbon for core, with the aluminium oxide containing transition metal and rare earth metal for shell.
Waste water wet oxidation is tested
Using embodiment and comparative example prepared catalyst to carry out waste water wet oxidation test, adopt bubbling bed reactor, with ozone for oxide isolation, test at room temperature, at a normal, other experimental conditions and result are listed in table 3 and table 4.
In table 3 and table 4, liquor is than the volume ratio for waste water and catalyst, and clearance is COD clearance.
Used raw material is phenol wastewater, wherein COD:1567mg/L, free phenol 0.85wt%.
Table 3 wet oxidation reaction condition and result
| Catalyst | Liquor ratio | The process time, h | Ozone concentration, mg/L | Clearance, % |
| A | 2.0 | 1.0 | 35 | 93.8 |
| B | 2.0 | 1.0 | 35 | 93.3 |
| C | 2.0 | 1.0 | 35 | 92.4 |
| D | 2.0 | 1.0 | 35 | 94.2 |
| E | 2.0 | 1.0 | 35 | 91.3 |
| DA | 2.0 | 1.0 | 35 | 81.1 |
| DB | 2.0 | 1.0 | 35 | 90.1 |
| DC | 2.0 | 1.0 | 35 | 89.5 |
| B | 1.5 | 1.0 | 35 | 92.5 |
| B | 1.5 | 1.0 | 50 | 93.4 |
| B | 2.5 | 1.4 | 35 | 93.1 |
| B | 3.0 | 1.6 | 30 | 90.6 |
| B | 5.0 | 2.0 | 25 | 90.1 |
Adopting the catalyst that the embodiment of the present invention is prepared with comparative example to process above-mentioned waste water under identical process conditions after 30 days, evaluation result is listed in table 4.
Table 4 stability test result
| Catalyst | Liquor ratio | The process time, sky | Ozone concentration, mg/L | Clearance, % |
| A | 2.0 | 30 | 35 | 91.7 |
| B | 2.0 | 30 | 35 | 91.3 |
| C | 2.0 | 30 | 35 | 90.9 |
| D | 2.0 | 30 | 35 | 93.1 |
| E | 2.0 | 30 | 35 | 90.3 |
| DA | 2.0 | 30 | 35 | 78.6 |
| DB | 2.0 | 30 | 35 | 73.3 |
| DC | 2.0 | 30 | 35 | 82.3 |
| B | 1.5 | 30 | 35 | 90.6 |
| B | 1.5 | 30 | 50 | 91.2 |
| B | 2.5 | 30 | 35 | 91.5 |
| B | 3.0 | 30 | 30 | 87.4 |
| B | 5.0 | 30 | 25 | 88.6 |
By table 4 fruit it can be seen that catalytic wet oxidation catalyst of the present invention is after using 30 days continuously, the COD clearance of handled phenol wastewater is all more than 85%, and free phenol does not detect.
Claims (14)
1. the ozone catalytic wet oxidation method of a phenol wastewater, its process includes: using ozone as oxide isolation, to contact at room temperature, at a normal with catalytic wet oxidation catalyst containing phenols wastewater and react, this catalyst includes following nucleocapsid structure component, this nucleocapsid structure component is with activated carbon for core, with the aluminium oxide containing transition metal and rare earth metal for shell, with the weight of activated carbon and aluminium oxide for benchmark, activated carbon accounts for 10% ~ 70%, and aluminium oxide accounts for 30% ~ 90%.
2. in accordance with the method for claim 1, it is characterised in that: in described catalyst, with the weight of activated carbon and aluminium oxide for benchmark, activated carbon accounts for 30% ~ 70%, and aluminium oxide accounts for 30% ~ 70%.
3. in accordance with the method for claim 1, it is characterised in that: in described catalyst, transition metal is the base metal in the 4th and 5 cycles in the periodic table of elements, and the granularity of activated carbon is 150 order ~ 300 orders.
4. in accordance with the method for claim 1, it is characterised in that: in described catalyst, transition metal is selected from one or more in vanadium, chromium, manganese, ferrum, cobalt, copper and titanium, and rare earth metal is one or more in lanthanum, cerium.
5. in accordance with the method for claim 1, it is characterized in that: described catalyst, with transition metal and rare earth metal for active metal component, with the weight of catalyst for benchmark, the content of transition metal oxide is 1% ~ 15%, the content of rare-earth oxide is 1% ~ 15%, and the content of activated carbon and aluminium oxide is 70% ~ 98%.
6. in accordance with the method for claim 1, it is characterised in that: adopt bubbling bed reactor or fixed bed reactors.
7. in accordance with the method for claim 6, it is characterised in that: when adopting bubbling bed reactor, operating condition is as follows: the volume ratio of catalyst and waste water is 1:1 ~ 1:10, and the response time is 0.25 ~ 5.0h, and ozone content is 10 ~ 100mg/L.
8. in accordance with the method for claim 6, it is characterised in that: when adopting bubbling bed reactor, operating condition is as follows: the volume ratio of catalyst and waste water is 1:1.5 ~ 1:5, and the response time is 0.3 ~ 2.0h, and ozone content is 20 ~ 70mg/L.
9. the method described in claim 7 or 8, it is characterised in that: described catalyst is powder catalyst, and the granularity of powder catalyst is 0.05 ~ 0.20mm.
10. in accordance with the method for claim 6, it is characterised in that: when adopting fixed bed reactors, operating condition is as follows: volume space velocity 0.3 ~ 3.0h during liquid-1, ozone content is 10 ~ 100mg/L, and the volume ratio of gas and waste water is 50 ~ 300.
11. in accordance with the method for claim 6, it is characterised in that: when adopting fixed bed reactors, operating condition is as follows: during liquid, volume space velocity is 0.5 ~ 2.0h-1, ozone content is 20 ~ 70mg/L, and the volume ratio of gas and waste water is 80 ~ 300.
12. the method described in claim 10 or 11, it is characterised in that described catalyst is preformed catalyst, granularity is 0.5 ~ 8.0mm.
13. the method described in claim 10 or 11, it is characterised in that the character of described preformed catalyst is as follows: specific surface area is 200 ~ 1000m2/ g, pore volume is 0.3 ~ 1.8cm3/ g, < 3wt%, side pressure strength is 100 ~ 300N/cm to rate of wear.
14. in accordance with the method for claim 1, it is characterised in that: in described phenol wastewater, COD is 600 ~ 40000mg/L, and free phenol content is at 0.2wt% ~ 1.2wt%.
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