CN105712461A - Catalytic wet oxidation method for acrylic acid and ester wastewater - Google Patents
Catalytic wet oxidation method for acrylic acid and ester wastewater Download PDFInfo
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- CN105712461A CN105712461A CN201410710573.3A CN201410710573A CN105712461A CN 105712461 A CN105712461 A CN 105712461A CN 201410710573 A CN201410710573 A CN 201410710573A CN 105712461 A CN105712461 A CN 105712461A
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Abstract
The invention discloses a catalytic wet oxidation method for acrylic acid and ester wastewater. The method includes contacting acrylic acid and its ester wastewater with a catalytic wet oxidation catalyst to carry out reaction. The catalyst includes the following core-shell structure component, and the core-shell structure component adopts activated carbon as the core, and employs alumina containing noble metals and rare earth metals as the shell. The catalyst used in the method has the advantages of good catalytic performance, strong wear resistance and good use stability, is in favor of improving the removal rate of organic matters in acrylic acid wastewater.
Description
Technical field
A kind of method that the present invention relates to CWO, especially for the method for the CWO of acrylicacidandesters waste water.
Background technology
In the present invention, acrylicacidandesters waste water refers to produced waste water in production acrylicacidandesters class process.
In recent years, along with acrylicacidandesters class industry fast development, acrylicacidandesters waste water be treated as day by day serious problem.COD in acrylicacidandesters waste water is 10000 ~ 100000mg/L, concentration is higher, wherein content of formaldehyde is 1wt% ~ 4wt%, toxicity is very big, additionally, wherein contain the gas chromatographies such as acrylic acid, acetic acid, formaldehyde, acrylic aldehyde, acrylic acid methyl ester., ethyl acrylate, complicated component so that the process of acrylicacidandesters waste water is very difficult.At present, process acrylicacidandesters waste water main method be burning method, but due to burning method costly, there is secondary pollution, additionally also have bioanalysis, catalytic wet air oxidation etc..Bioanalysis is divided into aerobic method, anaerobic process, Aerobic-anaerobic combination method, and bioanalysis is owing to existing the problems such as floor space is big, investment cost is high, economic feasibility is poor, technique is loaded down with trivial details, water outlet is not up to standard, in addition it is also necessary to solve further.CWO technology has reaction temperature and reaction pressure is relatively low, reaction capacity of decomposition is high, the feature such as equipment corrosion is little, operating cost is low, it is suitable for processing the organic wastewater of some high concentrations, high toxicity, difficult degradation, and without considering the toxicity of acrylicacidandesters waste water, and in acrylicacidandesters waste water, COD concentration is in its suitable treatment concentration range, therefore, by contrast, catalytic wet air oxidation more has application prospect.
Traditional wet air oxidation needs High Temperature High Pressure, not only energy consumption is high but also equipment material requirement is also high, therefore, the industrial traditional wet catalytic oxidation that is typically in is when processing organic wastewater, add catalyst, to reduce the activation energy of reaction, so that reaction can complete gentleer when and within the shorter time.Study more oxidant at present and have H2O2, Fenton reagent and ozone etc., 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.
The catalyst that article " Treatment of acrylic acid waste water by catalytic wet oxidation " (Jilin Institute of Chemical Technology journal, the 24th volume the 3rd phase in 2007) adopts is MnO2-CuO-CeO2-Fe2O3Composite oxides, at normal temperatures and pressures, with hydrogen peroxide for oxidant, COD clearance reaches 68%.Adopting these composite oxides is catalyst, and the clearance of its COD is relatively low.
CN200710048051.1 discloses a kind of method that high-concentration organic waste water in acroleic acid production processes, and including (1), oxidant and deionized water is hybridly prepared into oxidizing agent solution, is placed in oxidant tank；(2) acrylic acid production waste water and clear water are respectively placed in waste water and clean water tank, and in waste water, add catalyst；(3) first preheater being heated to 300-400 DEG C, reactor is heated to 400-600 DEG C；(4) high-pressure plunger pump sample introduction is opened, enter in reactor micropore ceramic tube after preheated, the pressurization respectively of waste water and oxidizing agent solution, carrying out supercritical water oxidation at pressure 22 ~ 28MPa and temperature 374 DEG C ~ 600 DEG C, clear water is by ceramic membrane outer wall infiltration into microporous earthenware；(5) process that water outlet is cooled and can realize qualified discharge after gas-liquid separation.Catalyst MnO wherein used2/γ-Al2O3.The method is higher to organic removal rate, but the method process is complicated, and operating condition is very harsh.
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.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of CWO method of acrylicacidandesters waste water.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 method of CWO of the present invention, its process includes: is contacted with catalytic wet oxidation catalyst by acrylicacidandesters waste water and reacts, this catalyst includes following nucleocapsid structure component, this nucleocapsid structure component is with activated carbon for core, with the aluminium oxide containing noble metal and rare earth metal for shell, with the weight of activated carbon and aluminium oxide for benchmark, activated carbon accounts for 10% ~ 70%, being preferably 30% ~ 70%, aluminium oxide accounts for 30% ~ 90%, it is preferred to 30% ~ 70%.
The granularity of described activated carbon is preferably 150 order ~ 300 orders.
In catalyst of the present invention, with the weight of catalyst for benchmark, the content that noble metal is counted with element is for 0.01% ~ 1.0%, and the content of rare earth metal is calculated as 1% ~ 15% with element, it is preferred to 1% ~ 10%, and the content of activated carbon and aluminium oxide is 89% ~ 98%.
In catalyst of the present invention, described noble metal is selected from one or several in Pt, Pd, Rh, Ru, and described rare earth metal is one or more in lanthanum, cerium, praseodymium, neodymium.
The catalyst of the present invention 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 ~ 0.20mm.Preformed catalyst can determine the size of granularity as required, is generally 0.5 ~ 8.0mm.
Containing auxiliary agent in the heretofore described aluminium oxide containing noble metal and rare earth metal, auxiliary agent can be the adjuvant component that carrier be commonly used, 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 character of preformed catalyst of the present invention 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 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 noble metal and the complex of rare earth metal；
(3) material after the plastic that step (2) obtains carry out aging, filter, washing, dry, obtain catalyst material；
(4) catalyst material of step (3) gained being made catalyst, the preparation of described catalyst preferably at least adopts one of following method:
A, by the catalyst material of step (3) gained, roasting under inert gas shielding, obtain catalyst；
B, by the catalyst material molding of step (3) gained, after drying, roasting under inert gas shielding, obtain catalyst；
C, by catalyst 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, 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.
Adopt coprecipitation to prepare aluminium oxide to be undertaken by process well known to those skilled in the art with noble metal and rare-earth metal complex.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), adopt coprecipitation to prepare aluminium oxide and noble metal and rare earth metal composite oxide be in aluminum source, noble metal source and rare earth metal source react with precipitant and carry out plastic, aluminum source is one or more in aluminum chloride, aluminum sulfate, aluminum nitrate, and precipitant used is usually one or several in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia etc..Noble 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 noble 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 the mixture of step (1) gained 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) being mixed with one or more of plastic material by this mixture, then plastic material carries 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 catalyst 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.
In the inventive method, described waste water comes from the waste water that acrylicacidandesters produces, COD is up to 10000 ~ 100000mg/L, wherein content of formaldehyde is at 1wt% ~ 4wt%, often contain acrylic acid, acetic acid, formaldehyde, acrylic aldehyde, acrylic acid methyl ester., the impurity such as gas chromatography such as ethyl acrylate, complicated component.
The processing method of acrylicacidandesters waste water of the present invention, adopt CWO method, use the wet oxidizing catalyst of the present invention, with oxygen-containing gas for oxide isolation, wherein the volumetric concentration of oxygen is 20% ~ 100%, oxygen-containing gas can be air or oxygen-enriched air, it is also possible to the mixing gas of oxygen and noble gas, it is preferred to use purity oxygen processes.Continuous operation type reactor can be adopted, it would however also be possible to employ intermittently operated formula reactor.When adopting continuous operation type reactor, it is possible to adopt fixed bed reactors, it would however also be possible to employ fluidized-bed reactor.
In the inventive method, when adopting continuous operation type reactor, operating condition is as follows: reaction temperature is 150 ~ 260 DEG C, and reaction gross pressure is 0.3 ~ 6.0MPa, and during liquid, volume space velocity is 0.3 ~ 3.0h-1, the volume ratio of oxygen and waste water is 50 ~ 300；Preferred operating condition is: reaction temperature 180 ~ 200 DEG C, reacts gross pressure 1.5 ~ 3.5MPa, and during liquid, volume space velocity is 0.5 ~ 2.0h-1, the volume ratio of oxygen and waste water is 80 ~ 300.
In the inventive method, during employing intermittently operated formula reactor, operating condition is as follows: reaction temperature is 150 ~ 260 DEG C, reaction gross pressure is 0.3 ~ 6.0MPa, response time is 0.5 ~ 3.0h, the volume ratio of oxygen and waste water is 50 ~ 300, the ratio of catalyst amount and waste water is 1 ~ 10g catalyst/L waste water, preferred operating condition is: reaction temperature 180 ~ 200 DEG C, reaction gross pressure 1.5 ~ 3.5MPa, response time 0.5 ~ 2h, the volume ratio of oxygen and waste water is 80 ~ 300, and the ratio of catalyst amount and waste water is 1 ~ 10g catalyst/L waste water.The nucleocapsid structure component that catalyst of the present invention adopts is by with activated carbon for core, with the aluminium oxide containing noble metal and rare earth metal for shell, make full use of activated carbon specific surface area big, high adsorption capacity and aluminium oxide aperture are big, the feature that pore volume is high, activated carbon is for the high adsorption capacity of organic molecule, Preferential adsorption organic molecule is by the diffusion of the outer surface inner surface of catalyst, so make the haptoreaction of the reactant aluminium oxide containing active metal first and 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, catalyst is made to have higher reactivity and stability in use, improve the service life of catalyst.
In the preparation process of catalyst of the present invention, the plastic process of aluminium oxide introduces activated carbon, so make alumina gel coating active charcoal, formed with activated carbon for core, the complex being shell with the aluminium oxide containing noble 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 the plastic process of aluminium oxide, 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, adds 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 to process acrylic acid wastewater, under the reaction condition relatively relaxed, can effectively reduce COD, and response speed is fast, 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 inventive method can adopt industrial commonly used continuous fixed-bed reactor, has wide practical use.
Detailed description of the invention
The specific surface area of catalyst 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, chloroplatinic acid, 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 after roasting 5 hours, impregnate with the impregnation liquid containing Pt-Ce; then dry 10 hours at 110 DEG C; under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst A, its composition in Table 2.
Embodiment 2
Joining in distilled water by Solid aluminum sulfate, cerous nitrate, rhodium 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-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 after roasting 5 hours, impregnate with the impregnation liquid containing Ru-Ce; then dry 10 hours at 110 DEG C; under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst B, its composition in Table 2.
Embodiment 3
Joining in distilled water by solid aluminum chloride, cerous nitrate, rhodium 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 after roasting 5 hours, impregnate with the impregnation liquid containing Ru-Ce; then dry 10 hours at 110 DEG C; under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst C, its composition in Table 2.
Embodiment 4
Joining in distilled water by Solid aluminum sulfate, Lanthanum (III) nitrate, chloroplatinic acid, 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 after roasting 5 hours, impregnate with the impregnation liquid containing Pt-La; then dry 10 hours at 110 DEG C; under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst D, its composition in Table 2.
Embodiment 6
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
The composition of table 2 catalyst and character
By catalyst property in table 2 it can be seen that adopt the catalyst property that saccharide obtains after processing activated carbon to be 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 gained catalyst material A-2 surface is essentially identical, all has the elemental carbon of trace.This further illustrates, and the catalyst material of the present invention is with activated carbon for core, with the aluminium oxide containing noble 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 fixed bed reactors, with oxygen for oxide isolation, oxygen concentration is 99v%, and its experimental condition and result are listed in table 3 and table 4.
Used raw material is acrylicacidandesters waste water, wherein COD:30000mg/L.
In table 3 and table 4, pressure is reaction gross pressure, and volume space velocity when air speed is liquid, gas liquid ratio is the volume ratio of oxygen and waste water, and clearance is COD clearance.
Table 3 wet oxidation reaction condition and result
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
By table 4 result it can be seen that catalytic wet oxidation catalyst of the present invention is after using 30 days continuously, the COD clearance of handled acrylicacidandesters waste water is all more than 90%.
Claims (16)
1. the method for an acrylicacidandesters Catalytic Wet Air Oxidation for Wastewater, its process includes: is contacted with catalytic wet oxidation catalyst by acrylicacidandesters waste water and reacts, this catalyst includes following nucleocapsid structure component, this nucleocapsid structure component is with activated carbon for core, with the aluminium oxide containing noble 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, noble metal is one or several in Pt, Pd, Rh, Ru, and rare earth metal is one or more in lanthanum, cerium, praseodymium, neodymium.
3. in accordance with the method for claim 1, it is characterised in that: in described catalyst, the granularity of activated carbon is 150 order ~ 300 orders.
4. in accordance with the method for claim 1, it is characterised in that: described catalyst, with the weight of activated carbon and aluminium oxide for benchmark, activated carbon accounts for 30% ~ 0%, and aluminium oxide accounts for 30% ~ 70%.
5. in accordance with the method for claim 1, it is characterized in that described catalyst, with the weight of catalyst for benchmark, the content of noble metal is calculated as 0.01% ~ 1.0% with element, the content of rare earth metal is calculated as 1.0% ~ 15.0% with element, and the content of activated carbon and aluminium oxide is 84% ~ 98%.
6. in accordance with the method for claim 1, it is characterised in that: with oxygen-containing gas for oxide isolation, wherein the volumetric concentration of oxygen is 20% ~ 100%.
7. the method described in claim 1 or 6, it is characterised in that: CWO adopts continuous operation type reactor.
8. in accordance with the method for claim 7, it is characterised in that: when adopting continuous operation type reactor, operating condition is as follows: reaction temperature is 150 ~ 260 DEG C, and reaction gross pressure is 0.3 ~ 6.0MPa, and during liquid, volume space velocity is 0.3 ~ 3.0h-1, the volume ratio of oxygen and waste water is 50 ~ 300.
9. in accordance with the method for claim 7, it is characterised in that: when adopting continuous operation type reactor, operating condition is as follows: reaction temperature 180 ~ 200 DEG C, reacts gross pressure 1.5 ~ 3.5MPa, and during liquid, volume space velocity is 0.5 ~ 2.0h-1, the volume ratio of oxygen and waste water is 80 ~ 300.
10. in accordance with the method for claim 7, it is characterised in that described catalyst is preformed catalyst, granularity is 0.5 ~ 8.0mm.
11. in accordance with the method for claim 10, 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.
12. the method described in claim 1 or 6, it is characterised in that: CWO adopts intermittently operated formula reactor.
13. in accordance with the method for claim 12, it is characterised in that described catalyst is powder catalyst, the granularity of powder catalyst is 0.05 ~ 0.20mm.
14. in accordance with the method for claim 12, it is characterized in that: during employing intermittently operated formula reactor, operating condition is as follows: reaction temperature is 150 ~ 260 DEG C, reaction gross pressure is 0.3 ~ 6.0MPa, response time is 0.5 ~ 3.0h, the volume ratio of oxygen and waste water is 50 ~ 300, and the ratio of catalyst amount and waste water is 1 ~ 10g catalyst/L waste water.
15. in accordance with the method for claim 12, it is characterized in that: during employing intermittently operated formula reactor, operating condition is as follows: reaction temperature 180 ~ 200 DEG C, reaction gross pressure 1.5 ~ 3.5MPa, response time 0.5 ~ 2.0h, the volume ratio of oxygen and waste water is 80 ~ 300, and the ratio of catalyst amount and waste water is 1 ~ 10g catalyst/L waste water.
16. in accordance with the method for claim 1, it is characterised in that: in described acrylicacidandesters waste water, COD is 10000 ~ 100000mg/L.
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