CN105709732A - Noble metal catalyst for catalytic wet oxidation and preparation method thereof - Google Patents
Noble metal catalyst for catalytic wet oxidation and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a noble metal catalyst for catalytic wet oxidation and a preparation method thereof. The catalyst comprises a following core-shell structure component. The core-shell structure component adopts activated carbon loaded with noble metal and rare earth metal as the core, and takes alumina or amorphous silica-alumina as the shell. According to the preparation method, an activated carbon slurry is introduced in a gel forming process of alumina or amorphous silica-alumina, and after gel forming, by means of aging and other steps, the catalyst can be obtained. The catalyst prepared by the method provided by the invention has high reaction activity and use stability.
Description
Technical field
The present invention relates to a kind of catalytic wet oxidation catalyst and preparation method thereof, especially for the noble metal catalyst and preparation method thereof of CWO.
Background technology
Increasingly stringent along with global environmental regulation, the Con trolling index of sewage qualified discharge requires more and more higher, under this form, waste water treatment by catalytic oxidation increasingly obtains attention and the employing of people, such as the CWO of high-concentration sewage, catalytic and oxidative electrolysis technology, photochemical catalytic oxidation, advanced oxidation etc..In waste water catalytic oxidation process, for obtaining desirable treatment effect and by reducing reaction temperature, reaction pressure to keep relatively low wastewater treatment expense, preparation have high-activity component, high intensity, high stability cheap catalyst become the key of waste water catalytic oxidation technologies application undoubtedly.
The catalyst of waste water catalytic oxidation is broadly divided into homogeneous catalyst and heterogeneous solid catalyst two class.
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, hydrogen peroxide, 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 solid catalyst, mainly with activated carbon, molecular sieve, amorphous alumina, titanium dioxide etc. for carrier, makees, with one or more in alkali metal, alkaline-earth metal, transition metal or Pt, Pd noble metal, the catalyst that active component is constituted.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 solid catalyst 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.
CN201110225789.7 discloses a kind of method utilizing discarded active amorphous alumina preparation benzene adsorption material, it be by cleaned for useless active amorphous aluminium oxide, filter, dried, adopt a kind of active amorphous aluminium oxide/absorbent charcoal composite material of cryogenic seal heat treatment mode preparation, benzene is had good adsorption effect.The method is by the organic matter carbonizing within amorphous alumina, and activated carbon is mainly distributed in the duct of amorphous alumina, so not only can block the duct of aluminium oxide, and such generated activated carbon skewness in aluminium oxide.
The preparation method that CN201110255525.6 discloses a kind of active amorphous aluminium oxide/absorbent charcoal composite material, be by waste aluminum sludge, activated carbon, binding agent through mixing, pelletize, old, molding, dry, sinter, rinse, drying and other steps makes active amorphous aluminium oxide/absorbent charcoal composite material.It is uneven that the method belongs to salic species and activated carbon physical mixing processes, aluminium oxide and activated carbon dispersion；And the mud impurity content height used, the amorphous alumina character of gained is unstable, it is impossible to repeat, and structure is complicated.
The preparation method that CN201010267074.3 discloses a kind of activated alumina composite reactive Carbon Materials, with aluminium hydroxide, activated carbon and binding agent for raw material, through mixing, pelletize, old, molding, dry, sinter, rinse, drying and other steps, the composite so obtained is still the physical mixture of aluminium oxide and activated carbon, aluminium oxide is uneven with activated carbon dispersion, and its combination property also needs further raising.
Summary of the invention
For the deficiencies in the prior art, the invention provides and a kind of there is catalytic performance is good, anti-wear performance is strong, stability in use is good noble metal catalyst for CWO and preparation method thereof.
The catalytic wet oxidation catalyst of the present invention, including following nucleocapsid structure component, this nucleocapsid structure component is with the activated carbon of carried noble metal and rare earth metal for core, with aluminium oxide or amorphous silica-alumina for shell, with the weight of activated carbon and aluminium oxide or activated carbon and amorphous silica-alumina for benchmark, activated carbon accounts for 10% ~ 70%, it is preferred to 30% ~ 70%, aluminium oxide or amorphous silica-alumina account 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%, the content of rare earth metal is calculated as 1.0% ~ 15.0% with element, it is preferably 1.0% ~ 10.0%, the content of activated carbon and aluminium oxide or activated carbon and amorphous silica-alumina is 84.0% ~ 98.0%, it is preferred to 89.0% ~ 98.0%.
In described amorphous silica-alumina, the weight content of silicon oxide is 10% ~ 90%, it is preferred to 30% ~ 70%.
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.
Heretofore described aluminium oxide or amorphous silica-alumina, auxiliary agent can for the conventional adjuvant component of 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 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) activated carbon of carried noble metal and rare earth metal is pulled an oar；
(2) in aluminium oxide or amorphous silica-alumina plastic process, the serosity that step (1) obtains is introduced；
(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, carried noble metal and the activated carbon making beating of rare earth metal described in step (1) 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 (1), the activated carbon of carried noble metal and rare earth metal adopts conventional method load, such as infusion process.Specific as follows: to be configured to impregnation liquid with precious metal salt and rare earth metal salt, then activated carbon granule is dipped in above-mentioned impregnation liquid, then drying and roasting, obtain the activated carbon of carried noble metal and rare earth metal, dipping therein can adopt noble metal and rare earth metal total immersion method, can also adopting sub-dip method, described dipping can adopt single-steeping, it would however also be possible to employ multiple maceration.Precious metal salt wherein used during preparation impregnation liquid and rare earth metal salt can adopt soluble-salt, and such as nitrate, chloride etc., those skilled in the art can determine according to practical situation.
In the inventive method, the activated carbon of step (1) preferably carried noble metal and rare earth metal 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 one or more in 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.
The plastic process of the aluminium oxide described in step of the present invention (2) or amorphous silica-alumina can be undertaken by process well known to those skilled in the art.The plastic process of aluminium oxide or amorphous silica-alumina is usually the neutralization course of reaction 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), aluminium oxide plastic is to adopt aluminum soluble salt to be neutralized the process of reaction with acidic precipitation agent or alkaline precipitating agent, aluminum soluble salt wherein used is one or more in aluminum chloride, aluminum sulfate, aluminum nitrate, acidic precipitation agent used is usually one or several in hydrochloric acid, sulphuric acid, nitric acid, oxalic acid, carbon dioxide etc., and alkaline precipitating agent used is usually one or several in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia etc..Aluminium oxide plastic can also adopt the method that meta-aluminate (such as sodium metaaluminate and/or potassium metaaluminate) and acid aluminium salt (in such as aluminum chloride, aluminum nitrate, aluminum sulfate one or more) are neutralized plastic.
In step of the present invention (2), amorphous silica-alumina plastic process can be undertaken by process well known to those skilled in the art.Plastic material generally comprises aluminum source (Al2(SO4)3、AlCl3、Al(NO3)3And NaAlO2Deng in one or more), silicon source (one or more in waterglass, Ludox and organic silicon-containing compound etc.), precipitant (NaOH, NH4OH or CO2Deng), using according to the different choice of plastic process, conventional mode of operation mainly has: (1) acid aluminium salt (Al2(SO4)3、AlCl3、Al(NO3)3) and basic aluminium salt (NaAlO2) or alkaline precipitating agent (NaOH, NH4OH) plastic, (2) basic aluminium salt (NaAlO are neutralized2) and acidic precipitation agent (CO2) neutralize plastic.Silicon source is typically in plastic process introducing plastic cans, it is also possible to neutralize plastic after aluminum source or precipitant mix again, add such as waterglass in basic aluminium salt or alkaline precipitating agent and be neutralized plastic, Ludox adds in acid aluminium salt and is neutralized plastic etc..Silicon source can also add after the precipitation of aluminum source in material.Two or more combination of aforesaid way can also be used.Said method is all well-known to those skilled in the art.
Described 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 ~ 8.0 hour is relatively adapted at 0.5 ~ 5.0 hour, it is preferred to 1.0 ~ 3.0 hours, 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) aluminium oxide or in amorphous silica-alumina plastic process, it is also possible to add 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 serosity of step (1) gained adopts the one or more combination of following manner: this serosity, in plastic process, is continuously added in plastic cans by (1)；(2) this serosity is charged first in plastic cans, then carries out plastic reaction；(3) this serosity is mixed with one or more of plastic material, then carry out plastic 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.
The nucleocapsid structure component that catalyst of the present invention adopts is by with the activated carbon of carried noble metal and rare earth metal for core, with aluminium oxide (or amorphous silica-alumina) for shell, make full use of activated carbon specific surface area big, high adsorption capacity and aluminium oxide (or amorphous silica-alumina) 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, reactant is so made first to contact with the aluminium oxide (or amorphous silica-alumina) as shell, deposition for impurity provides good space, the Properties of Activated Carbon promoting carried noble metal and rare earth metal plays better；On the other hand, aluminium oxide (or amorphous silica-alumina) has higher mechanical strength, provides good mechanical support and intensity for catalyst so that catalyst has good mechanical strength and anti-wear performance.This catalyst is particularly useful as catalytic wet oxidation catalyst, especially the catalytic wet oxidation catalyst of Love psychology.
In the preparation method of catalyst of the present invention, the activated carbon of preferred supported active metals processes through saccharide, so can make saccharide uniform adsorption on activated carbon surfaces externally and internally, make to be mixed in the carbohydrate breakdown carbonization in the middle of aluminium oxide (or amorphous silica-alumina) and activated carbon by follow-up roasting process, the activated carbon being newly formed connects aluminium oxide (or amorphous silica-alumina) and activated carbon, the combination making activated carbon and aluminium oxide (or amorphous silica-alumina) is tightr, be conducive to improving mechanical strength and the abrasion resisting performance of catalyst, and, activated carbon is more weak with the adhesion of active metal, activated carbon elder generation supported active metals, follow-up roasting process is carried out after adsorbing saccharide again, preferential and active metal attachment the activated carbon of newly-generated activated carbon is combined, it is coated on around active metal, active metal is in free and half free state in aqueous phase, the loss of active metal is not be provided providing sufficiently active while, the active metal that trace runs off enters liquid phase and participates in reaction with ionic condition, suitable adds reactivity, catalyst is made to have higher reactivity and stability in use.
Catalyst preparation process of the present invention is simple, convenient, it is easy to operation, is suitable for commercial production.
The catalyst of the present invention is applicable to CWO course of reaction, adopt air, oxygen-enriched air, ozone or peroxide as oxidant, continuous way or batch (-type) process high concentrated organic wastewater, are particularly well-suited to the CWO process improving temperature and reaction pressure.Using catalyst treatment waste water of the present invention can effectively reduce COD, that improves waste water can biochemical values.
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
Being joined by solid aluminum chloride in distilled water, 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 uses impregnation liquid containing Pt-Ce to impregnate, the activated carbon after dipping 120 DEG C dry 240 minutes, after lower 500 DEG C of roastings of nitrogen protection 4 hours; add mix homogeneously in D/W; 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
Solid aluminum sulfate being joined in distilled water, 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 uses impregnation liquid containing Rh-Ce to impregnate, the activated carbon after dipping 120 DEG C dry 240 minutes, after lower 500 DEG C of roastings of nitrogen protection 4 hours; add mix homogeneously in D/W; 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 roasting 5 hours, obtain catalyst B, its composition is in Table 2.
Embodiment 3
Solid aluminum sulfate being joined in distilled water, heating simultaneously is also stirred to dissolving, and obtains solution (a).It is 250gAl that solid sodium metaaluminate is configured to concentration2O3/ L sodium aluminate solution (b).Use impregnation liquid containing Rh-Ce to impregnate powdery coconut husk charcoal, the activated carbon after dipping 120 DEG C dry 240 minutes, after lower 500 DEG C of roastings of nitrogen protection 4 hours; add mix homogeneously in aqueous sucrose solution; liquid-solid volume ratio is 3:1, and then add water making beating, obtains serosity (c).Waterglass according to 1:2 dilution proportion in deionized water, be configured to solution (d).Take a plastic cans, insert the heating of 2L deionized water and stirring and add serosity (c) after 60 DEG C, open the valve of the container having (a), (b) simultaneously, control the pH=8.0 of system, in controlling 45 minutes, (a) is dripped off, close valve.Keeping temperature is 65 DEG C, pH=8.0, after stopping 20 minutes, adds solution (d) in system, calculates according to the content 55wt% of silicon dioxide in amorphous silica-alumina and added in 10 minutes.Then 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, obtains 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
Being joined by solid aluminum chloride in distilled water, 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 uses impregnation liquid containing Rh-Ce to impregnate, the activated carbon after dipping 120 DEG C dry 240 minutes, after lower 500 DEG C of roastings of nitrogen protection 4 hours; add mix homogeneously in D/W; 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-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
Solid aluminum sulfate being joined in distilled water, 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 uses impregnation liquid containing Pt-La to impregnate, the activated carbon after dipping 120 DEG C dry 240 minutes, after lower 500 DEG C of roastings of nitrogen protection 4 hours; add mix homogeneously in D/W; 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-5, then roasting 5 hours under 550 DEG C of conditions under nitrogen protection, pulverize and sieve and obtain powder catalyst J-5.The amount of plastic agents useful for same is listed in table 1.
Take catalyst material A-5100 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 E, its composition is in Table 2.
Embodiment 6
Repeat the synthesis of embodiment 2, without saccharide in plastic process, prepare catalyst material A-6 and powder catalyst J-6.
Preformed catalyst is prepared with embodiment 2, obtains catalyst F, and its composition is in Table 2.
Embodiment 7
Repeat the synthesis of embodiment 3, without saccharide in plastic process, prepare catalyst material A-7 and powder catalyst J-7.
Preformed catalyst is prepared with embodiment 3, obtains catalyst G, 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 carrier material PA-1 and powder carrier DF-1, its appearance white.
Take carrier material PA-1100 gram, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then dry 10 hours at 110 DEG C, roasting 5 hours under 550 DEG C of conditions, impregnate with the impregnation liquid containing Rh-Ce, then dry 10 hours at 110 DEG C, roasting 5 hours under 550 DEG C of conditions, obtain 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.Under nitrogen protection under 550 DEG C of conditions after roasting 5 hours, impregnate with the impregnation liquid containing Rh-Ce, then at 110 DEG C dry 10 hours, under nitrogen protection under 550 DEG C of conditions roasting 5 hours, obtain catalyst DB, its composition is in Table 2.
Comparative example 3
By activated carbon used in embodiment 2 with carrier 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.Under nitrogen protection under 550 DEG C of conditions after roasting 5 hours, impregnate with the impregnation liquid containing Rh-Ce, then at 110 DEG C dry 10 hours, under nitrogen protection under 550 DEG C of conditions roasting 5 hours, 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 | J-6 | J-7 |
| Aluminium salt, g | 723 | 471 | 125 | 677 | 187 | 471 | 125 |
| Sugar, g | 6 | 17 | 140 | 6 | 26 | - | - |
| Activated carbon, g | 118 | 140 | 770 | 111 | 130 | 147 | 829 |
| Chloroplatinic acid, g | 1.90 | - | - | - | 0.72 | - | - |
| Rhodium nitrate, g | - | 1.23 | 2.48 | 1.68 | - | 1.23 | 2.48 |
| Lanthanum (III) nitrate, g | - | - | - | - | 16.11 | - | - |
| Cerous nitrate, g | 91.65 | 42.28 | 108.66 | 83.68 | - | 42.28 | 108.66 |
The composition of table 2 catalyst and character
| Catalyst is numbered | A | B | C | D | E | F | G | DA | DB | DC |
| Pt, wt% | 0.26 | - | - | - | 0.49 | - | - | - | - | - |
| Rh, wt% | - | 0.31 | 0.26 | 0.23 | - | 0.49 | 0.27 | 0.31 | 0.30 | 0.31 |
| La, wt% | - | - | - | - | 9.30 | - | - | - | - | - |
| Ce, wt% | 10.70 | 9.73 | 10.63 | 10.44 | - | 9.45 | 10.43 | 9.73 | 9.63 | 9.82 |
| Specific surface area, m2/g | 434 | 558 | 663 | 435 | 533 | 529 | 629 | 262 | 812 | 502 |
| Pore volume, mL/g | 0.55 | 0.54 | 0.53 | 0.55 | 0.48 | 0.52 | 0.50 | 0.71 | 0.51 | 0.49 |
| Side pressure strength, N/cm | 223 | 187 | 165 | 228 | 155 | 167 | 152 | 239 | 45 | 164 |
| Abrasion, wt% | 0.50 | 0.60 | 0.70 | 0.60 | 0.70 | 0.70 | 0.83 | 0.28 | 4.55 | 0.90 |
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.
In the present invention, adopt X-ray photoelectron spectroscopy (XPS) that the element of embodiment 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-1 ~ A-7 surface is essentially identical, all has the elemental carbon of trace.This further illustrates, and the catalyst material of the present invention is with the activated carbon of carried noble metal and rare earth metal for core, with aluminium oxide or amorphous silica-alumina for shell.
Catalyst prepared by the invention described above embodiment and comparative example is evaluated.Evaluation test uses batch reactor, with hydrogen peroxide for oxide isolation, certain phenolic resin wastewater is carried out batch (-type) process.
Major pollutants COD:15000mg/L in waste water.
Treatment conditions are room temperature normal pressure, catalyst amount 1g/L, waste water 200mL, control ph 5 ~ 7, H2O2Concentration 800mg/L, stir speed (S.S.) 300rpm, time of staying 45min.Catalyst uses the result of handled waste water after 4 times to be listed in table 3.
Table 3 evaluation result
| Catalyst is numbered | B | C | F | G | DA | DB | DC |
| COD clearance, % | 98.0 | 97.1 | 95.4 | 95.8 | 84.5 | 96.2 | 94.1 |
From evaluation result it can be seen that adopt catalyst prepared by the inventive method, COD clearance is significantly higher.
Adopting the catalyst prepared with comparative example of the embodiment of the present invention to process above-mentioned waste water under identical process conditions, operate after 100 times, evaluation result is listed in table 4.
Table 4 estimation of stability result
| Catalyst is numbered | B | C | F | G | DA | DB | DC |
| COD clearance, % | 97.0 | 96.1 | 93.8 | 94.1 | 82.3 | 66.6 | 91.7 |
| Metal conservation rate in catalyst, % | 95.23 | 94.35 | 95.12 | 94.97 | 95.10 | 69.09 | 83.14 |
By table 4 result it can be seen that catalyst uses after 100 times, using catalyst activity prepared by the inventive method to reduce amplitude less, have good stability, the conservation rate of active metal substantially increases.
Claims (22)
1. a catalytic wet oxidation catalyst, including following nucleocapsid structure component, this nucleocapsid structure component is with the activated carbon of carried noble metal and rare earth metal for core, with aluminium oxide or amorphous silica-alumina for shell, with the weight of activated carbon and aluminium oxide or activated carbon and amorphous silica-alumina for benchmark, activated carbon accounts for 10% ~ 70%, and aluminium oxide or amorphous silica-alumina account for 30% ~ 90%.
2. the catalyst described in claim 1, it is characterised in that: described noble metal is one or several in Pt, Pd, Rh, Ru, and described rare earth metal is one or more in lanthanum, cerium, praseodymium, neodymium.
3. the catalyst described in claim 1, it is characterised in that: the granularity of described activated carbon is 150 order ~ 300 orders.
4. the catalyst described in claim 1, it is characterised in that: with the weight of activated carbon and aluminium oxide or activated carbon and amorphous silica-alumina for benchmark, activated carbon accounts for 30% ~ 70%, and aluminium oxide or amorphous silica-alumina account for 30% ~ 70%.
5. the catalyst described in claim 1, it is characterized in that in 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 or activated carbon and amorphous silica-alumina is 84.0% ~ 98.0%.
6. the catalyst described in claim 1, it is characterised in that in described amorphous silica-alumina, the weight content of silicon oxide is 10% ~ 90%, it is preferred to 30% ~ 70%.
7. the catalyst described in claim 1 or 3, it is characterised in that described catalyst or powder catalyst, or preformed catalyst, the granularity of powder catalyst is 0.05 ~ 0.20mm, and preformed catalyst granularity is 0.5 ~ 8.0mm.
8. the catalyst described in claim 7, 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.
9. the catalyst described in claim 1, it is characterised in that: containing auxiliary agent in described aluminium oxide or amorphous silica-alumina, auxiliary agent is one or more in titanium, zirconium, magnesium, zinc, and the weight content counted with element is for less than 10%.
10. the preparation method of the arbitrary described catalyst of claim 1 ~ 8, including:
(1) activated carbon of carried noble metal and rare earth metal is pulled an oar；
(2) in aluminium oxide or amorphous silica-alumina plastic process, the serosity that step (1) obtains is introduced；
(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 is made catalyst.
11. in accordance with the method for claim 10, it is characterised in that: the preparation of step (4) catalyst 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.
12. in accordance with the method for claim 10, it is characterised in that the character of step (1) described activated carbon is as follows: specific surface area 500 ~ 3000m2/ g, pore volume 0.5 ~ 1.8cm3/ g, average pore radius 1 ~ 10nm, granularity is 150 ~ 300 orders.
13. in accordance with the method for claim 10, it is characterised in that the making beating of activated carbon described in step (1) adopt 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.
14. in accordance with the method for claim 10, it is characterised in that carried noble metal and the activated carbon of rare earth metal described in step (1) first adopt saccharide to process, and then pull an oar, and described saccharide is carbon number is one or more in the saccharide of 3 ~ 20.
15. in accordance with the method for claim 14, it is characterised in that described saccharide consumption accounts for the 2% ~ 50% of activated carbon weight, it is preferred to 5% ~ 20%.
16. in accordance with the method for claim 14, it is characterised in that described saccharide is one or more in triose, tetrose, pentose, hexose, maltose, glucose, sucrose, it is preferred to one or more in glucose, sucrose.
17. in accordance with the method for claim 14, it is characterized in that: it is directly mixed with activated carbon by saccharide that saccharide processes activated carbon, or saccharide is dissolved in solvent and adds activated carbon, solvent therein is water, carbon number be 1 ~ 5 monohydric alcohol in one or more；When saccharide processes activated carbon, its liquid-solid volume ratio is below 10.
18. in accordance with the method for claim 10, it is characterised in that: the aluminium oxide described in step (2) or amorphous silica-alumina plastic process adopt the mode of the continuous acid-base titration of soda acid, or adopt two kinds of materials and flow the mode of neutralization.
19. in accordance with the method for claim 10, it is characterised in that: in step (2), the incorporation way of the serosity of step (1) gained adopts the one or more combination of following manner: this serosity, in plastic process, is continuously added in plastic cans by (1)；(2) this serosity is charged first in plastic cans, then carries out plastic reaction；(3) this serosity is mixed with one or more of plastic material, then carry out plastic reaction.
20. in accordance with the method for claim 10, it is characterised in that: the aluminium oxide described in step (2) or in amorphous silica-alumina plastic process, introduce adjuvant component, namely titanium, zirconium, magnesium, one or more in zinc.
21. in accordance with the method for claim 10, it is characterised in that: in step (3), described drying condition is as follows: dry 1 ~ 15 hour at 50 ~ 150 DEG C.
22. in accordance with the method for claim 11, it is characterized in that: in step (4), roasting condition described in method A is as follows: sintering temperature is 450 ~ 700 DEG C, roasting time is 1 ~ 10 hour, drying condition described in method B is at 80 ~ 200 DEG C, dry 1 ~ 15 hour, sintering temperature is 450 ~ 700 DEG C, roasting time is 1 ~ 10 hour, 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, roasting time is 1 ~ 10 hour, then then through molding, after drying, roasting under inert gas shielding, obtain catalyst, drying condition after molding is as follows: at 80 ~ 200 DEG C, dry 1 ~ 15 hour, roasting condition is as follows: sintering temperature is 450 ~ 700 DEG C, roasting time is 1 ~ 10 hour.
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