CN105618066A - Catalytic wet oxidation catalyst and preparation method thereof - Google Patents
Catalytic wet oxidation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalytic wet oxidation catalyst and a preparation method thereof. The catalyst comprises a core-shell structured component, the core-shell structured component adopts active carbon as a core and alumina or amorphous silica-alumina containing transition metals and rare earth metals as a shell, and the preparation method comprises the following steps: introducing an active carbon slurry in the gel formation process of co-precipitation process prepared alumina or amorphous silica-alumina, transition metals and rare earth metals, forming gel, and ageing to obtain the catalyst. The catalyst is especially suitable for being used as a catalytic wet oxidation catalyst, especially a catalytic wet oxidation catalyst of sewage from refinery, and has improved activity and use stability.
Description
Technical field
The present invention relates to a kind of catalytic wet oxidation catalyst and preparation method thereof, particularly containing catalytic wet oxidation catalyst of activated carbon and aluminium oxide or amorphous silica-alumina and preparation method thereof.
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, makes, 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 catalytic wet oxidation catalyst and preparation method thereof.
The catalytic wet oxidation catalyst of the present invention, including 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 or the amorphous silica-alumina containing transition metal and rare earth metal 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%.
In catalyst of the present invention, 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 of the present invention, 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 of the present invention, 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 or activated carbon and amorphous silica-alumina is 70% ~ 98%, it is preferred to 80% ~ 98%.
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.
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.
In the described amorphous silica-alumina containing transition metal and rare earth metal, with the weight of amorphous silica-alumina for benchmark, the content of silicon oxide is 10% ~ 90%, it is preferred to 30% ~ 70%.
The heretofore described aluminium oxide containing transition metal and rare earth metal or the amorphous silica-alumina containing 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 in the plastic process of aluminium oxide or amorphous silica-alumina and transition metal and rare-earth metal complex, introducing step (1) obtains;
(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 one or more in 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 or amorphous silica-alumina and transition metal and rare earth metal composite oxide can be undertaken by process well known to those skilled in the art. 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.
In step of the present invention (2), adopt coprecipitation to prepare amorphous silica-alumina and transition metal and rare earth metal composite oxide be aluminum source, silicon source, transition metal source and rare earth metal source (transition metal source be preferably in vanadium source, chromium source, manganese source, source of iron, cobalt source, copper source and titanium source one or more, one or more in lanthanum source, cerium source of rare earth metal source) react with precipitant and to carry out plastic. 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. 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 is that 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 ~ 8.0 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) adopts coprecipitation to prepare in the process of aluminium oxide or amorphous silica-alumina and transition metal and rare-earth metal complex, the adjuvant component that carrier is conventional can also be added, 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; obtaining catalyst, the drying condition after molding is as follows: at 80 ~ 200 DEG C, dry 1 ~ 15 hour; roasting condition is 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.
Catalyst of the present invention adopt nucleocapsid structure component be by with activated carbon be core, with the aluminium oxide (or amorphous silica-alumina) 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 (or amorphous silica-alumina) 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 elder generation and aluminium oxide (or amorphous silica-alumina) haptoreaction containing active metal as shell; On the other hand, aluminium oxide (or amorphous silica-alumina) 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, make catalyst have higher reactivity and stability in use, improve the service life of catalyst. This catalyst is particularly useful as catalytic wet oxidation catalyst, especially the catalytic wet oxidation catalyst of Love psychology, the stability of activity and use to improve catalyst.
In the preparation process of catalyst of the present invention, aluminium oxide (or amorphous silica-alumina) and introducing activated carbon in the plastic process of transition metal and rare-earth metal complex is prepared in coprecipitation, so make aluminium oxide (or amorphous silica-alumina) the colloid coating active charcoal containing transition metal and rare earth metal, formed with activated carbon for core, the complex being shell with the aluminium oxide (or amorphous silica-alumina) containing transition metal and rare earth metal, so fully utilize activated carbon specific surface area big, advantage and aluminium oxide (or amorphous silica-alumina) mechanical strength that absorption affinity is strong are high, aperture is big, the advantage of pore distribution concentration, aluminium oxide (or amorphous silica-alumina) coating active charcoal, activated carbon is made to be evenly distributed in aluminium oxide (or amorphous silica-alumina), aluminium oxide (or amorphous silica-alumina) 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 (or amorphous silica-alumina) simultaneously, catalyst is provided powerful specific surface area by activated carbon, activated carbon fine dispersion in aluminium oxide (or amorphous silica-alumina) 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 the aluminium oxide (or amorphous silica-alumina) prepared containing transition metal and 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 (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, 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, aluminium oxide (or amorphous silica-alumina) closely coating active charcoal can be promoted, 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.
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
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 sulfate, cerous nitrate, ferric nitrate, 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). Powdery coconut husk charcoal is added mix homogeneously in aqueous sucrose solution, and 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
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-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
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-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 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 | J-6 | J-7 |
| Aluminium salt, g | 1007 | 1284 | 142 | 1556 | 632 | 1284 | 142 |
| Sugar, g | 9 | 48 | 163 | 13 | 81 | - | - |
| Activated carbon, g | 165 | 383 | 880 | 255 | 440 | 402 | 948 |
| Cerous nitrate, g | 61 | 108 | 116 | 98 | - | 108 | 116 |
| Copper nitrate, g | 71 | 120 | - | - | 72 | 120 | - |
| Ferric nitrate, g | - | - | 230 | - | - | - | 230 |
| Manganese nitrate, g | - | - | - | 130 | - | - | - |
| Lanthanum (III) nitrate, g | - | - | - | - | 61 | - | - |
The composition of table 2 catalyst and character
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 or amorphous silica-alumina for shell.
Catalyst prepared by the invention described above embodiment and comparative example is evaluated. Catalyst packing is in bubbling bed reactor, with ozone for oxide isolation, containing phenol, sulfur-containing waste water, certain oil plant is carried out batch (-type) process.
Major pollutants COD:1500mg/L, S in waste water2-: 280mg/L, volatile phenol: 180mg/L.
Treatment conditions are room temperature normal pressure, catalyst amount 100g, waste water 200mL, ozone amount 35mg/L, time of staying 30min. 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, mg/L | 66.09 | 65.81 | 82.13 | 84.86 | 104.20 | 60.69 | 87.62 |
| S2-, mg/L | 0.56 | 0.65 | 1.98 | 0.79 | 7.50 | 0.81 | 3.37 |
| Volatile phenol, mg/L | 0.45 | 0.50 | 0.54 | 0.61 | 2.34 | 0.40 | 1.35 |
From table 3 evaluation result it can be seen that use catalyst prepared by the inventive method to have good activity.
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 using 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, mg/L | 86.90 | 87.30 | 101.04 | 109.08 | 135.38 | 233.28 | 124.46 |
| S2-, mg/L | 2.96 | 2.96 | 4.39 | 3.89 | 12.97 | 22.87 | 4.59 |
| Volatile phenol, mg/L | 0.58 | 1.29 | 2.53 | 2.97 | 9.57 | 26.99 | 3.21 |
| CeO in catalyst2, wt% | 3.95 | 2.62 | 3.92 | 2.53 | 3.98 | 2.17 | 3.05 |
| CuO in catalyst2, wt% | 3.91 | - | 3.81 | - | 3.87 | 2.11 | 3.01 |
| Fe in catalyst2O3, wt% | - | 2.47 | - | 2.59 | - | - | - |
By table 4 result it can be seen that use catalyst prepared by the inventive method to have good stability, catalyst metals turnover rate substantially reduces.
Claims (22)
1. a catalytic wet oxidation catalyst, including 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 or the amorphous silica-alumina containing transition metal and rare earth metal 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: 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%.
3. the catalyst described in claim 1, it is characterised in that: 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.
4. the catalyst described in claim 1, it is characterised in that: described transition metal is selected from one or more in vanadium, chromium, manganese, ferrum, cobalt, copper and titanium, and described rare earth metal is one or more in lanthanum, cerium.
5. the catalyst described in claim 1, it is characterised in that: with the weight of amorphous silica-alumina for benchmark, the content of silicon oxide is 10% ~ 90%, it is preferred to 30% ~ 70%.
6. the catalyst described in claim 1, it is characterized in that: with the weight of catalyst for benchmark, the weight content of transition metal oxide is 1% ~ 15%, the weight content of rare-earth oxide is 1% ~ 15%, and the weight content of activated carbon and aluminium oxide or activated carbon and amorphous silica-alumina is 70% ~ 98%.
7. the catalyst described in claim 1, it is characterised in that: described catalyst is the powder catalyst not needing molding, or preformed catalyst, and 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 ~ 250N/cm to rate of wear.
9. the catalyst described in claim 1, it is characterized in that: containing auxiliary agent in the described aluminium oxide containing transition metal and rare earth metal or the amorphous silica-alumina containing transition metal and rare earth metal, auxiliary agent is one or more in titanium, zirconium, magnesium, zinc, and the content counted with element is for less than 10%.
10. the preparation method of the arbitrary described catalyst of claim 1 ~ 8, including:
(1) by 150 order ~ 300 order activated carbon making beating;
(2) coprecipitation is being adopted to prepare the activated carbon serosity that in the plastic process of aluminium oxide or amorphous silica-alumina and transition metal and rare-earth metal complex, introducing step (1) obtains;
(3) material after the plastic that step (2) obtains carry out aging, filter, washing, dry;
(4) material of step (3) gained is made catalyst.
11. in accordance with the method for claim 10, it is characterised in that: the material of step (3) gained is made catalyst and is at least adopted one of following method by step (4):
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.
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.
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 the activated carbon described in step (1) first adopts saccharide to process, and then pulls an oar, 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 characterized in that: the coprecipitation described in step (2) prepares the neutralization course of reaction that the plastic process of aluminium oxide or amorphous silica-alumina and transition metal and rare earth metal composite oxide is acid material and alkaline material, plastic process adopts the mode of the continuous acid-base titration of soda acid, or adopts two kinds of materials and flow the mode of neutralization.
19. in accordance with the method for claim 10, it is characterized in that: the coprecipitation described in step (2) is prepared in the plastic process of aluminium oxide or amorphous silica-alumina and transition metal and rare earth metal composite oxide, introduce adjuvant component, namely titanium, zirconium, magnesium, one or more in zinc.
20. in accordance with the method for claim 10, it is characterized in that: in step (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) this mixture is mixed with one or more of coprecipitation reaction material, then carry out coprecipitation reaction.
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 was 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour; 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; drying condition after molding is as follows: at 80 ~ 200 DEG C; dry 1 ~ 15 hour, roasting condition was as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
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