CN105709743B - A kind of catalytic wet oxidation catalyst and its preparation method - Google Patents
A kind of catalytic wet oxidation catalyst and its preparation method Download PDFInfo
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- CN105709743B CN105709743B CN201410706805.8A CN201410706805A CN105709743B CN 105709743 B CN105709743 B CN 105709743B CN 201410706805 A CN201410706805 A CN 201410706805A CN 105709743 B CN105709743 B CN 105709743B
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Abstract
The invention discloses a kind of catalytic wet oxidation catalyst and preparation method thereof.The catalyst includes following core shell structure components, the core shell structure component is using the activated carbon of carrying transition metal as core, using the aluminium oxide containing rare earth metal or amorphous silica-alumina as shell, its preparation method is the activated carbon slurries that carrying transition metal is introduced during the plastic of aluminium oxide or amorphous silica-alumina and rare-earth metal complex, after plastic through aging and etc. obtain catalyst.Catalyst of the present invention has higher reactivity and stability in use.
Description
Technical field
The present invention relates to a kind of catalytic wet oxidation catalyst and preparation method thereof, particularly containing activated carbon and aluminium oxide or
Catalytic wet oxidation catalyst of amorphous silica-alumina and preparation method thereof.
Background technology
It is increasingly stringent with global environmental regulation, the Con trolling index of sewage qualified discharge require it is higher and higher, herein
Under form, waste water treatment by catalytic oxidation has increasingly obtained the attention and use of people, and the catalysis such as high-concentration sewage is wet
Formula oxidation, catalytic and oxidative electrolysis technology, photochemical catalytic oxidation, advanced oxidation etc..In waste water catalytic oxidation process, to obtain preferably place
Reason effect and by reducing reaction temperature, reaction pressure to keep relatively low wastewater treatment expense, prepare with high-activity component,
High intensity, the cheap catalyst of high stability undoubtedly become the key of waste water catalytic oxidation technologies application.
The catalyst of waste water catalysis oxidation is broadly divided into two class of homogeneous catalyst and heterogeneous solid catalyst.
Homogeneous catalyst is mainly included to produce Fenton reagent, the Fe of oxygen radical3+、Cu2+, the metal such as cobalt and manganese
Ion, by means of the effect of these homogeneous catalysts, organic component, sulfide, ammonia nitrogen in waste water etc. are by air, oxygen, smelly
The oxide isolations such as oxygen, hydrogen peroxide are oxidized into low molecular acid (low mass molecule alcohol or carbon dioxide), sulfate or thiosulfuric acid
Salt, nitrogen etc., make waste water reach the processing intent of decarburization, desulfurization and denitrogenation.Homogeneous oxidation catalyst prepare and using process compared with
To be simple, the metal salts such as iron, copper, cobalt, manganese generally can be directly selected to be made into aqueous solution or be directly thrown into handled waste water,
And used by being discharged in the water outlet after handling or regenerating Posterior circle.Using homogeneous catalytic oxidation, since metal active constituent is useless
Fully it can dissolve and disperse in water, generally can reach relatively stable water treatment effect, but there is reagent consumption is big, fortune
The row serious problems such as costly, metal loss and secondary pollution, cause its application to be subject to larger limitation.
Heterogeneous solid catalyst mainly with activated carbon, molecular sieve, amorphous alumina, titanium dioxide etc. for carrier, with
One or more in alkali metal, alkaline-earth metal, transition metal or Pt, Pd noble metal make the catalyst of active component composition.It is living
Property charcoal be black, hole are flourishing, specific surface area is big, adsorption capacity is strong made of carbonaceous material a kind of microcrystalline carbon.Activity
Charcoal property is stablized, acidproof, alkaline-resisting, heat-resisting, not soluble in water or organic solvent, easily regeneration, is a kind of environmentally friendly adsorbent, extensively
It is general to be applied to the fields such as Industrial " three Waste " improvement, food, medicine, carrier, semiconductor, battery and power storage.Currently used for useless
The heterogeneous solid catalyst of water process selects activated carbon as carrier mostly, but the catalysis for selecting activated carbon supported metal to prepare
Agent wear-resisting property is poor, and mechanical strength is not high, and the metal of load is easy to run off so that the application effect of activated-carbon catalyst has beaten folding
Button.Because having good chemical stability, large pore volume, there is amorphous alumina certain acidity, pore size distribution$ to concentrate, machine
The advantages that tool intensity is big, corrosion-resistant, is widely used in catalytic field, but amorphous alumina is in the presence of smaller than surface
Shortcoming, the absorption and conversion capability to organic matter are relatively small.
CN201110225789.7 discloses a kind of side that benzene adsorption material is prepared using discarded active amorphous aluminium oxide
Method, it be by useless active amorphous aluminium oxide is cleaned, filtering, it is dry after, prepared using cryogenic seal heat treatment mode a kind of
Active amorphous aluminium oxide/absorbent charcoal composite material, has good adsorption effect to benzene.This method is by amorphous alumina
Internal organic matter carbonizing, activated carbon are mainly distributed in the duct of amorphous alumina, so can not only block aluminium oxide
Duct, and the activated carbon so generated skewness in aluminium oxide.
CN201110255525.6 discloses a kind of preparation method of active amorphous aluminium oxide/absorbent charcoal composite material,
It is to pass through waste aluminum sludge, activated carbon, binding agent mix, be granulated, is aging, being molded, drying, sintering, rinsing, is dry
And etc. active amorphous aluminium oxide/absorbent charcoal composite material is made.This method belongs to salic species and activated carbon thing
Mixed process is managed, aluminium oxide and activated carbon disperse uneven；And used sludge impurity content is high, the amorphous of gained
Aluminium property is unstable, can not repeat, complicated.
CN201010267074.3 discloses a kind of preparation method of activated alumina composite reactive Carbon Materials, with hydroxide
Aluminium, activated carbon and binding agent are raw material, through mixing, being granulated, it is aging, be molded, dry, sintering, rinsing, drying and other steps, so
Obtained composite material is still the physical mixture of aluminium oxide and activated carbon, and aluminium oxide disperses uneven, its synthesis with activated carbon
Performance also needs to further improve.
The content of the invention
In view of the deficiencies of the prior art, have that catalytic performance is good, high mechanical strength the present invention provides one kind, wearability
Catalytic wet oxidation catalyst that energy is strong, stability in use is good and preparation method thereof.
The catalytic wet oxidation catalyst of the present invention, including following core shell structure components, the core shell structure component are with negative
The activated carbon of carried transition metal is core, using the aluminium oxide containing rare earth metal or the amorphous silica-alumina containing rare earth metal as shell, with work
Property charcoal and aluminium oxide or activated carbon and amorphous silica-alumina weight on the basis of, activated carbon accounts for 10% ~ 70%, be preferably 30% ~ 70%, oxidation
Aluminium or amorphous silica-alumina account for 30% ~ 90%, are preferably 30% ~ 70%.
In catalyst of the present invention, the transition metal is in the base metal in the 4th and 5 cycles in the periodic table of elements
One or more, the granularity of the activated carbon are the mesh of 150 mesh ~ 300.
In catalyst of the present invention, one or more of the transition metal in vanadium, chromium, manganese, iron, cobalt, copper and titanium.The present invention
In catalyst, the rare earth metal is lanthanum, the one or more in cerium.
In catalyst of the present invention, on the basis of the weight of catalyst, the content of transition metal oxide is 1% ~ 15%, preferably
For 1% ~ 10%, the content of rare-earth oxide is 1% ~ 15%, is preferably 1% ~ 10%, activated carbon and aluminium oxide or activated carbon and nothing
The content of amorphous silicon-alumina is 70% ~ 98%, is preferably 80% ~ 98%.
In the amorphous silica-alumina containing rare earth metal, on the basis of the weight of amorphous silica-alumina, the weight of silica contains
Measure as 10% ~ 90%, preferably 30% ~ 70%.
The catalyst of the present invention can be not required to molding powder catalyst or preformed catalyst.It is powdered
The granularity of catalyst is generally 0.05 ~ 0.20mm.Preformed catalyst can determine the size of granularity as needed, generally 0.5 ~
8.0mm。
The property of preformed catalyst of the present invention is as follows：Specific surface area is 200 ~ 1000m2/ g, pore volume are 0.3 ~ 1.8cm3/
G, rate of wear<3wt%, side pressure strength are 100 ~ 250N/cm.
Contain auxiliary agent in heretofore described aluminium oxide or amorphous silica-alumina, auxiliary agent can be selected from titanium, zirconium, magnesium, zinc etc.
Middle one or more, weight content based on the element are preferably 1% ~ 5% below 10%.
The preparation process of catalytic wet oxidation catalyst of the present invention, including：
(1) activated carbon of carrying transition metal is beaten；
(2) during the plastic of aluminium oxide or amorphous silica-alumina and rare-earth metal complex is prepared using coprecipitation
Introduce step（1）Obtained slurries；
(3) step（2）Material after obtained plastic carries out aging, filtering, washing, drying；
(4) by step（3）Catalyst is made in the material of gained, preferably at least using one of following methods：
A, by step（3）The material of gained, roasts under inert gas shielding, obtains catalyst；
B, by step（3）The material forming of gained, after drying, roasts under inert gas shielding, obtains catalyst；
C, by step（3）The material of gained roasts under inert gas shielding, then again through shaping, after dry, in inertia
Roasted under gas shield, obtain catalyst.
Conventional Powdered Activated Carbon commodity can be selected in step (1) the of the present invention activated carbon, such as all kinds of wood activated charcoals, fruit
Shell activated carbon, active carbon from coal；Can also select with wooden material, mineral material, plastics and discarded object, as timber, sawdust, charcoal,
It is coconut husk, fruit stone, shell, coal, gangue, petroleum coke, asphalt, polyvinyl chloride, polypropylene, organic resin, damaged tire, surplus
The various activated carbon products that remaining sludge etc. is obtained through traditional preparation methods.Activated carbon used in the present invention is powder activated
Charcoal, 150 ~ 300 mesh of granularity, 500 ~ 3000m of specific surface area2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius.
In the method for the present invention, step（1）The activated carbon mashing of the carrying transition metal is carried out using conventional method, and one
As using plus water, the one or more in low-carbon alcohols be beaten, wherein low-carbon alcohols are in the monohydric alcohol that carbon number is 1 ~ 5
It is one or more.Step（1）The activated carbon of middle carrying transition metal is loaded using conventional method, such as infusion process.It is specific as follows：
Maceration extract is configured to transition metal salt, then active carbon particle is dipped into above-mentioned maceration extract, then through dry and roasting, is obtained
It is therein to use single-steeping to the activated carbon of carrying transition metal, multiple maceration can also be used.Wherein prepare leaching
Transition metal salt used can use soluble-salt, such as nitrate, chloride etc. during stain liquid, and those skilled in the art can be with
Determined according to actual conditions.
In the method for the present invention, step（1）It is preferred that the activated carbon of carrying transition metal is first handled using carbohydrate, then beaten
Slurry.The carbohydrate is monosaccharide and disaccharide, the one or more in polysaccharide, and preferably carbon number is one in 3 ~ 20 carbohydrate
Kind is a variety of, such as：One or more in triose, tetrose, pentose, hexose, maltose, glucose, sucrose, more preferably Portugal
One or more in grape sugar, sucrose.The carbohydrate dosage accounts for the 2% ~ 50% of activated carbon weight, is preferably 5% ~ 20%.Carbohydrate
Processing activated carbon can directly mix carbohydrate with activated carbon, carbohydrate can also be dissolved in solvent and add activated carbon, wherein
Solvent for water, low-carbon alcohols（I.e. carbon number is 1 ~ 5 monohydric alcohol）In one or more.When carbohydrate handles activated carbon, its
Liquid consolidates volume ratio below 10, preferably 1 ~ 5.Carbohydrate processing activated carbon after, excessive liquid phase is preferably filtered to remove, then again into
Row mashing.Being beaten can use conventional method to carry out, and general use adds the one or more in water, low-carbon alcohols to be beaten, wherein
Low-carbon alcohols are the one or more in the monohydric alcohol that carbon number is 1 ~ 5.
Step of the present invention（2）In, aluminium oxide or amorphous silica-alumina and rare earth metal combined oxidation are prepared using coprecipitation
Thing can be carried out by process well known to those skilled in the art.The neutralization plastic process of usually acid material and alkaline material.
Plastic process can be by the way of the continuous acid-base titration of soda acid, can also be by the way of two kinds of material cocurrents neutralize.
Step of the present invention（2）In, it is in silicon source, dilute to prepare aluminium oxide and rare earth metal composite oxide using coprecipitation
Earth metal source carries out plastic with precipitating reagent reaction, and silicon source is aluminium chloride, the one or more in aluminum sulfate, aluminum nitrate, used
Precipitating reagent is usually the one or several kinds in sodium carbonate, sodium acid carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide etc..It is wherein used
Rare earth metal source generally use soluble metallic salt（Such as nitrate, chloride etc.）, can be according to metal salt solution used
Acid-base property, be mixed for being co-precipitated with corresponding acid material or alkaline material, can also first add plastic cans, it is then acid
Material carries out plastic with alkaline material, and above content those skilled in the art are according to known to coprecipitation.
Step of the present invention（2）In, using coprecipitation prepare amorphous silica-alumina and rare earth metal composite oxide be silicon source,
Silicon source, rare earth metal source and precipitating reagent reaction carry out plastic.Plastic material generally comprises silicon source（Al2(SO4)3、AlCl3、Al
(NO3)3And NaAlO2One or more in）, silicon source（One kind in waterglass, Ludox and organic silicon-containing compound etc. or
It is several）, precipitating reagent（NaOH、NH4OH or CO2Deng）, used according to the different selections of plastic process, conventional mode of operation is main
Have：（1）Acid aluminium salt（Al2(SO4)3、AlCl3、Al(NO3)3）With basic aluminium salt（NaAlO2）Or alkaline precipitating agent（NaOH、
NH4OH）Neutralize plastic,（2）Basic aluminium salt（NaAlO2）With acidic precipitation agent（CO2）Neutralize plastic.Silicon source is generally in plastic process
Middle introducing plastic cans, can also be with neutralizing plastic, as waterglass adds basic aluminium salt or alkalescence again after silicon source or precipitant mix
Neutralization plastic is carried out in precipitating reagent, Ludox, which is added in acid aluminium salt, to carry out neutralizing plastic etc..Silicon source can also add silicon source and sink
Behind shallow lake in material.Can also be by two or more combined use of aforesaid way.Generally adopt in rare earth metal source wherein used
Use soluble metallic salt（Such as nitrate, chloride etc.）, can be according to the acid-base property of metal salt solution used, with corresponding acid
Property material or alkaline material be mixed for being co-precipitated, can also first add plastic cans, then acid material is carried out with alkaline material
Plastic, above content are those skilled in the art according to known to coprecipitation.
The coprecipitation, plastic process generally carry out at room temperature ~ 85 DEG C, are relatively suitably for 40 ~ 80 DEG C, are preferably 50
~70℃.The plastic process generally carries out under certain pH value condition, and typical pH is 6.0 ~ 10.0, is relatively suitably for 7.0
~ 9.5, it is preferably 7.5 ~ 9.0.Step（3）The aging, condition are as follows：PH is 6.0 ~ 10.0, is preferably 7.0 ~ 9.5, aging
When time 0.25 ~ 8.0 is small, relatively it is adapted to when 0.5 ~ 5.0 is small, when being preferably 1.0 ~ 3.0 small, aging temperature is room temperature ~ 85 DEG C, excellent
Elect 40 ~ 80 DEG C as.Temperature and pH and temperature during neutralization and pH during aging is preferably identical.
In the present invention, step（2）Aluminium oxide or amorphous silica-alumina are with that during rare earth metal co-precipitation plastic, can also add
Enter the common adjuvant component of carrier, such as the one or more in titanium, zirconium, magnesium, zinc etc..
Step of the present invention（2）In, step（1）The incorporation way of the slurries of gained uses one or more of groups of following manner
Close：（1）During plastic, which is continuously added in plastic cans；（2）The slurries are charged first in plastic cans, then
Carry out plastic reaction；（3）The slurries are mixed with the one or more of plastic material, then carry out plastic reaction.
Step of the present invention（3）In, the mode of washing of the material is known in those skilled in the art, can be selected
Add the modes such as water washing, lower alcohols washing when mashing washing, filtering, the temperature of washing should be in the temperature model of room temperature ~ 90 DEG C
In enclosing, preferably 50 ~ 70 DEG C.The washing of the material carries out in the range of being generally 1.0 ~ 9.0 in pH, and preferably pH is 4.0 ~ 8.5.
Step of the present invention（3）Described in material should be free of or include containing minimal amount of heteroion, heteroion after washing, filtering
Na+、Cl-、SO4 2-、NO3 -、K+One or more in.
Step of the present invention（3）In, the material is after washing, filtering, and filter cake is dried, and drying mode can use
Natural drying, oven drying, spray drying, microwave drying or infra-red drying, the drying condition generally used are as follows：50 ~
When drying 1 ~ 15 is small at 150 DEG C.
Step of the present invention（4）In, method A is to obtain powder catalyst without shaping roasting direct.Roasting described in method A
Burning condition is as follows：Calcination temperature is 450 ~ 700 DEG C, when roasting time is 1 ~ 10 small.
Step of the present invention（4）In, method B and the shaping described in method C can carry out as needed, generally strip, circle
Column, spherical, irregular strip, special-shaped ball etc., granularity can determine as needed, be generally 0.5 ~ 8.0mm.The forming process
In, the one or more in shaping assistant such as adhesive, peptization acid, extrusion aid can be added as needed.
Step of the present invention（4）In, the drying condition described in method B is generally at 80 ~ 200 DEG C, when drying 1 ~ 15 is small, roasting
Temperature is generally 450 ~ 700 DEG C, roasting time be generally 1 ~ 10 it is small when.
Step of the present invention（4）In, in method C, by step（3）The material of gained roasts under inert gas shielding, described
Roasting condition it is as follows：Calcination temperature is 450 ~ 700 DEG C, when roasting time is 1 ~ 10 small.Then again through being molded, after dry,
Roasted under inert gas shielding, obtain catalyst, the drying condition after shaping is as follows：At 80 ~ 200 DEG C, when drying 1 ~ 15 is small, roasting
Burning condition is as follows：Calcination temperature is generally 450 ~ 700 DEG C, roasting time be generally 1 ~ 10 it is small when.
In the present invention, roasted under inert gas shielding, selected inert gas is generally nitrogen or argon gas.
The core shell structure component that catalyst of the present invention uses is using the activated carbon of carrying transition metal as core, with containing rare earth gold
The aluminium oxide of category（Or amorphous silica-alumina）For shell, so make the first aluminium oxide with as shell of reactant（Or amorphous silica-alumina）Connect
Touch after reacting, then reacted with being contacted as the activated carbon of stratum nucleare, make full use of aluminium oxide（Or amorphous silica-alumina）Aperture is big,
The characteristics of pore volume is high, mechanical strength is good, the same aluminium oxide of rare earth metal auxiliary agent（Or amorphous silica-alumina）Combination can effectively improve
Aluminium oxide（Or amorphous silica-alumina）Heat endurance；Make full use of that activated carbon specific surface area is big, adsorption capacity is strong, reaction is lived at the same time
Property it is high the characteristics of, activated carbon with transition metal combination can preferably using activated carbon surface nature and transition metal catalysis
Activity, makes catalyst have higher reactivity and stability in use.The catalyst is urged particularly useful as catalytic wet oxidation
The catalytic wet oxidation catalyst of agent, especially Love psychology, with the stability for improving the activity of catalyst and using.
In the preparation process of catalyst of the present invention, in particular by carbohydrate processing carrying transition metal activated carbon after again
Mashing, is then preparing aluminium oxide（Or amorphous silica-alumina）With being introduced during the plastic of rare-earth metal complex, carbohydrate is uniform
Absorption on the surfaces externally and internally of activated carbon, make to be mixed in aluminium oxide by follow-up roasting process（Or amorphous silica-alumina）And work
Property charcoal among carbohydrate breakdown charing, newly formed activated carbon connection aluminium oxide（Or amorphous silica-alumina）And activated carbon so that living
Property charcoal and aluminium oxide（Or amorphous silica-alumina）Combination it is even closer, furthermore due to the combination power of activated carbon and active metal compared with
It is weak, activated carbon elder generation supported active metals, then carried out after adsorbing carbohydrate in follow-up roasting process, newly-generated activated carbon preferentially with
The activated carbon of active metal attachment combines, and is coated on around active metal, and active metal is in free in water phase and half is free
State, is not easy to cause the loss of active metal while sufficient activity is provided, and the absorption for adding activated carbon inner surface is lived
Property position.It is therefore preferable that increase carbohydrate processing activated carbon, can promote aluminium oxide（Or amorphous silica-alumina）Closely parcel is lived
Property charcoal, be conducive to improve the mechanical strength and attrition resistance energy of catalyst, while reduce the loss of active metal on activated carbon,
And the utilization rate of the inner surface of activated carbon is improved, be conducive to improve the activity and stability of catalyst.
Catalyst preparation process of the present invention is simply, conveniently, easily operated, is adapted to industrial production.
The catalyst of the present invention is suitable for catalytic wet oxidation reaction process, using air, oxygen-enriched air, ozone or mistake
Oxide as oxidant, continous way or intermittent processing high concentrated organic wastewater, especially suitable for improve temperature and
The catalytic wet oxidation process of reaction pressure.COD can be effectively reduced using catalyst treatment waste water of the present invention, that improves waste water can
Biochemical values.
Embodiment
The specific surface area and pore volume of product of the present invention are measured using low temperature liquid nitrogen physisorphtion.Rate of wear is to use to turn
Cartridge type abrasion instrument measures（It is specifically shown in《Catalyst carrier prepares and application technology》（Petroleum industry publishing house, in May, 2002, Zhu Hong
Method is write, 4.5.4 sections）.Grained catalyst granularity is measured using laser particle size analyzer；Preformed catalyst granularity is using sieve
Point-score measures.In the present invention, wt% is mass fraction.
The preparation method of the present invention is further illustrated with reference to specific embodiment, but the scope of the present invention is not only
It is limited to the scope of these embodiments.
The property of commercially available powdery coconut husk charcoal used is as follows in the present invention：Specific surface area 928m2/ g, pore volume 1.0cm3/ g, put down
Equal pore radius 1.1nm, iodine sorption value 700mg/g, 200 mesh of granularity.
Embodiment 1
Solid aluminum chloride, cerous nitrate are added in distilled water, while heats and stirs to dissolving, obtains solution (a).Will
Concentrated ammonia liquor adds appropriate distilled water and is diluted to about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Cu, and 120
DEG C dry 240 minutes, when the lower 550 DEG C of roastings 4 of nitrogen protection are small, add in glucose solution and be uniformly mixed, liquid consolidates volume ratio
For 3：1, then plus water is beaten, and obtains slurries (c).After (a) is added in plastic cans and is heated with stirring to 60 DEG C, opening has
(b) valve of container, controls and system in tank is added drop-wise to pH=4.0 within 10 minutes, add (c) into tank at this time, continue to drip
Add (b), control in 30 minutes and system in tank is added drop-wise to pH=8.0.It is 60 DEG C to keep temperature, pH=8.0, when aging 1 is small, by tank
Interior material is filtered, and washing to no chlorion, filtering, when drying 10 is small at 110 DEG C by filter cake, obtains catalyst material A-
1, then pulverize and sieve to obtain powder catalyst J-1 when roasting 5 is small under the conditions of 550 DEG C under nitrogen protection.Used in plastic
The amount of reagent is listed in table 1.
100 grams of powder catalyst J-1 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then
When drying 10 is small at 110 DEG C, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, catalyst A is obtained, its composition is shown in Table 2.
Embodiment 2
Solid aluminum sulfate, cerous nitrate are added in distilled water, while heats and stirs to dissolving, obtains solution (a).Will
Concentrated ammonia liquor adds appropriate distilled water and is diluted to about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Cu, and 120
DEG C dry 240 minutes, when the lower 550 DEG C of roastings 4 of nitrogen protection are small, add in glucose solution and be uniformly mixed, liquid consolidates volume ratio
For 5：1, then plus water is beaten, and obtains activated carbon slurries (c).A plastic cans is taken, after (a) is added in tank and is heated with stirring to 60 DEG C,
Opening has the valve of the container of (b), controls and system in tank is added drop-wise to pH=4.0 within 10 minutes, open the valve of (c) container
Door, continues that (b) is added dropwise, controls in 30 minutes system in tank being added drop-wise to pH=8.0, control the valve of the container of (c), ensure this
When be added dropwise to complete.It is 60 DEG C to keep temperature, and pH=8.0, when aging 1 is small, material in tank is filtered, is washed to sulfate radical-free
Ion, filtering, when drying 10 is small at 110 DEG C by filter cake, obtains catalyst material A-2, then under nitrogen protection at 550 DEG C
Under the conditions of roasting 5 it is small when, pulverize and sieve to obtain powder catalyst J-2.The amount of plastic agents useful for same is listed in table 1.
100 grams of catalyst material A-2 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
When drying 10 is small at 110 DEG C, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, catalyst B is obtained, its composition is shown in Table 2.
Embodiment 3
Solid aluminum sulfate, cerous nitrate are added in distilled water, while heats and stirs to dissolving, obtains solution (a).Will
It is 250g Al that solid sodium metaaluminate, which is configured to concentration,2O3/ L sodium aluminate solutions (b).Powdery coconut husk charcoal is used into the dipping containing Fe
Liquid impregnates, 120 DEG C of drying 240 minutes, when the lower 550 DEG C of roastings 4 of nitrogen protection are small, adds uniformly mixed in aqueous sucrose solution, liquid
Gu volume ratio is 3：1, then plus water is beaten, and obtains slurries（c）.Waterglass is according to 1:2 dilution proportion in deionized water, is matched somebody with somebody
It is set to solution (d).A plastic cans is taken, inserts after 2L deionized waters are heated with stirring to 60 DEG C and adds slurries（c）, while open and have
(a), the valve of the container of (b), pH=8.0 of control system, control dripped off (a) in 45 minutes, closed valve.Keep temperature
Spend for 65 DEG C, pH=8.0, stop after twenty minutes, solution (d) is added into system, contain according to silica in amorphous silica-alumina
Amount 55wt% is calculated to be added in 10 minutes.Then when aging 1 is small, material in tank is filtered, wash to sulfate radical-free from
Son, filtering, when drying 10 is small at 110 DEG C by filter cake, obtains catalyst material A-3, then under nitrogen protection in 550 DEG C of bars
When roasting 5 is small under part, pulverize and sieve to obtain powder catalyst J-3.The amount of plastic agents useful for same is listed in table 1.
100 grams of catalyst material A-3 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
When drying 10 is small at 110 DEG C, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, catalyst C is obtained, its composition is shown in Table 2.
Embodiment 4
Solid aluminum chloride, cerous nitrate are added in distilled water, while heats and stirs to dissolving, obtains solution (a).Will
Concentrated ammonia liquor adds appropriate distilled water and is diluted to about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Mn, and 120
DEG C dry 240 minutes, when the lower 550 DEG C of roastings 4 of nitrogen protection are small, add in glucose solution and be uniformly mixed, liquid consolidates volume ratio
For 3：1, then plus water is beaten, and obtains activated carbon slurries (c).After (a) is added in plastic cans and is heated with stirring to 60 DEG C, opening is deposited
There is the valve of the container of (b), control and system in tank is added drop-wise to pH=4.0 within 10 minutes, add (c) into tank at this time, continue
It is added dropwise (b), controls in 30 minutes and system in tank is added drop-wise to pH=8.0.It is 60 DEG C to keep temperature, pH=8.0, will when aging 1 is small
Material is filtered in tank, and washing to no chlorion, filtering, when drying 10 is small at 110 DEG C by filter cake, obtains catalyst material
A-4, then pulverizes and sieves to obtain powder catalyst J-4 when roasting 5 is small under the conditions of 550 DEG C under nitrogen protection.Plastic institute
Table 1 is listed in the amount of reagent.
100 grams of catalyst material A-4 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
When drying 10 is small at 110 DEG C, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, catalyst D is obtained, its composition is shown in Table 2.
Embodiment 5
Solid aluminum sulfate, lanthanum nitrate are added in distilled water, while heats and stirs to dissolving, obtains solution (a).Will
Concentrated ammonia liquor adds appropriate distilled water and is diluted to about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Cu, and 120
DEG C dry 240 minutes, when the lower 550 DEG C of roastings 4 of nitrogen protection are small, add in glucose solution and be uniformly mixed, liquid consolidates volume ratio
For 3：1, then plus water is beaten, and obtains activated carbon slurries (c).A plastic cans is taken, after (a) is added in tank and is heated with stirring to 60 DEG C,
Opening has the valve of the container of (b), controls and system in tank is added drop-wise to pH=4.0 within 10 minutes, open the valve of (c) container
Door, continues that (b) is added dropwise, controls in 30 minutes system in tank being added drop-wise to pH=8.0, control the valve of the container of (c), ensure this
When be added dropwise to complete.It is 60 DEG C to keep temperature, and pH=8.0, when aging 1 is small, material in tank is filtered, is washed to sulfate radical-free
Ion, filtering, when drying 10 is small at 110 DEG C by filter cake, obtains catalyst material A-5, then under nitrogen protection at 550 DEG C
Under the conditions of roasting 5 it is small when, pulverize and sieve to obtain powder catalyst J-5.The amount of plastic agents useful for same is listed in table 1.
100 grams of catalyst material A-5 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
When drying 10 is small at 110 DEG C, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, catalyst E is obtained, its composition is shown in Table 2.
Embodiment 6
The synthesis of embodiment 2 is repeated, the not adding carbohydrate during plastic, is made catalyst material A-6 and powdered urges
Agent J-6.
Preformed catalyst is prepared with embodiment 2, obtains catalyst F, its composition is shown in Table 2.
Embodiment 7
The synthesis of embodiment 3 is repeated, the not adding carbohydrate during plastic, is made catalyst material A-7 and powdered urges
Agent J-7.
Preformed catalyst is prepared with embodiment 3, obtains catalyst G, its composition is shown in Table 2.
Comparative example 1
The synthesis of embodiment 2 is repeated, does not add activated carbon, transition metal and carbohydrate during plastic, obtained contrast is urged
Agent material PA-1 and powder catalyst DF-1, its appearance white.
100 grams of catalyst material PA-1 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
When drying 10 is small at 110 DEG C, when roasting 5 is small under the conditions of 550 DEG C, impregnated with the maceration extract containing Cu, it is then dry at 110 DEG C
10 it is small when, under the conditions of 550 DEG C roasting 5 it is small when, obtain catalyst DA, its composition is shown in Table 2.
Comparative example 2
Activated carbon 100g used in embodiment 2 is contacted to form paste with the peptization liquid containing nitric acid, extruded moulding, so
Afterwards at 110 DEG C it is dry 10 it is small when, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C after, obtain carrier, its appearance is black
Color.Impregnated with the maceration extract containing Ce-Cu, when then drying 10 is small at 110 DEG C, 5 are roasted under the conditions of 550 DEG C under nitrogen protection
Hour, catalyst DB is obtained, its composition is shown in Table 2.
Comparative example 3
By activated carbon used in embodiment 2 with carrier material PA-1 physical mixeds, with the peptization liquid contact containing nitric acid
Form paste, extruded moulding, then at 110 DEG C it is dry 10 it is small when, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C after,
Catalyst carrier DZ-C is obtained, wherein activated carbon and alumina content is same as Example 2, its appearance black.With the leaching containing Cu
Stain liquid impregnates, and when then drying 10 is small at 110 DEG C, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, obtains catalyst
DC, its composition are shown in Table 2.
1 plastic reagent quality of table
| Bearer number | J-1 | J-2 | J-3 | J-4 | J-5 | J-6 | J-7 |
| Aluminium salt, g | 1559 | 1029 | 201 | 1210 | 578 | 1029 | 201 |
| Sugar, g | 13 | 39 | 225 | 10 | 78 | - | - |
| Activated carbon, g | 256 | 307 | 1242 | 198 | 402 | 322 | 1337 |
| Cerous nitrate, g | 90 | 77 | 181 | 73 | - | 77 | 181 |
| Lanthanum nitrate, g | - | - | - | - | 60 | - | - |
The composition and property of 2 catalyst of table
| Catalyst is numbered | A | B | C | D | E | F | G | DA | DB | DC |
| CeO2, wt% | 3.55 | 3.83 | 2.89 | 3.70 | - | 3.80 | 2.85 | 3.86 | 3.84 | 3.86 |
| CuO, wt% | 3.52 | 3.84 | - | - | 2.97 | 3.86 | - | 3.85 | 3.86 | 3.86 |
| Fe2O3, wt% | - | - | 2.76 | - | - | - | 2.80 | - | - | - |
| MnO2, wt% | - | - | - | 3.59 | - | - | - | - | - | - |
| La2O3, wt% | - | - | - | - | 2.87 | - | - | - | - | - |
| Specific surface area, m2/g | 386 | 437 | 469 | 386 | 393 | 415 | 444 | 251 | 774 | 394 |
| Pore volume, mL/g | 0.47 | 0.38 | 0.33 | 0.47 | 0.28 | 0.36 | 0.31 | 0.63 | 0.46 | 0.34 |
| Side pressure strength, N/cm | 225 | 193 | 173 | 234 | 176 | 179 | 143 | 232 | 52 | 169 |
| Abrasion, wt% | 0.51 | 0.62 | 0.80 | 0.65 | 0.71 | 0.79 | 0.80 | 0.32 | 4.88 | 0.94 |
The catalyst obtained after activated carbon is handled using carbohydrate it can be seen from catalyst property in table 2 and does not add sugar
The catalyst that class obtains is compared, and bulk property is improved.
It is canescence as the catalyst material obtained by the embodiment of the present invention and the appearance of catalyst, without obvious black,
Illustrate that activated carbon becomes the core of catalyst.
In the present invention, using X-ray photoelectron spectroscopy（XPS）To 1 gained catalyst material table of embodiment 2 and comparative example
The element in face is analyzed.By analysis result as it can be seen that the element on 2 gained catalyst material A2 surfaces of embodiment forms and PA-1 groups
Into essentially identical, there is micro elemental carbon.This further illustrates that catalyst material of the invention is with carrying transition metal
Activated carbon is core, using the aluminium oxide containing rare earth metal or amorphous silica-alumina as shell.
Catalyst prepared by the embodiments of the present invention and comparative example is evaluated.Catalyst packing is in fixed bed reaction
In device, using air as oxide isolation, continous way processing is carried out to certain oil plant phenol wastewater.
Major pollutants COD in waste water：20000mg/L, free phenol：0.7wt%.
Treatment conditions：Volume space velocity 1.5h when 200 DEG C of temperature, pressure 6.0MPa, gas-liquid volume ratio 150, liquid-1.Catalyst
Using 10 when small after handled waste water the results are shown in table 3.
3 evaluation result of table
| Catalyst is numbered | B | C | F | G | DA | DB | DC |
| COD, mg/L | 455 | 457 | 547 | 564 | 685 | 394 | 582 |
| Free phenol, mg/L | 0.58 | 0.59 | 0.68 | 0.57 | 2.54 | 0.49 | 1.24 |
| BOD/COD | 0.62 | 0.53 | 0.52 | 0.50 | 0.41 | 0.64 | 0.48 |
Can be seen that the catalyst prepared using the method for the present invention from 3 evaluation result of table, in waste water COD reduce amplitude compared with
Greatly, BOD/COD substantially increases.
The catalyst prepared using the embodiment of the present invention and comparative example handles above-mentioned waste water under identical process conditions, makes
With 1000 it is small when after, evaluation result is listed in table 4.
4 estimation of stability result of table
| Catalyst is numbered | B | C | F | G | DA | DB | DC |
| COD, mg/L | 525 | 548 | 670 | 705 | 887 | 1536 | 868 |
| Free phenol, mg/L | 0.54 | 0.71 | 1.35 | 1.66 | 8.37 | 20.64 | 2.10 |
| BOD/COD | 0.67 | 0.54 | 0.53 | 0.50 | 0.40 | 0.23 | 0.41 |
| CeO in catalyst2, wt% | 3.78 | 2.64 | 3.74 | 2.61 | 3.81 | 2.02 | 2.89 |
| CuO in catalyst2, wt% | 3.82 | - | 3.78 | - | 3.77 | 2.14 | 2.98 |
| Fe in catalyst2O3, wt% | - | 2.53 | - | 2.42 | - | - | - |
The catalyst prepared it can be seen from 4 result of table using the method for the present invention is with good stability, and is catalyzed
In agent the loss of active metal be improved significantly.
Claims (24)
1. a kind of catalytic wet oxidation catalyst, including following core shell structure components, which is with load transitions
The activated carbon of metal is core, using the aluminium oxide containing rare earth metal or the amorphous silica-alumina containing rare earth metal as shell, with activated carbon and
On the basis of the weight of aluminium oxide or activated carbon and amorphous silica-alumina, activated carbon accounts for 10% ~ 70%, and aluminium oxide or amorphous silica-alumina account for
30%~90%；The transition metal is the one or more in vanadium, chromium, manganese, iron, cobalt, copper and titanium；The rare earth metal for lanthanum,
One or more in cerium.
2. catalyst described in accordance with the claim 1, it is characterised in that：With activated carbon and aluminium oxide or activated carbon and amorphous silicon
On the basis of the weight of aluminium, activated carbon accounts for 30% ~ 70%, and aluminium oxide or amorphous silica-alumina account for 30% ~ 70%.
3. catalyst described in accordance with the claim 1, it is characterised in that：The granularity of the activated carbon is the mesh of 150 mesh ~ 300.
4. catalyst described in accordance with the claim 1, it is characterised in that：On the basis of the weight of catalyst, transiting metal oxidation
The content of thing is 1% ~ 15%, the content 1% ~ 15% of rare-earth oxide, activated carbon and aluminium oxide or activated carbon and amorphous silicon
The content of aluminium is 70% ~ 98%.
5. catalyst described in accordance with the claim 1, it is characterised in that：On the basis of the weight of amorphous silica-alumina, silica
Weight content is 10% ~ 90%.
6. catalyst described in accordance with the claim 1, it is characterised in that：On the basis of the weight of amorphous silica-alumina, silica
Weight content is 30% ~ 70%.
7. catalyst described in accordance with the claim 1, it is characterised in that：The catalyst is to be not required to molding powdered catalytic
Agent, or preformed catalyst, the granularity of powder catalyst are 0.05 ~ 0.20mm, preformed catalyst granularity for 0.5 ~
8.0mm。
8. according to the catalyst described in claim 7, it is characterised in that：The property of the preformed catalyst is as follows：Compare surface
Product is 200 ~ 1000m2/ g, pore volume are 0.3 ~ 1.8cm3/ g, rate of wear<3wt%, side pressure strength are 100 ~ 250N/cm.
9. catalyst described in accordance with the claim 1, it is characterised in that：Contain auxiliary agent group in the aluminium oxide or amorphous silica-alumina
Point, the adjuvant component is titanium, the one or more in zirconium, magnesium, zinc, and weight content based on the element is less than 10%.
10. the preparation method of any catalyst of claim 1 ~ 8, including：
(1) activated carbon of carrying transition metal is beaten；
(2) prepared in coprecipitation and introduce step during the plastic of aluminium oxide or amorphous silica-alumina and rare-earth metal complex
（1）Obtained slurries；
(3) step（2）Material after obtained plastic carries out aging, filtering, washing, drying；
(4) by step（3）Catalyst is made in the material of gained.
11. in accordance with the method for claim 10, it is characterised in that：Step（4）By step（3）Catalysis is made in the material of gained
Agent is at least using one of following methods：
A, by step（3）The material of gained, roasts under inert gas shielding, obtains catalyst；
B, by step（3）The material forming of gained, after drying, roasts under inert gas shielding, obtains catalyst；
C, by step（3）The material of gained roasts under inert gas shielding, then again through shaping, after dry, in inert gas
The lower roasting of protection, obtains catalyst.
12. the method stated according to claim 10, it is characterised in that：The property of step (1) described activated carbon is as follows：Specific surface area
500~3000m2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius, granularity are the mesh of 150 mesh ~ 300.
13. in accordance with the method for claim 10, it is characterised in that step（1）Described activated carbon mashing using plus it is water, low
One or more in carbon alcohol are beaten, and wherein low-carbon alcohols are the one or more in the monohydric alcohol that carbon number is 1 ~ 5.
14. in accordance with the method for claim 10, it is characterised in that step（1）The activated carbon of the carrying transition metal is first
Handled using carbohydrate, be then beaten, the carbohydrate is the one or more in the carbohydrate that carbon number is 3 ~ 20；Carbohydrate
It is directly to mix carbohydrate with activated carbon to handle activated carbon, or carbohydrate is dissolved in solvent and adds activated carbon.
15. in accordance with the method for claim 14, it is characterised in that the carbohydrate dosage accounts for the 2% ~ 50% of activated carbon weight.
16. in accordance with the method for claim 14, it is characterised in that the carbohydrate dosage accounts for the 5% ~ 20% of activated carbon weight.
17. in accordance with the method for claim 14, it is characterised in that the carbohydrate is triose, tetrose, pentose, hexose, wheat
One or more in bud sugar, glucose, sucrose.
18. in accordance with the method for claim 14, it is characterised in that the carbohydrate is glucose, one kind in sucrose or more
Kind.
19. in accordance with the method for claim 14, it is characterised in that：Carbohydrate handles activated carbon, and solvent therein is water, carbon is former
Subnumber is the one or more in 1 ~ 5 monohydric alcohol；When carbohydrate handles activated carbon, liquid consolidates volume ratio below 10.
20. in accordance with the method for claim 10, it is characterised in that：Step（2）Described in aluminium oxide or amorphous silica-alumina
Plastic process with rare-earth metal complex is neutralized by the way of the continuous acid-base titration of soda acid, or using two kinds of material cocurrents
Mode.
21. in accordance with the method for claim 10, it is characterised in that：Step（2）Described in aluminium oxide or amorphous silica-alumina
During the plastic of rare-earth metal complex, adjuvant component is introduced, adjuvant component is titanium, zirconium, magnesium, one kind in zinc or more
Kind.
22. in accordance with the method for claim 10, it is characterised in that：Step（2）In, step（1）The introducing of the slurries of gained
Mode uses the one or more combination of following manner：（1）During plastic, which is continuously added in plastic cans；（2）
The slurries are charged first in plastic cans, then carry out plastic reaction；（3）The one or more of the slurries and plastic material are mixed
Close, then carry out plastic reaction.
23. in accordance with the method for claim 10, it is characterised in that：Step（3）In, the drying condition is as follows：50 ~
When drying 1 ~ 15 is small at 150 DEG C.
24. in accordance with the method for claim 11, it is characterised in that：Step（4）In, the roasting condition described in method A is as follows：
Calcination temperature is 450 ~ 700 DEG C, roasting time for 1 ~ 10 it is small when, drying condition described in method B be at 80 ~ 200 DEG C, dry 1 ~
15 it is small when, calcination temperature be 450 ~ 700 DEG C, roasting time for 1 ~ 10 it is small when；In method C, by step（3）The material of gained is lazy
Roasted under property gas shield, the roasting condition is as follows：Calcination temperature is 450 ~ 700 DEG C, when roasting time is 1 ~ 10 small, so
After dry, roasted under inert gas shielding through shaping again afterwards, obtain catalyst, the drying condition after shaping is as follows：80 ~
200 DEG C, when drying 1 ~ 15 is small, roasting condition is as follows：Calcination temperature is 450 ~ 700 DEG C, when roasting time is 1 ~ 10 small.
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| CN108114728B (en) * | 2017-12-28 | 2020-10-30 | 广东粤能净环保科技有限公司 | Method for preparing wet catalytic oxidation catalyst by using waste catalytic cracking catalyst |
| CN108114726B (en) * | 2017-12-28 | 2020-10-30 | 广东粤能净环保科技有限公司 | Method for preparing wet catalytic oxidation catalyst by using waste catalytic cracking catalyst |
| CN108014806B (en) * | 2017-12-28 | 2020-10-30 | 广东粤能净环保科技有限公司 | Method for preparing wet catalytic oxidation catalyst by using waste catalytic cracking catalyst |
| WO2019192179A1 (en) * | 2018-04-04 | 2019-10-10 | 清华大学 | Double-carrier ozone catalyst and modular catalytic oxidation wastewater treatment device |
| CN110433871A (en) * | 2019-08-09 | 2019-11-12 | 宜兴国际环保城科技发展有限公司 | A kind of disintegration-type tubular type free-radical oxidation method for preparing catalyst |
| CN111437830B (en) * | 2020-04-28 | 2021-07-13 | 浙江卫星能源有限公司 | Yolk-eggshell type SiO2-Al2O3Noble metal propane dehydrogenation catalyst and preparation method thereof |
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