CN105709746B - Catalytic wet oxidation catalyst and preparation method thereof - Google Patents
Catalytic wet oxidation catalyst and preparation method thereof Download PDFInfo
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- CN105709746B CN105709746B CN201410710304.7A CN201410710304A CN105709746B CN 105709746 B CN105709746 B CN 105709746B CN 201410710304 A CN201410710304 A CN 201410710304A CN 105709746 B CN105709746 B CN 105709746B
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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 and rare earth metal as core, using aluminum oxide or amorphous silica-alumina as shell, its preparation method is the slurries for the activated carbon that carrying transition metal and rare earth metal are introduced during aluminum oxide or amorphous silica-alumina plastic, and catalyst is obtained through steps such as agings after plastic.The catalyst 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 aluminum oxide or
Catalytic wet oxidation catalyst of amorphous silica-alumina and preparation method thereof.
Background technology
Increasingly strict with global environmental regulation, the Con trolling index of sewage qualified discharge requires more and more 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 turn into the key of waste water catalytic oxidation technologies application.
The catalyst of waste water catalysis oxidation is broadly divided into homogeneous catalyst and the class of heterogeneous solid catalyst two.
Homogeneous catalyst is mainly included to produce the Fenton reagent of oxygen radical, Fe3+、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., waste water is set to reach the processing intent of decarburization, desulfurization and denitrogenation.Homogeneous oxidation catalyst prepare and using process compared with
To be simple, it typically directly can be made into the aqueous solution from metal salts such as iron, copper, cobalt, manganese 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, because metal active constituent is useless
Fully it can dissolve and disperse in water, typically 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 by 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 stable, 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 is mostly from activated carbon as carrier, but the catalysis for selecting activated carbon supported metal to prepare
Agent anti-wear performance 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.For amorphous alumina because having good chemical stability, pore volume is big, there is 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 aluminum oxide
Method, it be by useless active amorphous aluminum oxide is cleaned, filtering, dry after, prepared using cryogenic seal heat treatment mode a kind of
Active amorphous aluminum 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 aluminum oxide
Duct, and the activated carbon so generated skewness in aluminum oxide.
CN201110255525.6 discloses a kind of preparation method of active amorphous aluminum oxide/absorbent charcoal composite material,
It is to pass through waste aluminum sludge, activated carbon, binding agent mix, be granulated, be old, being molded, drying, sintering, rinsing, drying
Active amorphous aluminum oxide/absorbent charcoal composite material is made etc. step.This method belongs to salic species and activated carbon thing
Mixed process is managed, aluminum 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 old, be molded, dry, sintering, rinsing, drying and other steps, so
Obtained composite is still the physical mixture of aluminum oxide and activated carbon, and aluminum oxide disperses uneven, its synthesis with activated carbon
Performance also needs further to improve.
The content of the invention
In view of the shortcomings of the prior art, the invention provides one kind with catalytic performance is good, anti-wear performance is strong, using steady
Qualitative good catalytic wet oxidation catalyst 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 and rare earth metal is core, using aluminum oxide or amorphous silica-alumina as shell, with activated carbon and aluminum oxide or
On the basis of the weight of activated carbon and amorphous silica-alumina, activated carbon accounts for 10% ~ 70%, preferably 30% ~ 70%, aluminum oxide or amorphous silicon
Aluminium accounts for 30% ~ 90%, preferably 30% ~ 70%.
In described amorphous silica-alumina, the weight content of silica is 10% ~ 90%, preferably 30% ~ 70%.
In catalyst of the present invention, described 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 described 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, described rare earth metal is the one or more in lanthanum, cerium.
In catalyst of the present invention, using transition metal and rare earth metal as active metal component, using the weight of catalyst as base
Standard, the content of transition metal oxide is 1% ~ 15%, preferably 1% ~ 10%, and the content of rare-earth oxide is 1% ~ 15%, excellent
Elect 1% ~ 10% as, activated carbon and aluminum oxide or the content of activated carbon and amorphous silica-alumina are 70% ~ 98%, preferably 80% ~ 98%.
The catalyst of the present invention can be the powder catalyst or preformed catalyst for being not required to shaping.It is powdered
The granularity of catalyst is generally 0.05 ~ 0.2mm.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.
Auxiliary agent can be contained in heretofore described aluminum oxide or amorphous silica-alumina, auxiliary agent, which can be that carrier is conventional, to be helped
One or more in agent component, such as titanium, zirconium, magnesium, zinc etc., the weight content in terms of element is below 10%, and preferably 1% ~ 5%.
The preparation process of catalytic wet oxidation catalyst of the present invention, including：
(1) activated carbon of carrying transition metal and rare earth metal is beaten；
(2) step is introduced during aluminum oxide or amorphous silica-alumina plastic（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, it is calcined under inert gas shielding, obtains catalyst；
B, by step（3）The material forming of gained, after drying, it is calcined under inert gas shielding, obtains catalyst；
C, by step（3）The material of gained is calcined under inert gas shielding, then again through shaping, after drying, in inertia
It is calcined under gas shield, obtains catalyst.
Conventional Powdered Activated Carbon commodity, such as all kinds of wood activated charcoals, fruit can be selected in step (1) the of the present invention activated carbon
Shell activated carbon, active carbon from coal；Can also select with wooden material, mineral material, plastics and discarded object, as timber, wood chip, 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. obtains through traditional preparation methods.Activated carbon used in the present invention is powder activated
Charcoal, the mesh of granularity 150 ~ 300,500 ~ 3000m of specific surface area2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius.
In the inventive method, step（1）The activated carbon mashing of described carrying transition metal and rare earth metal is using conventional
Method is carried out, and general using adding the one or more in water, low-carbon alcohols to be beaten, wherein low-carbon alcohols are that carbon number is 1 ~ 5
Monohydric alcohol in one or more.Step（1）The activated carbon of middle carrying transition metal and rare earth metal is born using conventional method
Carry, such as infusion process.It is specific as follows：Maceration extract is configured to transition metal salt and rare earth metal salt, then by activated carbon granule
It is dipped into above-mentioned maceration extract, then through drying and being calcined, obtains the activated carbon of carrying transition metal and rare earth metal, leaching therein
Stain can use transition metal and rare earth metal total immersion method, can also use sub-dip method, and described dipping, which can use, once to be soaked
Stain, multiple maceration can also be used.Transition metal salt used and rare earth metal salt can use when wherein preparing maceration extract
Soluble-salt, such as nitrate, chloride etc., those skilled in the art can determine according to actual conditions.
In the inventive method, step（1）It is preferred that the activated carbon of carrying transition metal and rare earth metal is first handled using carbohydrate,
Then it is beaten.Described carbohydrate is the one or more in monosaccharide and disaccharide, polysaccharide, and preferably carbon number is 3 ~ 20
One or more in carbohydrate, such as：One or more in triose, tetrose, pentose, hexose, maltose, glucose, sucrose,
One or more more preferably in glucose, sucrose.Described carbohydrate dosage accounts for the 2% ~ 50% of activated carbon weight, preferably 5%
~20%.Carbohydrate processing activated carbon can directly mix carbohydrate with activated carbon, carbohydrate can also be dissolved in solvent and add work
Property charcoal, solvent therein be water, low-carbon alcohols（I.e. carbon number is 1 ~ 5 monohydric alcohol）In one or more.Carbohydrate processing is lived
Property charcoal when, the solid volume ratio of its liquid is below 10, preferably 1 ~ 5.After carbohydrate processing activated carbon, excessive liquid phase is preferably crossed and filtered out
Go, be then beaten again.Being beaten can use conventional method to carry out, and general use adds the one or more in water, low-carbon alcohols to enter
Row mashing, 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）Described in aluminum oxide or the plastic process of amorphous silica-alumina can be by those skilled in the art
Well known process is carried out.The plastic process of amorphous alumina or amorphous silica-alumina is usually in acid material and alkaline material
And course of reaction.Plastic process can also use two kinds of material cocurrents to neutralize by the way of the continuous acid-base titration of soda acid
Mode.
Step of the present invention（2）In, aluminum oxide plastic is to be entered using aluminum soluble salt with acidic precipitation agent or alkaline precipitating agent
The process of row neutralization reaction, wherein aluminum soluble salt used is the one or more in aluminium chloride, aluminum sulfate, aluminum nitrate, institute
Acidic precipitation agent is usually the one or several kinds in hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, carbon dioxide etc., alkalescence used
Precipitating reagent is usually the one or several kinds in sodium carbonate, sodium acid carbonate, sodium hydroxide, potassium hydroxide, ammoniacal liquor etc..Aluminum oxide into
Glue can also use meta-aluminate（Such as sodium metaaluminate and/or potassium metaaluminate）With acid aluminium salt（Such as aluminium chloride, aluminum nitrate,
One or more in aluminum sulfate）The method for carrying out neutralizing plastic.
Step of the present invention（2）In, amorphous silica-alumina plastic process can be carried out by process well known to those skilled in the art.
Plastic material generally comprises silicon source（Al2(SO4)3、AlCl3、Al(NO3)3And NaAlO2One or more in）, silicon source（Water
One or more in glass, Ludox and organic silicon-containing compound etc.）, precipitating reagent（NaOH、NH4OH or CO2Deng）, according into
The different choice of glue process uses, and conventional mode of operation mainly has：（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）Sunk with acidity
Shallow lake agent（CO2）Neutralize plastic.Silicon source typically introduces plastic cans during plastic, can also with after silicon source or precipitant mix again
Plastic is neutralized, carries out neutralization plastic as waterglass is added in basic aluminium salt or alkaline precipitating agent, Ludox is added in acid aluminium salt
Carry out neutralizing plastic etc..Silicon source can also be added after silicon source precipitates in material.Can also by aforesaid way two or more
It is used in combination.The above method is well-known to those skilled in the art.
Described plastic process is typically carried out at room temperature ~ 85 DEG C, is relatively suitably for 40 ~ 80 DEG C, preferably 50 ~ 70 DEG C.Institute
The plastic process stated typically is carried out under certain pH value condition, and typical pH is 6.0 ~ 10.0, is relatively suitably for 7.0 ~ 9.5, excellent
Elect 7.5 ~ 9.0 as.Step（3）Described aging, condition are as follows：PH is 6.0 ~ 10.0, preferably 7.0 ~ 9.5, ageing time
0.25 ~ 8.0 hour, relatively it is adapted at 0.5 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours, aging temperature is room temperature ~ 85 DEG C, is preferably
40~80℃.Temperature and pH and temperature during neutralization and pH during aging is preferably identical.
In the present invention, step（2）During aluminum oxide or amorphous silica-alumina plastic, the conventional auxiliary agent of carrier can also be added
One or more in component, such as titanium, zirconium, magnesium, zinc etc., its addition can be selected according to being actually needed.
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, the slurries are 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 described 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 is carried out in the range of being typically 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, described 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 typically used are as follows：50 ~
Dried 1 ~ 15 hour 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：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
Step of the present invention（4）In, method B and the shaping described in method C can be carried out as needed, generally strip, circle
Column, spherical, irregular strip, special-shaped ball etc., granularity can determine as needed, generally 0.5 ~ 8.0mm.Described forming process
In, shaping assistant such as adhesive, peptization acid, the one or more in extrusion aid can be added as needed.
Step of the present invention（4）In, the drying condition described in method B is dried 1 ~ 15 hour generally at 80 ~ 200 DEG C, roasting
Temperature is generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
Step of the present invention（4）In, in method C, by step（3）The material of gained is calcined under inert gas shielding, described
Roasting condition it is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.Then again through being molded, after drying,
It is calcined under inert gas shielding, obtains catalyst, the drying condition after shaping is as follows：At 80 ~ 200 DEG C, dry 1 ~ 15 hour, roasting
Burning condition is as follows：Sintering temperature is generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
In the present invention, it is calcined 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 be by using the activated carbon of carrying transition metal and rare earth metal as
Core, with aluminum oxide（Or amorphous silica-alumina）For shell, make full use of that activated carbon specific surface area is big, adsorption capacity is strong and aluminum oxide（Or
Amorphous silica-alumina）The characteristics of aperture is big, pore volume is high, activated carbon is strong for the adsorption capacity of organic molecule, organic point of Preferential adsorption
The diffusion of the sub outer surface inner surface by catalyst, so make the first aluminum oxide with as shell of reactant（Or amorphous silicon
Aluminium）Contact, good space is provided for the deposition of impurity, promotes the Properties of Activated Carbon of carrying transition metal and rare earth metal more
Play well；On the other hand, aluminum oxide（Or amorphous silica-alumina）With higher mechanical strength, provided for catalyst good
Mechanical support and intensity so that catalyst has good mechanical strength and anti-wear performance.The catalyst is particularly useful as catalysis
The catalytic wet oxidation catalyst of wet oxidizing catalyst, especially Love psychology.
In the preparation method of catalyst of the present invention, the activated carbon of preferably supported active metals is handled through carbohydrate, can so be made
Carbohydrate uniform adsorption makes to be mixed in aluminum oxide on activated carbon surfaces externally and internally by follow-up roasting process（Or amorphous silica-alumina）
With the carbohydrate breakdown charing among activated carbon, the activated carbon connection aluminum oxide newly formed（Or amorphous silica-alumina）And activated carbon, make
Obtain activated carbon and aluminum oxide（Or amorphous silica-alumina）Combination it is even closer, be advantageous to improve the mechanical strength of catalyst and wear-resistant
Consumption energy, moreover, the adhesion of activated carbon and active metal is weaker, activated carbon elder generation supported active metals, then to adsorb carbohydrate laggard
The follow-up roasting process of row, activated carbon of the newly-generated activated carbon preferentially with active metal attachment are combined, and are coated on active metal
Around, active metal, in free and half free state, is not easy to cause active gold in aqueous phase while sufficient activity is provided
The loss of category, the active metal of micro loss enter liquid phase and participate in reacting with ionic condition, and appropriate adds reactivity, makes
Catalyst has higher reactivity and stability in use.
Catalyst preparation process of the present invention is simply, conveniently, easily operated, is adapted to industrial production.
The catalyst of the present invention is applied to CWO course of reaction, using air, oxygen-enriched air, ozone or mistake
Oxide is as oxidant, continous way or batch (-type) processing high concentrated organic wastewater, especially suitable for improve temperature and
The CWO 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 determined using low temperature liquid nitrogen physisorphtion.Rate of wear is to use to turn
Cartridge type abrasion instrument determines（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 determined 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, the mesh of granularity 200.
Embodiment 1
Solid aluminum chloride is added in distilled water, while heats and stirs to dissolving, obtains solution (a).By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Ce-Cu, leaching
Activated carbon after stain is dried 240 minutes at 120 DEG C, after lower 500 DEG C of nitrogen protection is calcined 4 hours, is added in D/W
Well mixed, the solid volume ratio of liquid is 3：1, then plus water is beaten, and obtains slurries (c).(a) is added in plastic cans and is stirred and is added
After hot to 60 DEG C, the valve for the container for having (b) is opened, controls and system in tank is added drop-wise to pH=4.0 within 10 minutes, now
(c) is added into tank, continues that (b) is added dropwise, controls in 30 minutes and system in tank is added drop-wise to pH=8.0.Keeping temperature is 60 DEG C,
PH=8.0, aging 1 hour, material in tank is filtered, and filter cake filtering, is dried 10 by washing to without chlorion at 110 DEG C
Hour, catalyst material A-1 is obtained, is then calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, pulverizes and sieves to obtain powder
Last shape catalyst J-1.The amount of plastic agents useful for same 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
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst A, its composition is shown in Table 2.
Embodiment 2
Solid aluminum sulfate is added in distilled water, while heats and stirs to dissolving, obtains solution (a).By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Ce-Cu, leaching
Activated carbon after stain is dried 240 minutes at 120 DEG C, and the lower 500 DEG C of roastings of nitrogen protection are added in D/W after 4 hours and mixed
Close uniformly, the solid volume ratio of liquid is 5：1, then plus water is beaten, and obtains activated carbon slurries (c).A plastic cans is taken, (a) is added simultaneously in tank
After being heated with stirring to 60 DEG C, open have (b) container valve, control 10 minutes within by system in tank be added drop-wise to pH=
4.0, the valve of (c) container is opened, continues that (b) is added dropwise, controls in 30 minutes and system in tank is added drop-wise to pH=8.0, control (c)
Container valve, guarantee be now added dropwise to complete.Keeping temperature is 60 DEG C, pH=8.0, aging 1 hour, material in tank is carried out
Filtering, is washed to sulfate radical-free ion, filtering, and filter cake is dried 10 hours at 110 DEG C, obtains catalyst material A-2, then
It is calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, pulverizes and sieves to obtain powder catalyst J-2.Plastic agents useful for same
Amount 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
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst B, its composition is shown in Table 2.
Embodiment 3
Solid aluminum sulfate is added in distilled water, while heats and stirs to dissolving, obtains solution (a).Solid is inclined
It is 250g Al that sodium aluminate, which is configured to concentration,2O3/ L sodium aluminate solutions (b).Powdery coconut husk charcoal is entered using the maceration extract containing Ce-Fe
Row is impregnated, and the activated carbon after dipping is dried 240 minutes at 120 DEG C, and the lower 500 DEG C of roastings of nitrogen protection add sucrose water after 4 hours
It is well mixed in solution, the solid volume ratio of liquid is 3：1, then plus water is beaten, and obtains slurries（c）.Waterglass is according to 1:2 ratio is dilute
Release in deionized water, be configured to solution (d).A plastic cans is taken, inserts and slurry is added after 2L deionized waters are heated with stirring to 60 DEG C
Liquid（c）, while open have (a), (b) container valve, pH=8.0 of control system, control 45 minutes in will (a) drop
It is complete, close valve.Keeping temperature is 65 DEG C, pH=8.0, after stopping 20 minutes, solution (d) is added into system, according to amorphous
The content 55wt% of silica is calculated and added in 10 minutes in sial.Then aging 1 hour, material in tank is filtered,
Washing filtering, filter cake is dried 10 hours at 110 DEG C, catalyst material A-3 is obtained, then in nitrogen to sulfate radical-free ion
It is calcined 5 hours under the conditions of 550 DEG C under gas shielded, pulverizes and sieves to obtain powder catalyst J-3.The amount row of plastic agents useful for same
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
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst C, its composition is shown in Table 2.
Embodiment 4
Solid aluminum chloride is added in distilled water, while heats and stirs to dissolving, obtains solution (a).By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Ce-Mn, leaching
Activated carbon after stain is dried 240 minutes at 120 DEG C, and the lower 500 DEG C of roastings of nitrogen protection are added in D/W after 4 hours and mixed
Close uniformly, the solid volume ratio of liquid is 3：1, then plus water is beaten, and obtains activated carbon slurries (c).(a) is added in plastic cans and is stirred and is added
After hot to 60 DEG C, the valve for the container for having (b) is opened, controls and system in tank is added drop-wise to pH=4.0 within 10 minutes, now
(c) is added into tank, continues that (b) is added dropwise, controls in 30 minutes and system in tank is added drop-wise to pH=8.0.Keeping temperature is 60 DEG C,
PH=8.0, aging 1 hour, material in tank is filtered, and filter cake filtering, is dried 10 by washing to without chlorion at 110 DEG C
Hour, catalyst material A-4 is obtained, is then calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, pulverizes and sieves to obtain powder
Last shape catalyst J-4.The amount of plastic agents useful for same is listed in table 1.
100 grams of catalyst material A-4 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst D, its composition is shown in Table 2.
Embodiment 5
Solid aluminum sulfate is added in distilled water, while heats and stirs to dissolving, obtains solution (a).By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing La-Cu, leaching
Activated carbon after stain is dried 240 minutes at 120 DEG C, and the lower 500 DEG C of roastings of nitrogen protection are added in D/W after 4 hours and mixed
Close uniformly, the solid volume ratio of liquid is 3：1, then plus water is beaten, and obtains activated carbon slurries (c).A plastic cans is taken, (a) is added simultaneously in tank
After being heated with stirring to 60 DEG C, open have (b) container valve, control 10 minutes within by system in tank be added drop-wise to pH=
4.0, the valve of (c) container is opened, continues that (b) is added dropwise, controls in 30 minutes and system in tank is added drop-wise to pH=8.0, control (c)
Container valve, guarantee be now added dropwise to complete.Keeping temperature is 60 DEG C, pH=8.0, aging 1 hour, material in tank is carried out
Filtering, is washed to sulfate radical-free ion, filtering, and filter cake is dried 10 hours at 110 DEG C, obtains catalyst material A-5, then
It is calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, pulverizes and sieves to obtain powder catalyst J-5.Plastic agents useful for same
Amount 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
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst E, its composition is shown in Table 2.
Embodiment 6
The synthesis of embodiment 2 is repeated, the not adding carbohydrate during plastic, catalyst material A-6 is made 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, catalyst material A-7 is made 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 and carbohydrate during plastic, comparative catalyst's carrier material is made
Expect PA-1 and powder carrier DF-1, its appearance white.
100 grams of carrier material PA-1 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
Dry 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C, impregnated with the maceration extract containing Ce-Cu, then at 110 DEG C
Dry 10 hours, be calcined 5 hours under the conditions of 550 DEG C, 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
Dried 10 hours at 110 DEG C afterwards, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain carrier, its outward appearance is black
Color.After being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Ce-Cu, then dried at 110 DEG C
10 hours, it is calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtains catalyst DB, 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
Paste is formed, extruded moulding, is then dried 10 hours at 110 DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection,
Catalyst carrier DZ-C is obtained, wherein activated carbon and alumina content is same as Example 2, its outward appearance black.Under nitrogen protection
After being calcined 5 hours under the conditions of 550 DEG C, impregnated with the maceration extract containing Ce-Cu, then dried 10 hours at 110 DEG C, nitrogen is protected
It is calcined 5 hours under the conditions of 550 DEG C under shield, obtains catalyst DC, its composition is shown in Table 2.
The plastic reagent quality of table 1
| Bearer number | J-1 | J-2 | J-3 | J-4 | J-5 | J-6 | J-7 |
| Aluminium salt, g | 1596 | 1035 | 176 | 1236 | 528 | 1035 | 176 |
| Sugar, g | 15 | 37 | 213 | 11 | 72 | - | - |
| Activated carbon, g | 262 | 308 | 1085 | 203 | 367 | 323 | 1175 |
| Cerous nitrate, g | 92 | 81 | 160 | 72 | - | 81 | 160 |
| Copper nitrate, g | 106 | 90 | - | - | 57 | 90 | - |
| Ferric nitrate, g | - | - | 303 | - | - | - | 303 |
| Manganese nitrate, g | - | - | - | 89 | - | - | - |
| Lanthanum nitrate, g | - | - | - | - | 50 | - | - |
The composition and property of the catalyst of table 2
| Catalyst is numbered | A | B | C | D | E | F | G | DA | DB | DC |
| CeO2, wt% | 3.53 | 4.01 | 2.89 | 3.60 | - | 3.92 | 2.87 | 3.97 | 3.96 | 4.04 |
| CuO, wt% | 3.56 | 3.89 | - | - | 2.72 | 3.86 | - | 3.85 | 3.85 | 3.86 |
| Fe2O3, wt% | - | - | 2.86 | - | - | - | 2.87 | - | - | - |
| MnO2, wt% | - | - | - | 3.31 | - | - | - | - | - | - |
| La2O3, wt% | - | - | - | - | 2.73 | - | - | - | - | - |
| Specific surface area, m2/g | 390 | 439 | 471 | 394 | 395 | 416 | 450 | 251 | 775 | 388 |
| Pore volume, mL/g | 0.45 | 0.35 | 0.30 | 0.46 | 0.26 | 0.34 | 0.28 | 0.64 | 0.41 | 0.32 |
| Side pressure strength, N/cm | 236 | 185 | 174 | 241 | 173 | 192 | 149 | 238 | 49 | 169 |
| Abrasion, wt% | 0.56 | 0.65 | 0.74 | 0.64 | 0.77 | 0.74 | 0.82 | 0.27 | 5.00 | 0.90 |
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 outward appearance of catalyst, without obvious black,
Illustrate that activated carbon turns into the core of catalyst.
In the present invention, using X-ray photoelectron spectroscopy（XPS）To embodiment and the gained catalyst material table of comparative example 1
The element in face is analyzed.From analysis result, the element composition on catalyst material A-1 ~ A-7 surfaces obtained by embodiment with
PA-1 compositions are essentially identical, there is micro elemental carbon.This further illustrates that catalyst material of the invention is with load transitions
The activated carbon of metal and rare earth metal is core, using aluminum oxide or amorphous silica-alumina as shell.
Catalyst prepared by the embodiments of the present invention and comparative example is evaluated.Evaluation test uses intermittent reaction
Device, using hydrogen peroxide as oxide isolation, batch (-type) processing is carried out to certain phenolic resin wastewater.
Major pollutants COD in waste water：15000mg/L.
Treatment conditions are room temperature normal pressure, catalyst amount 1g/L, waste water 200mL, control ph 5 ~ 7, H2O2Concentration 800mg/
L, stir speed (S.S.) 300rpm, residence time 45min.Catalyst is listed in table 3 using the result of handled waste water after 4 times.
The evaluation result of table 3
| Catalyst is numbered | B | C | F | G | DA | DB | DC |
| COD clearances, % | 95.40 | 95.36 | 94.66 | 94.28 | 93.03 | 96.08 | 94.21 |
The catalyst prepared using the inventive method is can be seen that from the evaluation result of table 3, COD clearances are significantly higher, say
Catalyst prepared by bright the inventive method has preferably activity.
The catalyst prepared using the embodiment of the present invention and comparative example handles above-mentioned waste water under identical process conditions, makes
After 100 times, evaluation result is listed in table 4.
The estimation of stability result of table 4
| Catalyst is numbered | B | C | F | G | DA | DB | DC |
| COD clearances, % | 94.60 | 94.33 | 93.15 | 92.97 | 90.15 | 87.03 | 91.19 |
| CeO in catalyst2, wt% | 3.77 | 2.69 | 3.73 | 2.53 | 3.78 | 2.10 | 2.96 |
| CuO in catalyst2, wt% | 3.65 | - | 3.61 | - | 3.66 | 2.01 | 2.78 |
| Fe in catalyst2O3, wt% | - | 2.71 | - | 2.58 | - | - | - |
The catalyst activity reduction amplitude prepared it can be seen from the result of table 4 using the inventive method is smaller, has good
Stability, the conservation rate of active metal substantially increases.
Claims (24)
1. a kind of catalytic wet oxidation catalyst, including following core shell structure components, the core shell structure component is with load transitions
The activated carbon of metal and rare earth metal is core, using aluminum oxide or amorphous silica-alumina as shell, with activated carbon and aluminum oxide or activated carbon
On the basis of the weight of amorphous silica-alumina, activated carbon accounts for 10% ~ 70%, and aluminum oxide or amorphous silica-alumina account for 30% ~ 90%；It is wherein described
Transition metal be one or more in vanadium, chromium, manganese, iron, cobalt, copper and titanium, described rare earth metal is lanthanum, one kind in cerium
It is or a variety of.
2. according to the catalyst described in claim 1, it is characterised in that：With activated carbon and aluminum oxide or activated carbon and amorphous silicon
On the basis of the weight of aluminium, activated carbon accounts for 30% ~ 70%, and aluminum oxide or amorphous silica-alumina account for 30% ~ 70%.
3. according to the catalyst described in claim 1, it is characterised in that：The granularity of described activated carbon is the mesh of 150 mesh ~ 300.
4. according to the catalyst described in claim 1, it is characterised in that：Using transition metal and rare earth metal as active metal group
Point, on the basis of the weight of catalyst, the content of transition metal oxide is 1% ~ 15%, and the content of rare-earth oxide is 1%
~ 15%, activated carbon and aluminum oxide or the content of activated carbon and amorphous silica-alumina are 70% ~ 98%.
5. according to the catalyst described in claim 1, it is characterised in that in described amorphous silica-alumina, the weight content of silica
For 10% ~ 90%.
6. according to the catalyst described in claim 1, it is characterised in that in described amorphous silica-alumina, the weight content of silica
For 30% ~ 70%.
7. according to the catalyst described in claim 1, it is characterised in that：Described catalyst is the powdered catalytic for being not required to shaping
Agent, or preformed catalyst, the granularity of powder catalyst are 0.05 ~ 0.20mm, preformed catalyst granularity is 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：Specific surface area
For 200 ~ 1000m2/ g, pore volume are 0.3 ~ 1.8cm3/ g, rate of wear<3wt%, side pressure strength are 100 ~ 250N/cm.
9. according to the catalyst described in claim 1, it is characterised in that：Contain auxiliary agent in the aluminum oxide or amorphous silica-alumina,
Auxiliary agent is the one or more in titanium, zirconium, magnesium, zinc, using the weight content that element is counted as less than 10%.
10. the preparation method of any catalyst of claim 1 ~ 8, including：
(1) activated carbon of carrying transition metal and rare earth metal is beaten；
(2) step is introduced during aluminum oxide or amorphous silica-alumina plastic（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, it is calcined under inert gas shielding, obtains catalyst；
B, by step（3）The material forming of gained, after drying, it is calcined under inert gas shielding, obtains catalyst；
C, by step（3）The material of gained is calcined under inert gas shielding, then again through shaping, after drying, in inert gas
Protection is lower to be calcined, and 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）Described carrying transition metal and rare earth metal
Activated carbon first using carbohydrate handle, be then beaten, described carbohydrate is one kind in the carbohydrate that carbon number is 3 ~ 20
It is or a variety of；Wherein, carbohydrate processing activated carbon is directly to mix carbohydrate with activated carbon, or carbohydrate is dissolved in solvent and added
Activated carbon.
15. in accordance with the method for claim 14, it is characterised in that described 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 described 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 described 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 described 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 original
Subnumber is the one or more in 1 ~ 5 monohydric alcohol；When carbohydrate handles activated carbon, the solid volume ratio of liquid is below 10.
20. in accordance with the method for claim 10, it is characterised in that：Step（2）Described in aluminum oxide or amorphous silica-alumina
Plastic process is by the way of the continuous acid-base titration of soda acid, or by the way of two kinds of material cocurrents neutralize.
21. in accordance with the method for claim 10, it is characterised in that：Step（2）Described in aluminum oxide or amorphous silica-alumina
During plastic, adjuvant component is introduced, adjuvant component is the one or more in titanium, zirconium, magnesium, zinc.
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, the slurries are 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, described drying condition is as follows：50 ~
Dried 1 ~ 15 hour 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：
Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, and drying condition described in method B is at 80 ~ 200 DEG C, dry 1 ~
15 hours, sintering temperature was 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour；In method C, by step（3）The material of gained is lazy
It is calcined under property gas shield, described roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, so
After drying, it is calcined under inert gas shielding through shaping again afterwards, obtains catalyst, the drying condition after shaping is as follows：80 ~
200 DEG C, dry 1 ~ 15 hour, roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
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