CN105709732B - Noble metal catalyst for catalytic wet oxidation and preparation method thereof - Google Patents
Noble metal catalyst for catalytic wet oxidation and preparation method thereof Download PDFInfo
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- CN105709732B CN105709732B CN201410710481.5A CN201410710481A CN105709732B CN 105709732 B CN105709732 B CN 105709732B CN 201410710481 A CN201410710481 A CN 201410710481A CN 105709732 B CN105709732 B CN 105709732B
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Abstract
The invention discloses a kind of for noble metal catalyst of catalytic wet oxidation and preparation method thereof.The catalyst includes following nucleocapsid components, the nucleocapsid component is using the activated carbon of carried noble metal and rare earth metal as core, using aluminium oxide or amorphous silica-alumina as shell, its preparation method is the activated carbon slurries that carried noble metal and rare earth metal are introduced during aluminium oxide or amorphous silica-alumina plastic, after plastic through aging and etc. obtain catalyst.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 for catalytic wet oxidation
Noble metal catalyst and preparation method thereof.
Background technology
Increasingly strict with global environmental regulation, the Con trolling index requirement of sewage qualified discharge 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 mainly includes the Fenton reagent, the Fe that generate oxygen radical3+、Cu2+, the metals 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 directly be selected to be made into aqueous solution or be directly thrown into handled waste water,
And it is used by discharge in treated water outlet or regeneration 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 of 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 the strong a kind of microcrystalline carbon of the black made of carbonaceous material, hole prosperity, large specific surface area, adsorption capacity.Activity
Charcoal property is stablized, acidproof, alkaline-resisting, heat-resisting, not soluble in water or organic solvent, easily regenerates, 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 that activated carbon supported metal is selected 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.Amorphous alumina is because with good chemical stability, large pore volume, with certain acidity, pore size distribution$ concentration, machine
The advantages that tool intensity is big, corrosion-resistant, is widely used in catalytic field, but amorphous alumina is small there are specific surface
Shortcoming, it is relatively small to the absorption and conversion capability of organic matter.
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 is unevenly distributed in aluminium oxide.
CN201110255525.6 discloses a kind of preparation method of active amorphous aluminium oxide/absorbent charcoal composite material,
Be by waste aluminum sludge, activated carbon, binding agent by mixing, granulation, it is aging, be molded, dry, be sintered, rinse, dry
And etc. active amorphous aluminium oxide/absorbent charcoal composite material is made.This method belongs to salic species and activated carbon object
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, granulation, it is aging, be molded, dry, be sintered, rinse, drying and other steps, so
Obtained composite material is still the physical mixture of aluminium oxide and activated carbon, and aluminium oxide disperses uneven, synthesis with activated carbon
Performance also needs to further improve.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides one kind with catalytic performance is good, wear-resisting property is strong, using steady
It is qualitative good for noble metal catalyst of catalytic wet oxidation and preparation method thereof.
The catalytic wet oxidation catalyst of the present invention, including following nucleocapsid components, which is with negative
The activated carbon of supported noble metal and rare earth metal is core, using aluminium oxide or amorphous silica-alumina as shell, with activated carbon and aluminium oxide or work
Property charcoal and amorphous silica-alumina weight on the basis of, activated carbon accounts for 10% ~ 70%, is preferably 30% ~ 70%, aluminium oxide or amorphous silica-alumina
30% ~ 90% is accounted for, is preferably 30% ~ 70%.
The granularity of the activated carbon is preferably the mesh of 150 mesh ~ 300.
In catalyst of the present invention, on the basis of the weight of catalyst, the content of noble metal based on the element is 0.01% ~ 1.0%,
The content of rare earth metal is preferably 1.0% ~ 10.0% based on the element for 1.0% ~ 15.0%, activated carbon and aluminium oxide or activated carbon and
The content of amorphous silica-alumina is 84.0% ~ 98.0%, is preferably 89.0% ~ 98.0%.
In the amorphous silica-alumina, the weight content of silica is 10% ~ 90%, is preferably 30% ~ 70%.
In catalyst of the present invention, one or several kinds of the noble metal in Pt, Pd, Rh, Ru, the rare earth
Metal is lanthanum, the one or more in cerium, praseodymium, neodymium.
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。
Heretofore described aluminium oxide or amorphous silica-alumina, auxiliary agent can be the common adjuvant component of carrier, such as titanium,
One or more in zirconium, magnesium, zinc etc., weight content based on the element is preferably 1% ~ 5% below 10%.
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.
The preparation process of catalytic wet oxidation catalyst of the present invention, including：
(1) activated carbon of carried noble metal and rare earth metal is beaten；
(2) step is introduced during aluminium oxide or amorphous silica-alumina plastic（1）Obtained slurries；
(3) step（2）Material after obtained plastic carries out aging, filtering, washing, drying, obtains catalyst material；
(4) by step（3）Catalyst is made in the catalyst material of gained, and the preparation of the catalyst preferably at least uses down
State one of method：
A, by step（3）The catalyst material of gained roasts under inert gas shielding, obtains catalyst；
B, by step（3）The catalyst material shaping of gained, after drying, roasts under inert gas shielding, is urged
Agent；
C, by step（3）The catalyst material of gained roasts under inert gas shielding, then again through being molded, after dry,
It is roasted under inert gas shielding, obtains 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 carried noble metal and rare earth metal uses routine side
Method carries out, and general using the one or more in water, low-carbon alcohols is added to be beaten, wherein low-carbon alcohols are that carbon number is 1 ~ 5
One or more in monohydric alcohol.Step（1）The activated carbon of middle carried noble metal and rare earth metal is loaded using conventional method, than
Such as infusion process.It is specific as follows：Maceration extract is configured to precious metal salt and rare earth metal salt, is then dipped into active carbon particle above-mentioned
In maceration extract, then through dry and roasting, the activated carbon of carried noble metal and rare earth metal is obtained, dipping therein may be employed
Noble metal and rare earth metal total immersion method, can also use sub-dip method, and the dipping may be employed single-steeping, can also use
Multiple maceration.Soluble-salt, such as nitre may be employed in precious metal salt used and rare earth metal salt when wherein preparing maceration extract
Hydrochlorate, chloride etc., those skilled in the art can determine according to actual conditions.
In the method for the present invention, step（1）It is preferred that the activated carbon of carried noble metal and rare earth metal is first handled using carbohydrate, so
After be beaten.The carbohydrate is monosaccharide and disaccharide, the one or more in polysaccharide, and preferably carbon number is 3 ~ 20 sugar
One or more in class, such as：One or more in triose, tetrose, pentose, hexose, maltose, sucrose, more preferably
One or more in glucose, sucrose.The carbohydrate dosage accounts for the 2% ~ 50% of activated carbon weight, is preferably 5% ~ 20%.Sugar
Class processing activated carbon can directly mix carbohydrate with activated carbon, and carbohydrate can also be dissolved in solvent and adds activated carbon,
In 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.After carbohydrate processing activated carbon, excessive liquid phase is preferably filtered to remove, Ran Houzai
It is beaten.Conventional method progress can be used in mashing, and general use adds the one or more in water, low-carbon alcohols to be beaten,
Middle 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 aluminium oxide or the plastic process of amorphous silica-alumina can be by those skilled in the art
Well known process carries out.The plastic process of aluminium oxide or amorphous silica-alumina is usually the neutralization reaction of acid material and alkaline material
Process.The mode of the continuous acid-base titration of soda acid may be employed in plastic process, can also be in a manner that two kinds of material cocurrents neutralize.
Step of the present invention（2）In, aluminium oxide plastic be using aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent into
The process of row neutralization reaction, wherein aluminum soluble salt used is aluminium chloride, the one or more in 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, ammonium hydroxide etc..Aluminium 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 of Deng）, silicon source（Water
One or more of glass, Ludox and organic silicon-containing compound etc.）, precipitating reagent（NaOH、NH4OH or CO2Deng）, according into
The different selections of glue process use, 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）It sinks with acidity
Shallow lake agent（CO2）Neutralize plastic.Silicon source generally 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
It carries out neutralizing plastic etc..Silicon source can also be added in 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.
The plastic process generally carries out at room temperature ~ 85 DEG C, is relatively suitably for 40 ~ 80 DEG C, is preferably 50 ~ 70 DEG C.Institute
The plastic process stated generally carries 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）The aging, condition are as follows：PH is 6.0 ~ 10.0, is preferably 7.0 ~ 9.5, ageing time
0.25 ~ 8.0 it is small when, be relatively suitble to when 0.5 ~ 5.0 is small, be preferably 1.0 ~ 3.0 it is small when, aging temperature be room temperature ~ 85 DEG C, be preferably
40~80℃.Temperature and pH and temperature during neutralization and pH during aging is preferably identical.
In the present invention, step（2）During aluminium oxide or amorphous silica-alumina plastic, the common auxiliary agent of carrier can also be added in
One or more in component, such as titanium, zirconium, magnesium, zinc etc., addition can make choice according to actual needs.
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
It closes：（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 with the one or more of plastic material are mixed, 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 generally carries out in the range of pH is 1.0 ~ 9.0, and preferably pH is 4.0 ~ 8.5.
Step of the present invention（3）Described in material washing, filtering after should be free of or containing minimal amount of heteroion, heteroion includes
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 may be employed
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 shape, 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 in 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 catalyst material of gained roasts under inert gas shielding
It burns, the roasting condition is as follows：Calcination temperature is 450 ~ 700 DEG C, when roasting time is 1 ~ 10 small.Then done again through shaping
It after dry, is roasted under inert gas shielding, obtains catalyst, the drying condition after shaping is as follows：At 80 ~ 200 DEG C, dry 1 ~ 15
Hour, roasting condition is as follows：Calcination temperature is generally 450 ~ 700 DEG C, roasting time be generally 1 ~ 10 it is small when.
It in the present invention, is roasted under inert gas shielding, selected inert gas is generally nitrogen or argon gas.
The nucleocapsid component that catalyst of the present invention uses be by using the activated carbon of carried noble metal and rare earth metal as core,
With aluminium oxide（Or amorphous silica-alumina）For shell, make full use of activated carbon large specific surface area, adsorption capacity strong and aluminium oxide（Or without fixed
Shape sial）The characteristics of aperture is big, pore volume is high, activated carbon is strong for the adsorption capacity of organic molecule, Preferential adsorption organic molecule by
The diffusion of the outer surface inner surface of catalyst so makes the first aluminium oxide with as shell of reactant（Or amorphous silica-alumina）It connects
It touches, provides good space for the deposition of impurity, the Properties of Activated Carbon of carried noble metal and rare earth metal is promoted preferably to send out
It waves；On the other hand, aluminium oxide（Or amorphous silica-alumina）With higher mechanical strength, good machinery branch is provided for catalyst
Support and intensity so that catalyst has good mechanical strength and wear-resisting property.The catalyst is particularly useful as catalytic wet oxygen
Change the catalytic wet oxidation catalyst of 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 aluminium oxide on activated carbon surfaces externally and internally by subsequent roasting process（Or amorphous silica-alumina）
With the carbohydrate breakdown charing among activated carbon, the activated carbon connection aluminium oxide newly formed（Or amorphous silica-alumina）And activated carbon, make
Obtain activated carbon and aluminium oxide（Or amorphous silica-alumina）Combination it is even closer, be conducive to improve the mechanical strength of catalyst and wear-resistant
Consumption energy, moreover, the combination power of activated carbon and active metal is weaker, activated carbon elder generation supported active metals, then to adsorb carbohydrate laggard
The subsequent 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 while sufficient activity is provided in water phase
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 suitble 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.
Specific 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 further illustrated the present invention 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 is put down
Equal pore radius 1.1nm, iodine sorption value 700mg/g, 200 mesh of granularity.
Embodiment 1
Solid aluminum chloride is added in distilled water, while heats and stirs to dissolving, obtains solution (a).By concentrated ammonia liquor
It adds in appropriate distilled water and is diluted to about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Pt-Ce, leaching
Activated carbon after stain is 240 minutes dry at 120 DEG C, when the lower 500 DEG C of roastings 4 of nitrogen protection are small after, add in glucose solution
It is uniformly mixed, liquid consolidates volume ratio as 3：1, then plus water is beaten, and obtains slurries (c).(a) is added in plastic cans and is stirred and is added
System in tank is added drop-wise to pH=4.0, at this time to after 60 DEG C, opening the valve for the container for having (b) by heat within control 10 minutes
(c) is added in into tank, continues that (b) is added dropwise, controls in 30 minutes and system in tank is added drop-wise to pH=8.0.It is 60 DEG C to keep temperature,
When aging 1 is small, material in tank is filtered for pH=8.0, washing to no chlorion, filtering, by filter cake dry 10 at 110 DEG C
Hour, catalyst material A-1 is obtained, then pulverizes and sieves to obtain powder when roasting 5 is small under the conditions of 550 DEG C under nitrogen protection
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
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, 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
It adds in appropriate distilled water and is diluted to about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Rh-Ce, leaching
Activated carbon after stain is 240 minutes dry at 120 DEG C, when the lower 500 DEG C of roastings 4 of nitrogen protection are small after, add in glucose solution
It is uniformly mixed, liquid consolidates volume ratio as 3：1, then plus water is beaten, and obtains activated carbon slurries (c).A plastic cans is taken, (a) is added in tank
And 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 added dropwise to complete at this time.It is 60 DEG C to keep temperature, and when aging 1 is small, material in tank is carried out for pH=8.0
Filtering is washed to sulfate radical-free ion, and filtering when drying 10 is small at 110 DEG C by filter cake, obtains catalyst material A-2, then
Under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, pulverize and sieve 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
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, 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
Sodium aluminate is configured to concentration as 250g Al2O3/ L sodium aluminate solutions (b).By powdery coconut husk charcoal using the maceration extract containing Rh-Ce into
Row dipping, the activated carbon after dipping is 240 minutes dry at 120 DEG C, when the lower 500 DEG C of roastings 4 of nitrogen protection are small after, add in sucrose water
It is uniformly mixed in solution, liquid consolidates volume ratio as 3：1, then plus water is beaten, and obtains slurries（c）.Waterglass is according to 1:2 ratio is dilute
It releases in deionized water, is configured to solution (d).A plastic cans is taken, inserts and slurry is added in after 2L deionized waters are heated with stirring to 60 DEG C
Liquid（c）, open simultaneously have (a), (b) container valve, pH=8.0 of control system, control 45 minutes in will (a) drop
It is complete, close valve.It is 65 DEG C to keep temperature, pH=8.0, stops after twenty minutes, solution (d) is added in into system, according to amorphous
The content 55wt% calculating of silica added in 10 minutes in sial.Then when aging 1 is small, material in tank is filtered,
Washing to sulfate radical-free ion, filtering when drying 10 is small at 110 DEG C by filter cake, obtains catalyst material A-3, then in nitrogen
Under gas shielded when roasting 5 is small under the conditions of 550 DEG C, pulverize and sieve 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
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, 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
It adds in appropriate distilled water and is diluted to about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Rh-Ce, leaching
Activated carbon after stain is 240 minutes dry at 120 DEG C, when the lower 500 DEG C of roastings 4 of nitrogen protection are small after, add in glucose solution
It is uniformly mixed, liquid consolidates volume ratio as 3：1, then plus water is beaten, and obtains activated carbon slurries (c).(a) is added in plastic cans and is stirred
After being heated 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, this
When add in (c) into tank, continue that (b) is added dropwise, system in tank is added drop-wise to pH=8.0 by control in 30 minutes.It is 60 to keep temperature
DEG C, when aging 1 is small, material in tank is filtered for pH=8.0, washing to no chlorion, filtering, and filter cake is done at 110 DEG C
It is dry 10 it is small when, obtain catalyst material A-4, then under nitrogen protection under the conditions of 550 DEG C roasting 5 it is small when, pulverize and sieve
To powder 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
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, 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
It adds in appropriate distilled water and is diluted to about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is impregnated using the maceration extract containing Pt-La, leaching
Activated carbon after stain is 240 minutes dry at 120 DEG C, when the lower 500 DEG C of roastings 4 of nitrogen protection are small after, add in glucose solution
It is uniformly mixed, liquid consolidates volume ratio as 3：1, then plus water is beaten, and obtains activated carbon slurries (c).A plastic cans is taken, (a) is added in tank
And 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 added dropwise to complete at this time.It is 60 DEG C to keep temperature, and when aging 1 is small, material in tank is carried out for pH=8.0
Filtering is washed to sulfate radical-free ion, and filtering when drying 10 is small at 110 DEG C by filter cake, obtains catalyst material A-5, then
Under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, pulverize and sieve 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
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, 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, and 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, and 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, 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
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 Rh-Ce, then at 110 DEG C
When drying 10 is small, when roasting 5 is small under the conditions of 550 DEG C, catalyst DA is obtained, 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, appearance is black
Color.Under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C after, impregnated with the maceration extract containing Rh-Ce, it is then dry at 110 DEG C
10 it is small when, under nitrogen protection when roasting 5 is small under the conditions of 550 DEG C, obtain catalyst DB, 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, appearance black.Under nitrogen protection
It after when roasting 5 is small under the conditions of 550 DEG C, is impregnated with the maceration extract containing Rh-Ce, when then drying 10 is small at 110 DEG C, nitrogen is protected
Under shield when roasting 5 is small under the conditions of 550 DEG C, catalyst DC is obtained, composition is 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 | 723 | 471 | 125 | 677 | 187 | 471 | 125 |
| Sugar, g | 6 | 17 | 140 | 6 | 26 | - | - |
| Activated carbon, g | 118 | 140 | 770 | 111 | 130 | 147 | 829 |
| Chloroplatinic acid, g | 1.90 | - | - | - | 0.72 | - | - |
| Rhodium nitrate, g | - | 1.23 | 2.48 | 1.68 | - | 1.23 | 2.48 |
| Lanthanum nitrate, g | - | - | - | - | 16.11 | - | - |
| Cerous nitrate, g | 91.65 | 42.28 | 108.66 | 83.68 | - | 42.28 | 108.66 |
The composition and property of 2 catalyst of table
| Catalyst is numbered | A | B | C | D | E | F | G | DA | DB | DC |
| Pt, wt% | 0.26 | - | - | - | 0.49 | - | - | - | - | - |
| Rh, wt% | - | 0.31 | 0.26 | 0.23 | - | 0.49 | 0.27 | 0.31 | 0.30 | 0.31 |
| La, wt% | - | - | - | - | 9.30 | - | - | - | - | - |
| Ce, wt% | 10.70 | 9.73 | 10.63 | 10.44 | - | 9.45 | 10.43 | 9.73 | 9.63 | 9.82 |
| Specific surface area, m2/g | 434 | 558 | 663 | 435 | 533 | 529 | 629 | 262 | 812 | 502 |
| Pore volume, mL/g | 0.55 | 0.54 | 0.53 | 0.55 | 0.48 | 0.52 | 0.50 | 0.71 | 0.51 | 0.49 |
| Side pressure strength, N/cm | 223 | 187 | 165 | 228 | 155 | 167 | 152 | 239 | 45 | 164 |
| Abrasion, wt% | 0.50 | 0.60 | 0.70 | 0.60 | 0.70 | 0.70 | 0.83 | 0.28 | 4.55 | 0.90 |
The catalyst property obtained after activated carbon is handled using carbohydrate it can be seen from catalyst property in table 2 to obtain
Improve.
It is canescence as the catalyst material obtained by the embodiment of the present invention and the appearance of catalyst, without apparent 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 and comparative example
The element in face is analyzed.By analysis result as it can be seen that the element on catalyst material A-1 ~ A-7 surfaces obtained by embodiment form and
PA-1 compositions are essentially identical, there is micro elemental carbon.This further illustrates catalyst material of the invention is so that your gold loaded
Belong to and the activated carbon of rare earth metal is core, using aluminium 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
Using hydrogen peroxide as oxide isolation, intermittent processing is carried out to certain phenolic resin wastewater for device.
Major pollutants COD in waste water：15000mg/L.
Treatment conditions be 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 use 4 times after handled waste water the results are shown in tables 3.
3 evaluation result of table
| Catalyst is numbered | B | C | F | G | DA | DB | DC |
| COD removal rates, % | 98.0 | 97.1 | 95.4 | 95.8 | 84.5 | 96.2 | 94.1 |
From evaluation result as can be seen that the catalyst prepared using the method for the present invention, COD removal rates are significantly higher.
The catalyst prepared using the embodiment of the present invention and comparative example handles above-mentioned waste water under identical process conditions, transports
After turning 100 times, 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 removal rates, % | 97.0 | 96.1 | 93.8 | 94.1 | 82.3 | 66.6 | 91.7 |
| Metal conservation rate in catalyst, % | 95.23 | 94.35 | 95.12 | 94.97 | 95.10 | 69.09 | 83.14 |
By catalyst it can be seen from 4 result of table using after 100 times, the catalyst activity prepared using the method for the present invention is dropped
Low amplitude is smaller, with good stability, and the conservation rate of active metal substantially increases.
Claims (24)
1. a kind of catalytic wet oxidation catalyst, including following nucleocapsid components, which is so that your gold loaded
Belong to and the activated carbon of rare earth metal is core, using aluminium oxide or amorphous silica-alumina as shell, with activated carbon and aluminium oxide or activated carbon and
On the basis of the weight of amorphous silica-alumina, activated carbon accounts for 10% ~ 70%, and aluminium oxide or amorphous silica-alumina account for 30% ~ 90%；Wherein, it is described
Noble metal be the one or several kinds in Pt, Pd, Rh, Ru, the rare earth metal is lanthanum, cerium, praseodymium, one kind in neodymium or more
Kind.
2. 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.
3. 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%.
4. catalyst described in accordance with the claim 1, it is characterised in that in the catalyst, using the weight of catalyst as base
Standard, the content of noble metal is based on the element 0.01% ~ 1.0%, and the content of rare earth metal is based on the element 1.0% ~ 15.0%, activated carbon
It is 84.0% ~ 98.0% with the content of aluminium oxide or activated carbon and amorphous silica-alumina.
5. catalyst described in accordance with the claim 1, it is characterised in that in the amorphous silica-alumina, the weight content of silica
For 10% ~ 90%.
6. catalyst described in accordance with the claim 1, it is characterised in that in the amorphous silica-alumina, the weight content of silica
For 30% ~ 70%.
7. catalyst described in accordance with the claim 1, it is characterised in that the catalyst either powder catalyst or
It is preformed catalyst, the granularity of powder catalyst is 0.05 ~ 0.20mm, and 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 is
200 ~1000m2/ g, pore volume are 0.3 ~ 1.8cm3/ g, rate of wear<3wt%, side pressure strength are 100 ~ 300N/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, 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 carried noble metal and rare earth metal is beaten；
(2) step is introduced during aluminium oxide or amorphous silica-alumina plastic（1）Obtained slurries；
(3) step（2）Material after obtained plastic carries out aging, filtering, washing, drying, obtains catalyst material；
(4) by step（3）Catalyst is made in the catalyst material of gained.
11. according to the method for claim 10, it is characterised in that：Step（4）The preparation of catalyst at least uses following sides
One of method：
A, by step（3）The catalyst material of gained roasts under inert gas shielding, obtains catalyst；
B, by step（3）The catalyst material shaping of gained, after drying, roasts under inert gas shielding, obtains catalyst；
C, by step（3）The catalyst material of gained roasts under inert gas shielding, then again through shaping, after dry, lazy
It is roasted under property gas shield, obtains catalyst.
12. according to the method for claim 10, it is characterised in that the property of step (1) described activated carbon is as follows：Specific surface
500 ~ 3000m of product2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius, granularity are 150 ~ 300 mesh.
13. according to 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. according to the method for claim 10, it is characterised in that step（1）The carried noble metal and rare earth metal
Activated carbon is first handled using carbohydrate, is then beaten, the carbohydrate be one kind in the carbohydrate that carbon number is 3 ~ 20 or
It is a variety of；Wherein, carbohydrate processing activated carbon is that carbohydrate is directly mixed with activated carbon or carbohydrate is dissolved in solvent to add work
Property charcoal.
15. according to the method for claim 14, it is characterised in that the carbohydrate dosage accounts for the 2% ~ 50% of activated carbon weight.
16. according to the method for claim 14, it is characterised in that the carbohydrate dosage accounts for the 5% ~ 20% of activated carbon weight.
17. according to 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. according to the method for claim 14, it is characterised in that the carbohydrate is glucose, one kind in sucrose or more
Kind.
19. according to 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. according to the method for claim 10, it is characterised in that：Step（2）Described in aluminium oxide or amorphous silica-alumina
Plastic process is by the way of the continuous acid-base titration of soda acid or in a manner that two kinds of material cocurrents neutralize.
21. according to 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
It closes, then carries out plastic reaction.
22. according to the method for claim 10, it is characterised in that：Step（2）Described in aluminium oxide or amorphous silica-alumina
During plastic, adjuvant component is introduced, adjuvant component is titanium, the one or more in zirconium, magnesium, zinc.
23. according to 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. according to 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 is 450 ~ 700 DEG C, roasting time for 1 ~ 10 it is small when, in method C, by step（3）The catalyst material of gained
Material roasts under inert gas shielding, and the roasting condition is as follows：Calcination temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10
Hour, then after dry, roasted under inert gas shielding through shaping again, obtain catalyst, the drying condition after shaping is such as
Under：At 80 ~ 200 DEG C, when drying 1 ~ 15 is small, roasting condition is as follows：Calcination temperature is 450 ~ 700 DEG C, and roasting time is small for 1 ~ 10
When.
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