CN105709733B - A kind of noble metal catalyst and preparation method thereof for catalytic wet oxidation - Google Patents
A kind of noble metal catalyst and preparation method thereof for catalytic wet oxidation Download PDFInfo
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- CN105709733B CN105709733B CN201410710483.4A CN201410710483A CN105709733B CN 105709733 B CN105709733 B CN 105709733B CN 201410710483 A CN201410710483 A CN 201410710483A CN 105709733 B CN105709733 B CN 105709733B
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Abstract
The noble metal catalyst and preparation method thereof that the invention discloses a kind of for catalytic wet oxidation.The catalyst includes following nucleocapsid components, the nucleocapsid component is using activated carbon as core, using containing noble metal and rare earth metal aluminium oxide or amorphous silica-alumina as shell, preparation method is to prepare to introduce activated carbon slurries during aluminium oxide or amorphous silica-alumina and noble metal and rare-earth metal complex plastic using coprecipitation, after plastic through aging and etc. obtain catalyst.Catalytic wet oxidation catalyst of the catalyst particularly useful as catalytic wet oxidation catalyst, especially Love psychology, with the stability for improving the activity of catalyst and using.
Description
Technical field
The present invention relates to a kind of catalytic wet oxidation catalysts and preparation method thereof, are especially used for catalytic wet oxidation
Noble metal catalyst and preparation method thereof.
Background technology
It is increasingly strict with global environmental regulation, the Con trolling index of sewage qualified discharge require it is higher and higher, herein
Under form, waste water treatment by catalytic oxidation has increasingly obtained the attention and use of people, and the catalysis such as high-concentration sewage is wet
Formula oxidation, catalytic and oxidative electrolysis technology, photochemical catalytic oxidation, advanced oxidation etc..In waste water catalytic oxidation process, to obtain ideal place
Reason effect and by reducing reaction temperature, reaction pressure to keep lower 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 includes mainly to generate the Fenton reagent of oxygen radical, Fe3+、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 recycled after being discharged or regenerate in being discharged by treated.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 consumptions 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 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 for selecting activated carbon supported metal to prepare
Agent wear-resisting property is poor, and mechanical strength is not high, and the metal of load is easy to run off so that the application effect of activated-carbon catalyst has beaten folding
Button.Amorphous alumina is because having good chemical stability, large pore volume to 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 that there are specific surfaces is small for amorphous alumina
Disadvantage, it is relatively small to the absorption and conversion capability of organic matter.
CN201110225789.7 discloses a kind of side preparing benzene adsorption material using discarded active amorphous aluminium oxide
Method, it is that useless active amorphous aluminium oxide is cleaned, filters, after drying, is 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, can not only block aluminium oxide in this way
Duct, and the activated carbon generated in this way 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, binder 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 dispersion are 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 binder are raw material, through mixing, granulation, it is aging, be molded, dry, be sintered, rinse, drying and other steps, in this way
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 increase.
Invention content
In view of the deficiencies of the prior art, have that catalytic performance is good, wear-resisting property is strong, using steady the present invention provides one kind
The qualitative good noble metal catalyst and preparation method thereof for catalytic wet oxidation.
The catalytic wet oxidation catalyst of the present invention, including following nucleocapsid components, which is with work
Property charcoal be core, using the aluminium oxide containing noble metal and rare earth metal or the amorphous silica-alumina containing noble metal and rare earth metal as shell, with
On the basis of activated carbon and the weight of aluminium oxide or activated carbon and amorphous silica-alumina, activated carbon accounts for 10% ~ 70%, preferably 30% ~ 70%,
Aluminium oxide or amorphous silica-alumina account for 30% ~ 90%, 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 1% ~ 15%, preferably 1% ~ 10% based on the element, activated carbon and aluminium oxide or activated carbon and amorphous silicon
The content of aluminium is 89% ~ 98%.
In the amorphous silica-alumina containing noble metal and rare earth metal, on the basis of the weight of amorphous silica-alumina, oxidation
The content of silicon is 10% ~ 90%, 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 one or more in lanthanum, cerium, praseodymium, neodymium.
The catalyst of the present invention can be not required to molding powder catalyst, can also be preformed catalyst.It is powdered
The granularity of catalyst is generally 0.05 ~ 0.20mm.Preformed catalyst can determine the size of granularity as needed, generally 0.5 ~
8.0mm。
The heretofore described aluminium oxide containing noble metal and rare earth metal or the amorphous silicon containing noble metal and rare earth metal
Contain auxiliary agent in aluminium, auxiliary agent can be one or more in carrier common adjuvant component, such as titanium, zirconium, magnesium, zinc etc., with member
The weight content of element meter is 10% hereinafter, preferably 1% ~ 5%.
The property of preformed catalyst of the present invention is as follows：Specific surface area is 200 ~ 1000m20.3 ~ 1.8cm of/g, Kong Rongwei3/
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) the mesh activated carbon of 150 mesh ~ 300 is beaten；
(2) aluminium oxide or amorphous silica-alumina and the compound of noble metal and rare earth metal are being prepared using coprecipitation
Step is introduced during plastic（1）Obtained activated carbon slurries；
(3) step（2）Material after obtained plastic carries out aging, is filtered, washed, dries, and 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 protection, obtains catalyst；
B, by step（3）The catalyst material of gained is molded, and after drying, is roasted, is urged under inert gas protection
Agent；
C, by step（3）The catalyst material of gained roasts under inert gas protection, then again through molding, after dry,
It roasts under inert gas protection, 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 waste, as timber, sawdust, charcoal,
Coconut husk, shell, coal, gangue, petroleum coke, asphalt, polyvinyl chloride, polypropylene, organic resin, damaged tire, remains fruit stone
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, hole hold 0.5 ~ 1.8cm3/ g, 1 ~ 10nm of average pore radius.
In the method for the present invention, step（1）The described activated carbon mashing is carried out using conventional method, it is general using plus it is water, low
One or more in carbon alcohol are beaten, and wherein low-carbon alcohols are one or more in the monohydric alcohol that carbon atom number is 1 ~ 5.
In the method for the present invention, step（1）It is preferred that activated carbon first uses carbohydrate to handle, then it is beaten.The carbohydrate
It is one or more in the carbohydrate that preferably carbon atom number is 3 ~ 20 for one or more of monosaccharide and disaccharide, polysaccharide, such as：
It is one or more in triose, tetrose, pentose, hexose, maltose, sucrose, one kind or more more preferably in glucose, sucrose
Kind.The carbohydrate dosage accounts for the 2% ~ 50% of activated carbon weight, preferably 5% ~ 20%.Carbohydrate handles activated carbon can be straight by carbohydrate
It connects and is mixed with activated carbon, carbohydrate can also be dissolved in solvent and add activated carbon, solvent therein is water, low-carbon alcohols（That is carbon
The monohydric alcohol that atomicity is 1 ~ 5）In it is one or more.Carbohydrate handle activated carbon when, liquid consolidate volume ratio 10 hereinafter, it is preferred that
1 ~ 5.After carbohydrate handles activated carbon, excessive liquid phase is preferably filtered to remove, and is then beaten again.Conventional side can be used in mashing
Method carries out, it is general using plus water, low-carbon alcohols in it is one or more be beaten, it is 1 ~ 5 that wherein low-carbon alcohols, which are carbon atom number,
It is one or more in monohydric alcohol.
Preparing aluminium oxide or amorphous silica-alumina using coprecipitation can be by ability with noble metal and rare-earth metal complex
Process known to field technique personnel carries out.The neutralization plastic process of usually acid material and alkaline material.Plastic process can be with
It, can also be in such a way that two kinds of material cocurrents neutralize by the way of the continuous acid-base titration of soda acid.
Step of the present invention（2）In, preparing aluminium oxide and noble metal and rare earth metal composite oxide using coprecipitation is
It is reacted with precipitating reagent in silicon source, noble metal source and rare earth metal source and carries out plastic, silicon source is in aluminium chloride, aluminum sulfate, aluminum nitrate
It is one or more, precipitating reagent used is usually one in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide etc.
Kind is several.Noble metal source used in it and rare earth metal source generally use soluble metallic salt（Such as nitrate, chlorination
Object etc.）, can be mixed for corresponding acid material or alkaline material coprecipitated according to the acid-base property of metal salt solution used
It forms sediment, plastic cans can also first be added, then acid material carries out plastic, above content those skilled in the art root with alkaline material
Known to coprecipitation.
Step of the present invention（2）In, amorphous silica-alumina and noble metal and rare earth metal combined oxidation are prepared using coprecipitation
Object is that progress plastic is reacted in silicon source, silicon source, noble metal source and rare earth metal source with precipitating reagent.Plastic material generally comprises silicon source
（Al2(SO4)3、AlCl3、Al(NO3)3And NaAlO2One or more of Deng）, silicon source（Waterglass, Ludox and organic siliceous
One or more of compound etc.）, precipitating reagent（NaOH、NH4OH or CO2Deng）, it is used according to the different selections of plastic process,
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）Plastic is neutralized,（2）Basic aluminium salt（NaAlO2）With acidic precipitation agent（CO2）Neutralize plastic.Silicon
Source generally introduces plastic cans during plastic, can also with neutralize plastic again after silicon source or precipitant mix, such as waterglass plus
Enter and carry out neutralization plastic in basic aluminium salt or alkaline precipitating agent, Ludox, which is added in acid aluminium salt, to carry out neutralizing plastic etc..Silicon source
It can also be added after silicon source precipitates in material.It can also be by two or more combined use of aforesaid way.Used in it
Noble metal source and rare earth metal source generally use soluble metallic salt（Such as nitrate, chloride etc.）, can be according to gold used
The acid-base property for belonging to salting liquid is mixed for being co-precipitated, plastic cans can also first be added with corresponding acid material or alkaline material,
Then acid material carries out plastic with alkaline material, and the above content is those skilled in the art according to known to coprecipitation.
The coprecipitation, plastic process generally carry out at room temperature ~ 85 DEG C, are relatively suitably for 40 ~ 80 DEG C, preferably 50
~70℃.The plastic process generally carries out under certain pH value condition, and typical pH is 6.0 ~ 10.0, is relatively suitably for 7.0
~ 9.5, preferably 7.5 ~ 9.0.Step（3）The aging, condition are as follows：PH is 6.0 ~ 10.0, preferably 7.0 ~ 9.5, aging
0.25 ~ 8.0 hour time was relatively suitble at 0.5 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours, and aging temperature is room temperature ~ 85 DEG C, excellent
It is selected as 40 ~ 80 DEG C.Temperature and pH when aging with when neutralizing temperature and pH it is preferably identical.
In the present invention, step（2）The process of aluminium oxide and noble metal and rare-earth metal complex is prepared using coprecipitation
In, it can also be added one or more in carrier common adjuvant component, such as titanium, zirconium, magnesium, zinc etc., addition can be with
It is selected according to actual needs.
Step of the present invention（2）In, step（1）The incorporation way of the mixture of gained uses the one or more of following manner
Combination：（1）During coprecipitation reaction, which is continuously added in plastic cans；（2）The mixture is charged first into
In glue tank, coprecipitation reaction is then carried out；（3）The mixture is mixed with the one or more of plastic material, then plastic object
Material carries out coprecipitation 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 minimal amount of heteroion should be free of or contained after washing, filtering, heteroion includes
Na+、Cl-、SO4 2-、NO3 -、K+It is 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 used
Natural drying, oven drying, spray drying, microwave drying or infra-red drying, the drying condition generally used are as follows：50 ~
It is 1 ~ 15 hour dry at 150 DEG C.
Step of the present invention（4）In, method A is to obtain powder catalyst without molding roasting direct.Roasting described in method A
Burning condition is as follows：Calcination temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
Step of the present invention（4）In, the molding described in method B and method C can carry out as needed, generally strip, circle
Column, spherical shape, irregular strip, special-shaped ball etc., granularity can determine as needed, generally 0.5 ~ 8.0mm.The forming process
In, it can be added as needed one or more in shaping assistant such as adhesive, peptization acid, extrusion aid.
Step of the present invention（4）In, the drying condition described in method B is 1 ~ 15 hour dry 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 catalyst material of gained roasts under inert gas protection
It burns, the roasting condition is as follows：Calcination temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.Then it is done again through molding
It after dry, roasts under inert gas protection, obtains catalyst, drying condition after molding 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, and roasting time is generally 1 ~ 10 hour.
It in the present invention, is roasted under inert gas protection, selected inert gas is generally nitrogen or argon gas.
The nucleocapsid component that catalyst of the present invention uses be by using activated carbon as core, with containing noble metal and rare earth metal
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 it is amorphous
Sial）The characteristics of aperture is big, Kong Ronggao, activated carbon is strong for the adsorption capacity of organic molecule, and Preferential adsorption organic molecule is by urging
The diffusion of the outer surface inner surface of agent makes reactant first and the aluminium oxide containing active metal as shell in this way（Or nothing
Amorphous silicon-alumina）Haptoreaction, on the other hand, aluminium oxide（Or amorphous silica-alumina）With active metal binding force compared with activated carbon with
The binding force of active metal is strong, is not easy to cause the loss of active metal while providing sufficient activity, make catalyst have compared with
High reactivity and stability in use, improves the service life of catalyst.The catalyst is particularly useful as catalytic wet oxidation
The catalytic wet oxidation catalyst of catalyst, especially Love psychology, with the stability for improving the activity of catalyst and using.
In the preparation process of catalyst of the present invention, in aluminium oxide（Or amorphous silica-alumina）Plastic during introduce activity
Charcoal makes aluminium oxide in this way（Or amorphous silica-alumina）Colloid wraps up activated carbon, is formed using activated carbon as core, to contain noble metal and rare earth
The aluminium oxide of metal（Or amorphous silica-alumina）For the compound of shell, activated carbon large specific surface area, adsorption capacity are fully utilized in this way
Strong advantage and aluminium oxide（Or amorphous silica-alumina）The advantages of high mechanical strength, aperture is big, pore distribution concentration, aluminium oxide（Or nothing
Amorphous silicon-alumina）Activated carbon is wrapped up, activated carbon is made to be evenly distributed on aluminium oxide（Or amorphous silica-alumina）In, aluminium oxide（Or it is amorphous
Sial）Provide good mechanical support and intensity so that catalyst has good mechanical strength and wear-resisting property, while former
Material passes through shell aluminium oxide（Or amorphous silica-alumina）Duct be diffused into the inner surface of activated carbon, activated carbon carries for catalyst
Powerful specific surface area is supplied, activated carbon is in aluminium oxide（Or amorphous silica-alumina）In fine dispersion make the utilization rate of activated carbon
It is improved, the surface of activated carbon has obtained more fully utilizing, and has to the performance and stability that improve catalyst
Good facilitation.
In the preparation process of catalyst of the present invention, in particular by being beaten again after carbohydrate processing activated carbon, then in oxygen
Change aluminium（Or amorphous silica-alumina）Plastic during introduce, carbohydrate is uniformly adsorbed on the surfaces externally and internally of activated carbon, by rear
Continuous roasting process makes to be mixed in aluminium oxide（Or amorphous silica-alumina）With the carbohydrate breakdown charing among activated carbon, the work newly formed
Property charcoal connect aluminium oxide（Or amorphous silica-alumina）And activated carbon so that activated carbon and aluminium oxide（Or amorphous silica-alumina）Combination more
Step up close, inner surface of the carbohydrate through the new Activated Carbon Modification original activated carbon being decomposed to form on activated carbon inner surface increases work
The adsorption activity position of property charcoal inner surface.It is therefore preferable that increasing carbohydrate handles activated carbon, aluminium oxide can be promoted（Or amorphous silicon
Aluminium）Activated carbon is closely wrapped up, is conducive to the mechanical strength and attrition resistance energy that improve catalyst, and improve activated carbon
Inner surface utilization rate, be conducive to improve catalyst activity and stability.
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 implementation mode
The specific surface area and Kong Rong 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 range of these embodiments.
The property of commercially available powdery coconut husk charcoal used in the present invention is as follows：Specific surface area 928m2/ g, hole hold 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, cerous nitrate, chloroplatinic acid are added in distilled water, while heating and stirring to dissolving, is obtained molten
Liquid (a).Appropriate distilled water is added in concentrated ammonia liquor and is diluted to about 10wt% weak aqua ammonias (b).Glucose solution is added in powdery coconut husk charcoal
In be uniformly mixed, liquid consolidate volume ratio be 3：1, then plus water is beaten, and obtains slurries (c).(a) is added in plastic cans and stirs
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 (c) is added 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, material in tank is filtered by pH=8.0, aging 1 hour, washing to no chlorion, filtering, and filter cake is done at 110 DEG C
Dry 10 hours, catalyst material A-1 is obtained, then roasts 5 hours, pulverizes and sieves under the conditions of 550 DEG C under nitrogen protection
To powder 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
It is 10 hours dry at 110 DEG C, it is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, obtains catalyst A, composition is shown in Table 2.
Embodiment 2
Solid aluminum sulfate, cerous nitrate, rhodium nitrate are added in distilled water, while heating and stirring to dissolving, is obtained molten
Liquid (a).Appropriate distilled water is added in concentrated ammonia liquor and is diluted to about 10wt% weak aqua ammonias (b).Glucose solution is added in powdery coconut husk charcoal
In be uniformly mixed, liquid consolidate volume ratio be 3：1, then plus water is beaten, and obtains activated carbon slurries (c).A plastic cans is taken, is added in tank
(a) and after being heated with stirring to 60 DEG C the valve for the container for having (b), is opened, system in tank is added drop-wise to by control within 10 minutes
The valve of (c) container is opened in pH=4.0, continues that (b) is added dropwise, controls in 30 minutes system in tank being added drop-wise to pH=8.0, controls
(c) valve of container, guarantee are added dropwise to complete at this time.Keep temperature be 60 DEG C, pH=8.0, aging 1 hour, by material in tank into
Row filtering, washing to sulfate radical-free ion, filtering is 10 hours dry at 110 DEG C by filter cake, obtains catalyst material A-2, so
It is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection afterwards, pulverizes and sieves to obtain powder catalyst J-2.Plastic agents useful for same
Amount be listed in table 1.
100 grams of catalyst material A-2 is taken, contacts to form paste with the peptization liquid containing nitric acid, then extruded moulding exists
It is 10 hours dry at 110 DEG C, it is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, obtains catalyst B, composition is shown in Table 2.
Embodiment 3
Solid aluminum sulfate, cerous nitrate, rhodium nitrate are added in distilled water, while heating and stirring to dissolving, is obtained molten
Liquid (a).Solid sodium metaaluminate is configured to a concentration of 250g Al2O3/ L sodium aluminate solutions (b).Sugarcane is added in powdery coconut husk charcoal
It is uniformly mixed in sugar aqueous solution, it is 3 that liquid, which consolidates volume ratio,：1, then plus water is beaten, and obtains slurries（c）.Waterglass is according to 1:2 ratio
Example dilution in deionized water, is configured to solution (d).Add after taking a plastic cans, merging 2L deionized waters to be heated with stirring to 60 DEG C
Enter slurries（c）, open simultaneously have (a), (b) container valve, pH=8.0 of control system, control 45 minutes in will
(a) it drips off, closes valve.It is 65 DEG C to keep temperature, pH=8.0, stops after twenty minutes, solution (d) is added into system, according to
The content 55wt% calculating of silica adds in 10 minutes in amorphous silica-alumina.Then aging 1 hour, by material in tank into
Row filtering, washing to sulfate radical-free ion, filtering is 10 hours dry at 110 DEG C by filter cake, obtains catalyst material A-3, so
It is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection afterwards, pulverizes and sieves to obtain powder catalyst J-3.Plastic agents useful for same
Amount be listed in table 1.
100 grams of catalyst material A-3 is taken, contacts to form paste with the peptization liquid containing nitric acid, then extruded moulding exists
It is 10 hours dry at 110 DEG C, it is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, obtains catalyst C, composition is shown in Table 2.
Embodiment 4
Solid aluminum chloride, cerous nitrate, rhodium nitrate are added in distilled water, while heating and stirring to dissolving, is obtained molten
Liquid (a).Appropriate distilled water is added in concentrated ammonia liquor and is diluted to about 10wt% weak aqua ammonias (b).Glucose solution is added in powdery coconut husk charcoal
In be uniformly mixed, liquid consolidate volume ratio be 3：1, then plus water is beaten, and obtains activated carbon slurries (c).(a) is added in plastic cans and stirs
It mixes after being heated to 60 DEG C, opens the valve for the container for having (b), control and system in tank is added drop-wise to pH=4.0 within 10 minutes,
(c) is added into tank at this time, 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 to keep temperature
DEG C, material in tank is filtered by pH=8.0, aging 1 hour, washing to no chlorion, filtering, and filter cake is done at 110 DEG C
Dry 10 hours, catalyst material A-4 is obtained, then roasts 5 hours, pulverizes and sieves under the conditions of 550 DEG C under nitrogen protection
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, then extruded moulding exists
It is 10 hours dry at 110 DEG C, it is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, obtains catalyst D, composition is shown in Table 2.
Embodiment 5
Solid aluminum sulfate, lanthanum nitrate, chloroplatinic acid are added in distilled water, while heating and stirring to dissolving, is obtained molten
Liquid (a).Appropriate distilled water is added in concentrated ammonia liquor and is diluted to about 10wt% weak aqua ammonias (b).Glucose solution is added in powdery coconut husk charcoal
In be uniformly mixed, liquid consolidate volume ratio be 3：1, then plus water is beaten, and obtains activated carbon slurries (c).A plastic cans is taken, is added in tank
(a) and after being heated with stirring to 60 DEG C the valve for the container for having (b), is opened, system in tank is added drop-wise to by control within 10 minutes
The valve of (c) container is opened in pH=4.0, continues that (b) is added dropwise, controls in 30 minutes system in tank being added drop-wise to pH=8.0, controls
(c) valve of container, guarantee are added dropwise to complete at this time.Keep temperature be 60 DEG C, pH=8.0, aging 1 hour, by material in tank into
Row filtering, washing to sulfate radical-free ion, filtering is 10 hours dry at 110 DEG C by filter cake, obtains catalyst material A-5, so
It is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection afterwards, pulverizes and sieves to obtain powder catalyst J-5.Plastic agents useful for same
Amount be listed in table 1.
100 grams of catalyst material A-5 is taken, contacts to form paste with the peptization liquid containing nitric acid, then extruded moulding exists
It is 10 hours dry at 110 DEG C, it is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, obtains catalyst E, composition is shown in Table 2.
Embodiment 6
The synthesis for repeating embodiment 2, not adding carbohydrate during plastic are made catalyst material A-6 and powdered urge
Agent J-6.
Preformed catalyst is prepared with embodiment 2, and catalyst F is obtained, and composition is shown in Table 2.
Embodiment 7
The synthesis for repeating embodiment 3, not adding carbohydrate during plastic are made catalyst material A-7 and powdered urge
Agent J-7.
Preformed catalyst is prepared with embodiment 3, and catalyst G is obtained, and composition is shown in Table 2.
Comparative example 1
The synthesis for repeating embodiment 2, does not add activated carbon and carbohydrate during plastic, and comparative catalyst's material is made
PA-1 and powder catalyst DF-1, appearance white.
Preformed catalyst is prepared with embodiment 2, and catalyst DA is obtained, and 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
It is 10 hours dry at 110 DEG C afterwards, after being roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, carrier is obtained, appearance is black
Color.Then dipping method supported active metals component is used, catalyst DB is obtained, composition is shown in Table 2.
Comparative example 3
By activated carbon used in embodiment 2 with catalyst material PA-1 physical mixeds, connect with the peptization liquid containing nitric acid
It touches and forms paste, extruded moulding is then 10 hours dry at 110 DEG C, is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection
Afterwards, catalyst carrier DZ-C is obtained, wherein activated carbon and alumina content is same as Example 2, appearance black.Then it uses
Dipping method supported active metals component, obtains catalyst DC, and composition is shown in Table 2.
1 plastic reagent quality of table
The composition and property of 2 catalyst of table
The catalyst property obtained after activated carbon is handled it can be seen from catalyst property in table 2 using carbohydrate to obtain
Improve.
Appearance by catalyst material and catalyst obtained by the embodiment of the present invention is canescence, without apparent black,
Illustrate that activated carbon becomes the core of catalyst material and catalyst.
In the present invention, using X-ray photoelectron spectroscopy（XPS）To 1 gained catalyst material table of embodiment 2 and comparative example
The element in face is analyzed.By analysis result as it can be seen that the element on 2 surfaces gained catalyst material A-2 of embodiment forms and PA-1
It forms essentially identical, there is micro elemental carbon.This further illustrate, catalyst material of the invention be using activated carbon as core,
Using containing noble metal and rare earth metal aluminium oxide or amorphous silica-alumina as shell.
Catalyst prepared by the embodiments of the present invention and comparative example is evaluated.Catalyst is carried out using simulated wastewater
Evaluation.Acrylic acid wastewater, COD 30000mg/L are prepared, pH value of solution is 6~7, is evaluated in small fixed reactor.
The volume space velocity 2.0h in 45 DEG C for the treatment of temperature, liquid-1, the waste water is continuously urged under the reaction condition of gas-liquid volume ratio 200
Dampness elimination formula airoxidation, handling result are listed in table 3.
3 evaluation result of table
| Catalyst is numbered | B | C | F | G | DA | DB | DC |
| COD removal rates, % | 96.6 | 95.4 | 94.2 | 94.1 | 83.8 | 96.1 | 91.6 |
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, even
After reforwarding turns 1000h, 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, % | 95.7 | 94.1 | 92.5 | 92.5 | 80.7 | 66.8 | 88.8 |
| Metal conservation rate in catalyst, % | 94.39 | 94.35 | 94.11 | 94.00 | 94.42 | 68.26 | 83.49 |
After the catalyst prepared by the method for the present invention it can be seen from 4 result of table is using 1000h, active reduction amplitude is smaller,
With good stability, the conservation rate of active metal obviously increases.
Claims (24)
1. a kind of catalytic wet oxidation catalyst, including following nucleocapsid components, which is to be with activated carbon
Core, using the aluminium oxide containing noble metal and rare earth metal or the amorphous silica-alumina containing noble metal and rare earth metal as shell, with activated carbon
With on the basis of the weight of aluminium oxide or activated carbon and amorphous silica-alumina, activated carbon accounts for 10% ~ 70%, and aluminium oxide or amorphous silica-alumina account for
30%~90%；The noble metal is the one or several kinds in Pt, Pd, Rh, Ru, and the rare earth metal is lanthanum, cerium, praseodymium, neodymium
In it is one or more.
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
The content of standard, noble metal is 0.01% ~ 1.0% based on the element, and the content of rare earth metal is 1.0% ~ 15.0% based on the element, activated carbon
It is 84% ~ 98% 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：On the basis of the weight of amorphous silica-alumina, silica
Content is 10% ~ 90%.
6. catalyst described in accordance with the claim 1, it is characterised in that：On the basis of the weight of amorphous silica-alumina, silica
Content is 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. catalyst according to claim 7, it is characterised in that the property of the preformed catalyst is as follows：Specific surface area is
200 ~1000m20.3 ~ 1.8cm of/g, Kong Rongwei3/ 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：The aluminium oxide containing noble metal and rare earth metal contains
Contain adjuvant component in the amorphous silica-alumina of noble metal and rare earth metal, adjuvant component is titanium, zirconium, magnesium, one kind in zinc or more
Kind, weight content based on the element is 10% or less.
10. the preparation method of any catalyst of claim 1 ~ 8, including：
(1) the mesh activated carbon of 150 mesh ~ 300 is beaten；
(2) in the plastic for preparing aluminium oxide or amorphous silica-alumina and noble metal and the compound of rare earth metal using coprecipitation
Step is introduced in the process（1）Obtained activated carbon slurries；
(3) step（2）Material after obtained plastic carries out aging, is filtered, washed, dries, and 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 protection, obtains catalyst；
B, by step（3）The catalyst material of gained is molded, and after drying, is roasted under inert gas protection, is obtained catalyst；
C, by step（3）The catalyst material of gained roasts under inert gas protection, then again through molding, 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, hole hold 0.5 ~ 1.8cm3/ g, 1 ~ 10nm of average pore radius.
13. according to the method for claim 10, it is characterised in that step（1）The described activated carbon mashing using plus it is water, low
One or more in carbon alcohol are beaten, and wherein low-carbon alcohols are one or more in the monohydric alcohol that carbon atom number is 1 ~ 5.
14. according to the method for claim 10, it is characterised in that step（1）The activated carbon first uses carbohydrate to handle,
Then it is beaten, the carbohydrate is one or more in the carbohydrate that carbon atom number is 3 ~ 20；Carbohydrate handles activated carbon
Carbohydrate is directly mixed with activated carbon, or carbohydrate is dissolved in solvent and adds activated carbon.
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
It is 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 original
It is one or more in the monohydric alcohol that subnumber is 1 ~ 5；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 coprecipitation prepare aluminium oxide
Or the plastic process of amorphous silica-alumina and noble metal and the compound of rare earth metal be acid material and alkaline material neutralization it is anti-
Process is answered, plastic process is by the way of the continuous acid-base titration of soda acid, or in such a way 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 activated carbon slurries of gained
Incorporation way use following manner one or more combination：（1）During coprecipitation reaction, which is connected
It is continuous to be added in plastic cans；（2）The activated carbon slurries are charged first in plastic cans, coprecipitation reaction is then carried out；（3）By the work
Property charcoal slurries and coprecipitation reaction material one or more mix, then carry out coprecipitation reaction.
22. according to the method for claim 10, it is characterised in that：Step（2）Described in coprecipitation prepare aluminium oxide
Or during the plastic of the compound of amorphous silica-alumina and noble metal and rare earth metal, introduce adjuvant component, adjuvant component be titanium,
It is 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 ~
It is 1 ~ 15 hour dry 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, and roasting time is 1 ~ 10 hour, the drying condition described in method B be at 80 ~ 200 DEG C, dry 1 ~
15 hours, calcination temperature was 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, in method C, by step（3）The catalyst material of gained
Material roasts under inert gas protection, and the roasting condition is as follows：Calcination temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10
Hour, then roasts under inert gas protection after dry through molding again, obtain catalyst, drying condition after molding is such as
Under：At 80 ~ 200 DEG C, 1 ~ 15 hour dry, roasting condition is as follows：Calcination temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 small
When.
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