CN104667920B - 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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Abstract
The invention discloses a noble metal catalyst for catalytic wet oxidation and a preparation method thereof. The catalyst comprises a carrier, an active metal ingredient and an auxiliary, wherein the active metal ingredient is one or more of Pt, Pd, Rh and Ru, and the auxiliary is rare-earth metal; and the carrier uses activated carbon as a core, and amorphous alumina as a shell. The preparation method comprises the following steps: introducing activated carbon slurry into the process of gelling amorphous alumina, and preparing a carrier material by means of aging and other steps; and preparing the carrier, and loading the active metal ingredient and the auxiliary. According to the catalyst, a reactant firstly contacts and reacts with alumina serving as the shell layer, and is contacted with the activated carbon serving as the core layer to react, so that the advantages of alumina and activated carbon can be sufficiently utilized, the catalyst has relatively high reaction activity and using stability, and the service life of the catalyst can be prolonged.
Description
Technical field
The present invention relates to a kind of catalytic wet oxidation catalyst and preparation method thereof, particularly for CWO
Noble metal catalyst and preparation method thereof.
Background technology
With increasingly strict, the Con trolling index requirement more and more higher of sewage qualified discharge of global environmental regulation, herein
Under form, waste water treatment by catalytic oxidation has increasingly obtained the attention and use of people, and the catalysis of 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 the wastewater treatment expense by reducing reaction temperature, reaction pressure to keep relatively low, prepare have high-activity component,
High intensity, the cheap catalyst of high stability undoubtedly turn into the key of waste water catalytic oxidation technologies application.
The catalyst of waste water catalysis oxidation is broadly divided into homogeneous catalyst and the class of heterogeneous solid catalyst two.
Homogeneous catalyst mainly includes producing Fenton reagent, the Fe of oxygen radical3+、Cu2+, the metal such as cobalt and manganese
Ion, by means of the effect of these homogeneous catalysts, organic component, sulfide, ammonia nitrogen in waste water etc. are by air, oxygen, smelly
The oxide isolations such as oxygen, hydrogen peroxide are oxidized into low molecular acid (low mass molecule alcohol or carbon dioxide), sulfate or thiosulfuric acid
Salt, nitrogen etc., make waste water reach the processing intent of decarburization, desulfurization and denitrogenation.Homogeneous oxidation catalyst prepare and using process compared with
For simple, typically directly can be made into the aqueous solution from slaines such as iron, copper, cobalt, manganese or be directly thrown into handled waste water,
And by processing after water outlet in discharge or regeneration Posterior circle use.Using homogeneous catalytic oxidation, because metal active constituent is useless
Can fully be dissolved in water and disperseed, typically can reach relatively stable water treatment effect, but exist that reagent consumption is big, fortune
The serious problems such as row costly, metal loss and secondary pollution, cause its application to be subject to larger limitation.
Heterogeneous solid catalyst is mainly with activated carbon, molecular sieve, amorphous alumina, titanium dioxide etc. as carrier, with
One or more in alkali metal, alkaline-earth metal, transition metal or Pt, Pd noble metal make the catalyst that active component is constituted.It is living
Property charcoal be made up of carbonaceous material black, hole is flourishing, specific surface area is big, a high adsorption capacity class microcrystalline carbon.Activity
Charcoal is stable in properties, acidproof, alkaline-resisting, heat-resisting, water insoluble or organic solvent, easily regeneration, is a kind of environmentally friendly adsorbent, extensively
It is general to be applied to the fields such as Industrial " three Waste " improvement, food, medicine, carrier, semiconductor, battery and power storage.Currently used for useless
The heterogeneous solid catalyst of water process selects the catalysis of activated carbon supported metal preparation mostly from activated carbon as carrier
Agent anti-wear performance is poor, and mechanical strength is not high, and the metal of load is easy to run off so that the application effect of activated-carbon catalyst has beaten folding
Button.Amorphous alumina is because having good chemical stability, and pore volume is big, with certain acidity, pore size distribution$ concentration, machine
Tool intensity is big, it is corrosion-resistant the advantages of, be widely used in catalytic field, but amorphous alumina to there is specific surface small
Shortcoming, the absorption and conversion capability to organic matter is relatively small.
CN201110225789.7 discloses a kind of side that benzene adsorption material is prepared using discarded active amorphous aluminum oxide
Method, it be by useless active amorphous aluminum oxide is cleaned, filtering, dry after, prepared using cryogenic seal heat treatment mode a kind of
Active amorphous aluminum oxide/absorbent charcoal composite material, has good adsorption effect to benzene.The method is by amorphous alumina
Internal organic matter carbonizing, activated carbon is mainly distributed in the duct of amorphous alumina, so can not only block aluminum oxide
Duct, and the activated carbon for so being generated skewness in aluminum oxide.
CN201110255525.6 discloses a kind of preparation method of active amorphous aluminum oxide/absorbent charcoal composite material,
Be by waste aluminum sludge, activated carbon, binding agent by mixing, granulation, it is old, be molded, dry, sinter, rinse, dry
Active amorphous aluminum oxide/absorbent charcoal composite material is made etc. step.The method belongs to salic species and activated carbon thing
Reason mixed process, aluminum oxide and activated carbon dispersion are uneven；And the sludge impurity content that is used is high, the amorphous of gained
Aluminium property is unstable, it is impossible to repeat, complex structure.
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 old, be molded, dry, sinter, rinse, drying and other steps, so
The composite for obtaining is still the physical mixture of aluminum oxide and activated carbon, and aluminum oxide disperses uneven, its synthesis with activated carbon
Performance also needs further raising.
The content of the invention
In view of the shortcomings of the prior art, have that catalytic performance is good, anti-wear performance strong the invention provides one kind, using steady
Qualitative good noble metal catalyst for CWO and preparation method thereof.
Catalytic wet oxidation catalyst of the invention, the catalyst includes carrier, active metal component and auxiliary agent, wherein with
One or several in Pt, Pd, Rh, Ru are active metal component, and rare earth metal is auxiliary agent, and carrier is with 150 mesh ~ 300 mesh
Activated carbon be core, with amorphous alumina as shell, wherein activated carbon accounts for the 10% ~ 70% of vehicle weight, preferably 30% ~ 70%,
Aluminum oxide accounts for the 30% ~ 90% of vehicle weight, preferably 30% ~ 70%.
In catalyst of the present invention, with one or several in precious metals pt, Pd, Rh, Ru as active component, rare earth metal
Be auxiliary agent, on the basis of the weight of catalyst, noble metal with the content that element is counted be 0.01% ~ 1.0%, the content of rare earth metal with
Element is calculated as 1% ~ 15%.
In catalyst of the present invention, described rare earth metal is one or more in lanthanum, cerium, praseodymium, neodymium.
Catalyst of the invention can be the powder catalyst, or preformed catalyst for being not required to shaping.It is powdered
The granularity of catalyst is generally 0.05 ~ 0.2mm.Preformed catalyst can as needed determine the size of granularity, generally 0.5 ~
8.0mm。
The property of preformed catalyst of the present invention is as follows：Specific surface area is 200 ~ 1000m2/ g, pore volume is 0.3 ~ 1.8cm3/
G, rate of wear<3wt%, side pressure strength is 100 ~ 250N/cm.
The preparation process of catalytic wet oxidation catalyst of the present invention, including：
(1) by 150 mesh ~ 300 mesh activated carbon mashing；
(2) step is introduced during amorphous alumina plastic（1）The activated carbon slurries for obtaining；
(3) step（2）Material after the plastic for obtaining carries out aging, filtering, washing, dries, and obtains catalyst carrier material
Material；
(4) by step（3）The carrier material of gained is made catalyst carrier, and the preparation of the catalyst carrier is preferably at least
Using one of following methods：
A, by step（3）The carrier material of gained, is calcined under inert gas shielding, obtains catalyst carrier；
B, by step（3）The carrier material shaping of gained, after drying, is calcined under inert gas shielding, is catalyzed
Agent carrier；
C, by step（3）The carrier material of gained is calcined under inert gas shielding, then again through shaping, after drying,
It is calcined under inert gas shielding, obtains catalyst carrier；
(5) step（4）Active metal component and auxiliary agent are impregnated in the catalyst carrier of gained, is then dried, in indifferent gas
The lower roasting of body protection, obtains catalytic wet oxidation catalyst.
Step (1) the of the present invention activated carbon can select conventional Powdered Activated Carbon commodity, 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, such as timber, wood chip, charcoal,
It is coconut husk, fruit stone, shell, coal, gangue, petroleum coke, asphalt, polyvinyl chloride, polypropylene, organic resin, damaged tire, surplus
The various activated carbon products that remaining sludge etc. is obtained through traditional preparation methods.Activated carbon used in the present invention is powder activated
Charcoal, the mesh of granularity 150 ~ 300,500 ~ 3000m of specific surface area2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius.
In the inventive method, step（1）Described activated carbon mashing is carried out using conventional method, it is general using adding water, it is low
It is beaten for one or more in carbon alcohol, wherein low-carbon alcohols are that carbon number is one or more in 1 ~ 5 monohydric alcohol.
In the inventive method, step（1）It is preferred that activated carbon is first processed using carbohydrate, then it is beaten.Described carbohydrate
Be one or more in monosaccharide and disaccharide, polysaccharide, preferably carbon number for 3 ~ 20 carbohydrate, for example：Triose, tetrose, penta
One or more in sugar, hexose, maltose, sucrose, more preferably one or more in glucose, sucrose.Described sugar
Class consumption accounts for the 2% ~ 50% of activated carbon weight, preferably 5% ~ 20%.Carbohydrate treatment activated carbon can be by carbohydrate directly and activated carbon
Mixing, it is also possible to be dissolved in carbohydrate and activated carbon is added in solvent, solvent therein is water, low-carbon alcohols（I.e. carbon number is 1 ~ 5
Monohydric alcohol）In one or more.During carbohydrate treatment activated carbon, its liquid consolidates volume ratio below 10, preferably 1 ~ 5.Carbohydrate
After treatment activated carbon, excessive liquid phase is preferably filtered to remove, and is then beaten again.Mashing can be carried out using conventional method, and one
As one or more using adding water, in low-carbon alcohols be beaten, wherein low-carbon alcohols are carbon number in 1 ~ 5 monohydric alcohol
One or more.
Step of the present invention（2）Described in the plastic process of amorphous alumina can be by well known to those skilled in the art
Process is carried out.The plastic process of amorphous alumina is usually the neutralization reaction process of acid material and alkaline material.Plastic mistake
Journey can be by the way of the continuous acid-base titration of soda acid, it would however also be possible to employ the mode that two kinds of material cocurrents are neutralized.
Step of the present invention（2）In, aluminum oxide plastic is entered with acidic precipitation agent or alkaline precipitating agent using aluminum soluble salt
The process of row neutralization reaction, wherein aluminum soluble salt used is one or more in aluminium chloride, aluminum sulfate, aluminum nitrate, institute
Acidic precipitation agent is usually one or several in hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, carbon dioxide etc., alkalescence used
Precipitating reagent is usually one or several in sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor etc..Aluminum oxide into
Glue can also use meta-aluminate（Such as sodium metaaluminate and/or potassium metaaluminate）With acid aluminium salt（Such as aluminium chloride, aluminum nitrate,
One or more in aluminum sulfate）The method for carrying out neutralizing plastic.Described plastic process is typically carried out at room temperature ~ 85 DEG C,
Relatively it is suitably for 40 ~ 80 DEG C, preferably 50 ~ 70 DEG C.Described plastic process is typically carried out under certain pH value condition, typically
PH is 6.0 ~ 10.0, is relatively suitably for 7.0 ~ 9.5, preferably 7.5 ~ 9.0.Step（3）Described is aging, and condition is as follows：PH is 6.0
~ 10.0, preferably 7.0 ~ 9.5, ageing time 0.25 ~ 8 hour is relatively adapted at 0.5 ~ 5 hour, preferably 1 ~ 3 hour, aging temperature
It is room temperature ~ 85 DEG C to spend, preferably 40 ~ 80 DEG C.Temperature and pH when aging are preferably identical with temperature and pH when neutralizing.
Step of the present invention（2）In, step（1）The incorporation way of the mixture of gained uses one or more of following manner
Combination：（1）During plastic neutralization reaction, the mixture is continuously added in plastic cans；（2）The mixture is charged first to
In plastic cans, then will prepare in the acid material and alkaline material of amorphous alumina and plastic；（3）By the mixture with into
One or more mixing of glue material, then in plastic material and plastic.
Step of the present invention（3）In, the mode of washing of described material is known in those skilled in the art, can be selected
Add water the modes such as washing, lower alcohols washing when mashing washing, filtering, and the temperature of washing should be in the temperature model of room temperature ~ 90 DEG C
In enclosing, preferably 50 ~ 70 DEG C.It is to be carried out in the range of 1.0 ~ 9.0 in pH that the washing of the material is general, 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, after washing, filtering, filter cake is dried described material, and drying mode can be used
Natural drying, oven drying, spray drying, microwave drying or infra-red drying, the general drying condition for using are as follows：50 ~
Dried 1 ~ 15 hour at 150 DEG C.
Step of the present invention（4）In, method A is to obtain powdered catalytic agent carrier without shaping roasting direct.Described in method A
Roasting condition it is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
Step of the present invention（4）In, the shaping described in method B and method C can be carried out as needed, generally strip, circle
Column, spherical, irregular strip, special-shaped ball etc., granularity can determine as needed, generally 0.5 ~ 8.0mm.Described forming process
In, can as needed add 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 generally at 80 ~ 200 DEG C, is dried 1 ~ 15 hour, 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 carrier material of gained is calcined under inert gas shielding,
Described roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.Then again through shaping, dry
Afterwards, it is calcined under inert gas shielding, obtains catalyst carrier, the drying condition after shaping is as follows：At 80 ~ 200 DEG C, dry 1 ~
15 hours, roasting condition was as follows：Sintering temperature is generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
In the present invention, it is calcined under inert gas shielding, selected inert gas is generally nitrogen or argon gas.
Step of the present invention（5）In, carrier impregnation metal component can be spray, or saturation dipping, or
Supersaturation dipping.
Step of the present invention（5）In, after catalyst dipping, drying condition is generally at 80 ~ 200 DEG C, is dried 1 ~ 15 hour, roasting
Burn temperature and be generally 450 ~ 700 DEG C, roasting time is generally 1 ~ 10 hour.
Step of the present invention（5）In, during carrier impregnation active metal component, generally carried out using the maceration extract containing active metal
Dipping.Maceration extract is prepared using conventional method, will noble metal（One or more in platinum, palladium, ruthenium and rhodium）And rare earth metal
Predecessor be dissolved in solvent in be formulated.
The carrier that catalyst of the present invention is used is made up of the compound with activated carbon as core, with amorphous alumina as shell
, so make reactant first with as shell oxide contact react after, then contact with as the activated carbon of stratum nucleare carry out instead
Should, make full use of that aluminum oxide aperture is big, pore volume is high and activated carbon specific surface area is big, high adsorption capacity the characteristics of and active component
With the synergy of auxiliary agent, make catalyst that there is reactivity and stability in use higher, improve the service life of catalyst.
The catalyst is particularly useful as catalytic wet oxidation catalyst, especially the catalytic wet oxidation catalyst of Love psychology, to carry
The activity of high catalyst and the stability for using.
In the preparation process of catalyst of the present invention, activated carbon is introduced during the plastic of amorphous alumina, so made
Amorphous alumina colloid wraps up activated carbon, is formed with activated carbon as core, and the compound with amorphous alumina as shell is so comprehensive
Conjunction make use of activated carbon specific surface area big, the strong advantage of absorption affinity and aluminum oxide high mechanical strength, and aperture is big, pore distribution concentration
Advantage, aluminum oxide parcel activated carbon, activated carbon is evenly distributed in aluminum oxide, aluminum oxide provide good mechanical support and
Intensity so that catalyst has good mechanical strength and anti-wear performance, while raw material is spread by the duct of shell aluminum oxide
To the inner surface of activated carbon, activated carbon is there is provided powerful specific surface area for catalyst, and activated carbon is good in aluminum oxide
Good dispersion causes that the utilization rate of activated carbon is improved, and the surface of activated carbon has obtained more fully utilizing, and is catalyzed to improving
The performance and stability of agent have good facilitation.
In the preparation process of catalyst carrier of the present invention, in particular by being beaten again after carbohydrate treatment activated carbon, then
Introduced during the plastic of amorphous alumina, carbohydrate is uniformly adsorbed on the surfaces externally and internally of activated carbon, by follow-up
Roasting process makes to be mixed in the carbohydrate breakdown charing in the middle of aluminum oxide and activated carbon, new activated carbon connection aluminum oxide and the work for being formed
Property charcoal so that the combination of activated carbon and aluminum oxide is even closer, new activity of the carbohydrate on activated carbon inner surface through being decomposed to form
The inner surface of the former activated carbon of charcoal modification, increased the adsorption activity position of activated carbon inner surface.It is therefore preferable that increase carbohydrate treatment living
Property charcoal, aluminum oxide can be promoted closely to wrap up activated carbon, be conducive to improve catalyst mechanical strength and attrition resistance
Energy, and the utilization rate of the inner surface of activated carbon is improve, be conducive to improving the activity and stability of catalyst.
Catalyst preparation process of the present invention is simple, convenient, it is easy to operate, and is adapted to industrial production.
Specific embodiment
The specific surface area and pore volume of product of the present invention are determined using low temperature liquid nitrogen physisorphtion.Rate of wear is to use to turn
Cartridge type abrasion instrument is determined（It is specifically shown in《Catalyst carrier is prepared and application technology》（Petroleum industry publishing house, in May, 2002, Zhu Hong
Method is write, 4.5.4 sections）.Powder carrier and catalyst grain size are determined using laser particle size analyzer；Shaping carrier and catalysis
Agent granularity is measured using sieve method.In the present invention, wt% is mass fraction.
Preparation method of the invention is further illustrated with reference to specific embodiment, but the scope of the present invention is not only
It is limited to the scope of these embodiments.
Commercially available powdery coconut husk charcoal specific surface area 928m used in the present invention2/ g, pore volume 1.0cm3/ g, average pore radius
1.1nm, iodine sorption value 700mg/g, the mesh of granularity 200.
Embodiment 1
Solid aluminum chloride is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Add appropriate distilled water diluting into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is well mixed in adding D/W, liquid
Gu volume ratio is 3：1, then add water mashing, obtains slurries (c).After (a) is added in the plastic cans and being heated with stirring to 60 DEG C,
Opening has the valve of the container of (b), and system in tank is added drop-wise to pH=4.0 by control within 10 minutes, is now added in tank
C (), continues that (b) is added dropwise, system in tank is added drop-wise to pH=8.0 by control in 30 minutes.Keeping temperature is 60 DEG C, and pH=8.0 is aging
1 hour, material in tank is filtered, to without chlorion, filter cake is dried 10 hours, carried by filtering at 110 DEG C for washing
Body materials A -1, is then calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, pulverizes and sieves and obtains powder carrier J-1.Into
The amount of glue agents useful for same is listed in table 1.
100 grams of powder carrier J-1 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
Dried 10 hours at 110 DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Pt-Ce, so
Dried 10 hours at 110 DEG C afterwards, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst A, its composition is shown in Table
2。
Embodiment 2
Solid aluminum sulfate is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Add appropriate distilled water diluting into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is well mixed in adding D/W, liquid
Gu volume ratio is 3：1, then add water mashing, obtains activated carbon slurries (c).A plastic cans is taken, (a) is added in tank and is heated with stirring to
After 60 DEG C, opening has the valve of the container of (b), and system in tank is added drop-wise to pH=4.0 by control within 10 minutes, is opened (c) and is held
The valve of device, continues that (b) is added dropwise, and system in tank is added drop-wise to pH=8.0 by control in 30 minutes, controls the valve of the container of (c),
Guarantee is now added dropwise to complete.Keeping temperature is 60 DEG C, and pH=8.0 aging 1 hour, material in tank is filtered, washing to nothing
Sulfate ion, filtering dries 10 hours filter cake at 110 DEG C, obtains carrier material A-2, then exists under nitrogen protection
It is calcined 5 hours under the conditions of 550 DEG C, pulverizes and sieves and obtain powder carrier J-2.The amount of plastic agents useful for same is listed in table 1.
100 grams of carrier material A-2 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then 110
Dried 10 hours at DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Ru-Ce, then
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst B, its composition is shown in Table 2.
Embodiment 3
Solid aluminum sulfate is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.Solid is inclined
Sodium aluminate is configured to concentration for 250g Al2O3/ L sodium aluminate solutions (b).Mix during powdery coconut husk charcoal is added into aqueous sucrose solution
Uniformly, the solid volume ratio of liquid is 3：1, then add water mashing, obtains slurries（c）.A plastic cans is taken, the stirring of 2L deionized waters is inserted and is added
Slurries are added after hot to 60 DEG C（c）, while open have (a), the valve of the container of (b), the pH=8.0 of control system, control
(a) is dripped off in 45 minutes, closes valve.Keeping temperature is 60 DEG C, and pH=8.0 aging 1 hour, material in tank was carried out
Filter, washing to sulfate radical-free ion, filtering dries 10 hours filter cake at 110 DEG C, carrier material A-3 is obtained, then in nitrogen
It is calcined 5 hours under the conditions of 550 DEG C under gas shielded, pulverizes and sieves and obtain powder carrier J-3.The amount of plastic agents useful for same is listed in
Table 1.
100 grams of carrier material A-3 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then 110
Dried 10 hours at DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Ru-Ce, then
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst C, its composition is shown in Table 2.
Embodiment 4
Solid aluminum chloride is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Add appropriate distilled water diluting into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is well mixed in adding D/W, liquid
Gu volume ratio is 3：1, then add water mashing, obtains activated carbon slurries (c).(a) is added in plastic cans and 60 DEG C are heated with stirring to
Afterwards, the valve of the container for having (b) is opened, system in tank is added drop-wise to pH=4.0 by control within 10 minutes, is now added in tank
Enter (c), continue that (b) is added dropwise, system in tank is added drop-wise to pH=8.0 by control in 30 minutes.Keeping temperature is 60 DEG C, pH=8.0, always
Change 1 hour, material in tank is filtered, to without chlorion, filter cake is dried 10 hours, obtained by filtering at 110 DEG C for washing
Carrier material A-4, is then calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, pulverizes and sieves and obtains powder carrier J-4.
The amount of plastic agents useful for same is listed in table 1.
100 grams of carrier material A-4 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then 110
Dried 10 hours at DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Ru-Ce, then
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst D, its composition is shown in Table 2.
Embodiment 5
Solid aluminum sulfate is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Add appropriate distilled water diluting into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is well mixed in adding D/W, liquid
Gu volume ratio is 3：1, then add water mashing, obtains activated carbon slurries (c).A plastic cans is taken, (a) is added in tank and is heated with stirring to
After 60 DEG C, opening has the valve of the container of (b), and system in tank is added drop-wise to pH=4.0 by control within 10 minutes, is opened (c) and is held
The valve of device, continues that (b) is added dropwise, and system in tank is added drop-wise to pH=8.0 by control in 30 minutes, controls the valve of the container of (c),
Guarantee is now added dropwise to complete.Keeping temperature is 60 DEG C, and pH=8.0 aging 1 hour, material in tank is filtered, washing to nothing
Sulfate ion, filtering dries 10 hours filter cake at 110 DEG C, obtains carrier material A-5, then exists under nitrogen protection
It is calcined 5 hours under the conditions of 550 DEG C, pulverizes and sieves and obtain powder carrier J-5.The amount of plastic agents useful for same is listed in table 1.
100 grams of carrier material A-5 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then 110
Dried 10 hours at DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Pt-La, then
Dried 10 hours at 110 DEG C, be calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst E, its composition is shown in Table 2.
Embodiment 6
The synthesis of embodiment 2 is repeated, without carbohydrate during plastic, catalyst carrier material A-6 and powder is obtained
Shape carrier J-6.
Preformed catalyst is prepared with embodiment 2, obtains preformed catalyst F, and its composition is shown in Table 2.
Embodiment 7
The synthesis of embodiment 3 is repeated, without carbohydrate during plastic, catalyst carrier material A-7 and powder is obtained
Shape carrier J-7.
Preformed catalyst is prepared with embodiment 3, obtains preformed catalyst G, and its composition is shown in Table 2.
Comparative example 1
The synthesis of embodiment 2 is repeated, without activated carbon and carbohydrate during plastic, comparative catalyst's carrier material is obtained
Material PA-1 and powder carrier DF-1, its appearance white.
Preformed catalyst is prepared with embodiment 2, obtains preformed catalyst DA, and its composition is shown in Table 2.
Comparative example 2
By 100 grams of activated carbon used in embodiment 2, contact to form paste with the peptization liquid containing nitric acid, extruded moulding,
Then dried 10 hours at 110 DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain carrier, its outward appearance is
Black.Then using the method dipping active metal component of embodiment 2, catalyst DB is obtained, its composition is shown in Table 2.
Comparative example 3
By activated carbon used in embodiment 2 with carrier material PA-1 physical mixeds, contacted with the peptization liquid containing nitric acid
Paste is formed, then extruded moulding dries 10 hours at 110 DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection,
Carrier is obtained, wherein activated carbon content is 50wt%, and alumina content is 50wt%, its outward appearance black.Then using embodiment 2
Method impregnates active metal component, obtains catalyst DC, and its composition is shown in Table 2.
The plastic reagent quality of table 1
The composition and property of the catalyst of table 2
Be can be seen that by catalyst property in table 2 and obtained using the catalyst property obtained after carbohydrate treatment activated carbon
Improve.
The outward appearance of carrier material and carrier as obtained by the embodiment of the present invention is canescence, without obvious black, explanation
Activated carbon turns into the core of carrier material and carrier.
In the present invention, using X-ray photoelectron spectroscopy（XPS）To embodiment and the resulting vehicle material surface of comparative example 1
Element be analyzed.From analysis result, element composition and the PA-1 groups on embodiment resulting vehicle -1 ~ A-7 of materials A surfaces
Into essentially identical, there is micro elemental carbon.This is further illustrated, and carrier material of the invention is with activated carbon as core, with oxygen
It is shell to change aluminium dry glue.
Evaluating catalyst is carried out using simulated wastewater.
Sodium sulfite waste water is prepared, COD is that 12000mg/L pH value of solution is 6~7, is commented in small-sized flow reactor
Valency.In 45 DEG C for the treatment of temperature, volume space velocity 2.0h-1, it is wet that the reaction condition of gas-liquid volume ratio 200 carries out continuous catalysis to the waste water
Formula airoxidation.Result is listed in table 3.
The evaluation result of table 3
| Catalyst is numbered | B | F | G | DA | DB | DC |
| COD clearances, % | 98.0 | 95.6 | 95.1 | 84.4 | 96.0 | 93.1 |
From evaluation result as can be seen that having obvious reduction through the waste water COD after treatment, the COD removals to phenol wastewater
Rate is all more than 90%.After continuously running 1000h, evaluation result is listed in table 4.
The estimation of stability result of table 4
Catalyst can be seen that using after 1000h by the result of table 4, the catalyst activity base of the inventive method preparation is used
Originally it is not changed in, with good stability.
The present invention uses the noble metal with excellent catalytic activity as active component, adds rare earth metal as auxiliary agent,
Rare earth metal has good coordinative role with noble metal, increased the stability and activity of catalyst and reduces cost, has
There is good application prospect.
Claims (22)
1. a kind of catalytic wet oxidation catalyst, the catalyst includes carrier, active metal component and auxiliary agent, wherein with Pt, Pd,
One or several in Rh, Ru are active metal component, and rare earth metal is auxiliary agent, and carrier is with the activity of 150 mesh ~ 300 mesh
Charcoal be core, with amorphous alumina as shell, wherein activated carbon accounts for the 10% ~ 70% of vehicle weight, and aluminum oxide accounts for the 30% of vehicle weight
~90%。
2. according to the catalyst described in claim 1, it is characterised in that described rare earth metal is the one kind in lanthanum, cerium, praseodymium, neodymium
Or it is various.
3. according to the catalyst described in claim 1, it is characterised in that in described catalyst, activated carbon accounts for vehicle weight
30% ~ 70%, aluminum oxide accounts for the 30% ~ 70% of vehicle weight.
4., according to the catalyst described in claim 1, it is characterised in that in described catalyst, the weight with catalyst is as base
Standard, the content of noble metal is calculated as 0.01% ~ 1.0% with element, and the content of rare earth metal is calculated as 1.0% ~ 15.0% with element.
5. according to the catalyst method described in claim 1, it is characterised in that the property of the activated carbon is as follows：Specific surface area
500~3000m2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius.
6. according to the catalyst described in claim 1, it is characterised in that described catalyst or powder catalyst, or
It is preformed catalyst, the granularity of powder catalyst is 0.05 ~ 0.2mm, and preformed catalyst granularity is 0.5 ~ 8.0mm.
7. according to the catalyst described in claim 6, it is characterised in that the property of described preformed catalyst is as follows：Specific surface area
It is 200 ~ 1000m2/ g, pore volume is 0.3 ~ 1.8cm3/ g, rate of wear<3wt%, side pressure strength is 100 ~ 300N/cm.
8. the preparation method of any catalyst of claim 1 ~ 7, including：
(1) activated carbon of 150 mesh ~ 300 mesh is beaten；
(2) step is introduced during amorphous alumina plastic（1）The activated carbon slurries for obtaining；
(3) step（2）Material after the plastic for obtaining carries out aging, filtering, washing, dries, and obtains catalyst carrier material；
(4) by step（3）The carrier material of gained is made catalyst carrier；
(5) step（4）Active metal component and auxiliary agent are impregnated in the catalyst carrier of gained, is then dried, in inert gas
The lower roasting of protection, obtains catalytic wet oxidation catalyst.
9. in accordance with the method for claim 8, it is characterised in that：Step（4）The preparation of catalyst carrier is at least using following
One of method：
A, by step（3）The carrier material of gained, is calcined under inert gas shielding, obtains catalyst carrier；
B, by step（3）The carrier material shaping of gained, after drying, is calcined under inert gas shielding, obtains catalyst load
Body；
C, by step（3）The carrier material of gained is calcined under inert gas shielding, then again through shaping, after drying, in inertia
It is calcined under gas shield, obtains catalyst carrier.
10. in accordance with the method for claim 8, it is characterised in that the property of step (1) described activated carbon is as follows：Specific surface area
500~3000m2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius.
11. in accordance with the method for claim 8, it is characterised in that step（1）Described activated carbon mashing use adds water, low-carbon (LC)
It is beaten for one or more in alcohol, wherein low-carbon alcohols are that carbon number is one or more in 1 ~ 5 monohydric alcohol.
12. in accordance with the method for claim 8, it is characterised in that step（1）Described activated carbon is first processed using carbohydrate, so
After be beaten, described carbohydrate for carbon number for 3 ~ 20 carbohydrate；Carbohydrate treatment activated carbon be by carbohydrate directly with activity
Charcoal mixes, or carbohydrate is dissolved in activated carbon is added in solvent, solvent therein be water, carbon number for 1 ~ 5 monohydric alcohol
In one or more.
13. in accordance with the method for claim 12, it is characterised in that described carbohydrate consumption accounts for the 2% ~ 50% of activated carbon weight.
14. in accordance with the method for claim 12, it is characterised in that described carbohydrate consumption accounts for the 5% ~ 20% of activated carbon weight.
15. in accordance with the method for claim 12, it is characterised in that described carbohydrate is triose, tetrose, pentose, hexose, wheat
One or more in bud sugar, sucrose.
16. in accordance with the method for claim 12, it is characterised in that described carbohydrate is the one kind or many in glucose, sucrose
Kind.
17. in accordance with the method for claim 12, it is characterised in that：During carbohydrate treatment activated carbon, the solid volume ratio of liquid 10 with
Under.
18. in accordance with the method for claim 8, it is characterised in that：Step（2）Described in amorphous alumina plastic mistake
Journey is the neutralization reaction process of acid material and alkaline material, plastic process by the way of the continuous acid-base titration of soda acid, or
By the way of two kinds of material cocurrents are neutralized.
19. in accordance with the method for claim 8, it is characterised in that：Step（2）In, step（1）The activated carbon slurries of gained
Incorporation way uses the one or more combination of following manner：（1）During plastic neutralization reaction, the activated carbon slurries are connected
In continuous addition plastic cans；（2）The activated carbon slurries are charged first in plastic cans, the acidity of amorphous alumina then will be prepared
In material and alkaline material and plastic；（3）One or more by the activated carbon slurries with plastic material mix, then plastic thing
Material neutralizes plastic.
20. in accordance with the method for claim 8, it is characterised in that：Step（3）In, described drying condition is as follows：50 ~
Dried 1 ~ 15 hour at 150 DEG C.
21. in accordance with the method for claim 9, it is characterised in that：Step（4）In, the roasting condition described in method A is as follows：
Sintering temperature be 450 ~ 700 DEG C, roasting time be 1 ~ 10 hour, the drying condition described in method B be at 80 ~ 200 DEG C, dry 1 ~
15 hours, sintering temperature was 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, in method C, by step（3）The carrier material of gained
It is calcined under inert gas shielding, described roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 small
When, then again through shaping, after drying, it is calcined under inert gas shielding, catalyst carrier is obtained, the drying condition after shaping is such as
Under：At 80 ~ 200 DEG C, dry 1 ~ 15 hour, roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 small
When.
22. in accordance with the method for claim 8, it is characterised in that：Step（5）In, drying condition is, at 80 ~ 200 DEG C, to dry
1 ~ 15 hour, sintering temperature condition was 450 ~ 700 DEG C and is calcined 1 ~ 10 hour.
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| KR20040075656A (en) * | 2003-02-20 | 2004-08-30 | 안호근 | SiO2-coated TEDA impregnated activated carbon and Al2O3-coated TEDA impregnated activated carbon for cobalt removal in wastewater and it's preparation method |
| CN102125842A (en) * | 2010-01-19 | 2011-07-20 | 华东理工大学 | Multiphase wet oxidation catalyst and preparation method thereof |
| CN103041810A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Cellulosic ethanol wastewater treatment catalyst, preparation method thereof and wastewater treatment method |
| CN103041811A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of catalytic wet oxidation catalyst and treatment method of organic wastewater |
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| KR20040075656A (en) * | 2003-02-20 | 2004-08-30 | 안호근 | SiO2-coated TEDA impregnated activated carbon and Al2O3-coated TEDA impregnated activated carbon for cobalt removal in wastewater and it's preparation method |
| CN102125842A (en) * | 2010-01-19 | 2011-07-20 | 华东理工大学 | Multiphase wet oxidation catalyst and preparation method thereof |
| CN103041810A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Cellulosic ethanol wastewater treatment catalyst, preparation method thereof and wastewater treatment method |
| CN103041811A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of catalytic wet oxidation catalyst and treatment method of organic wastewater |
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