CN104667918B - Noble metal catalyst for CWO and preparation method thereof - Google Patents
Noble metal catalyst for CWO and preparation method thereof Download PDFInfo
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- CN104667918B CN104667918B CN201310620990.4A CN201310620990A CN104667918B CN 104667918 B CN104667918 B CN 104667918B CN 201310620990 A CN201310620990 A CN 201310620990A CN 104667918 B CN104667918 B CN 104667918B
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Abstract
The invention discloses a kind of for noble metal catalyst of CWO and preparation method thereof.The catalyst includes carrier and the active metal component and auxiliary agent that are supported on carrier, wherein with the one or several kinds in Pt, Pd, Rh, Ru for active metal component, rare earth metal is auxiliary agent, carrier is using activated carbon as core, using amorphous silica-alumina as shell, its preparation method is the introducing activated carbon slurries during amorphous silica-alumina plastic, carrier material is obtained through steps such as agings after plastic, carrier back loading active metal component and auxiliary agent is made.Catalyst of the present invention make reactant first with as the amorphous silica-alumina haptoreaction of shell after, contact and reacted with the activated carbon as stratum nucleare again, make full use of the advantage of amorphous silica-alumina and activated carbon, make catalyst that there is higher reactivity and stability in use, improve the service life of catalyst.
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
Increasingly strict with global environmental regulation, the Con trolling index of sewage qualified discharge requires more and more higher, herein
Under form, waste water treatment by catalytic oxidation has increasingly obtained the attention and use of people, and the catalysis 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 by reducing reaction temperature, reaction pressure to keep relatively low wastewater treatment expense, prepare with high-activity component,
High intensity, the cheap catalyst of high stability undoubtedly turn into the key that waste water catalytic oxidation technologies are applied.
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
To be simple, it typically directly can be made into the aqueous solution from metal salts such as iron, copper, cobalt, manganese or be directly thrown into handled waste water,
And discharge or regeneration Posterior circle are used in the water outlet after handling.Using homogeneous catalytic oxidation, because metal active constituent is useless
Fully it can dissolve and disperse in water, typically can reach relatively stable water treatment effect, but exist that reagent consumption is big, fortune
The row serious problems such as costly, metal loss and secondary pollution, cause its application by larger limitation.
Heterogeneous solid catalyst mainly with activated carbon, molecular sieve, aluminum oxide, titanium dioxide etc. for carrier, with alkali metal,
One or more in alkaline-earth metal, transition metal or Pt, Pd noble metal make the catalyst of active component composition.Activated carbon is
The black that is made up of carbonaceous material, hole are flourishing, specific surface area is big, a class microcrystalline carbon of high adsorption capacity.Activated carbon property
Stable, acidproof, alkaline-resisting, heat-resisting, water insoluble or organic solvent, easily regeneration, are a kind of environmentally friendly adsorbent, extensive use
In fields such as Industrial " three Waste " improvement, food, medicine, carrier, semiconductor, battery and power storages.Currently used for wastewater treatment
Heterogeneous solid catalyst mostly from activated carbon as carrier, but merely from activated carbon supported metal prepare catalyst
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 is made a discount.
Amorphous silica-alumina is strong with stronger acidity, pore size distribution$ concentration, machinery because with good chemical stability, pore volume is big
Degree it is big, corrosion-resistant the advantages of, be widely used in catalytic field, but amorphous silica-alumina have the shortcomings that it is smaller than surface,
The simple catalytic mechanical intensity height prepared from amorphous silica-alumina, pore size distribution is more concentrated, and pore volume is big, but smaller than surface,
Absorption and conversion capability to organic matter is relatively weak.
CN201110225789.7 discloses a kind of method for preparing benzene adsorption material using discarded activated alumina, and it is
By waste activated alumina it is cleaned, filtering, dry after, a kind of activated alumina/work is prepared using cryogenic seal heat treatment mode
Property carbon composite, has good adsorption effect to benzene.This method is by the organic matter carbonizing inside aluminum oxide, activated carbon master
It is distributed in the duct of aluminum oxide, so can not only blocks the duct of aluminum oxide, and the activated carbon so generated is in oxygen
Change skewness in aluminium.
CN201110255525.6 discloses a kind of preparation method of active alumina/active carbon composite material, is by aluminium
Section bar factory industrial sludge, activated carbon, binding agent through mixing, granulation, it is old, be molded, dry, sintering, rinsing, drying and other steps
Active alumina/active carbon composite material is made.This method belongs to salic species and activated carbon physical mixing processes,
Aluminum oxide and activated carbon disperse uneven；And used sludge impurity content is high, the Properties of Alumina of gained is unstable, it is impossible to
Repeat, it is complicated.
CN201010267074.3 discloses a kind of preparation method of activated alumina composite reactive Carbon Materials, with hydroxide
Aluminium, activated carbon and binding agent are raw material, through mixing, granulation, it is old, be molded, dry, sinter, rinse, drying and other steps, so
Obtained composite is still the physical mixture of aluminum oxide and activated carbon, and aluminum oxide disperses uneven with activated carbon, and it is integrated
Performance also needs further raising.
The content of the invention
In view of the shortcomings of the prior art, the invention provides one kind with catalytic performance is good, anti-wear performance is strong, using steady
It is qualitative good for noble metal catalyst of CWO and preparation method thereof.
The catalytic wet oxidation catalyst of the present invention, the catalyst includes carrier, active metal component and auxiliary agent, wherein with
One or several kinds in Pt, Pd, Rh, Ru are active metal component, and rare earth metal is auxiliary agent, and carrier is with the mesh of 150 mesh ~ 300
Activated carbon be core, using amorphous silica-alumina as shell, wherein activated carbon accounts for the 10% ~ 70% of vehicle weight, preferably 30% ~ 70%, nothing
Amorphous silicon-alumina accounts for the 30% ~ 90% of vehicle weight, preferably 30% ~ 70%.
In catalyst of the present invention, with the one or several kinds in precious metals pt, Pd, Rh, Ru for active metal component, rare earth
Metal is auxiliary agent, on the basis of the weight of catalyst, the content of noble metal is calculated as 0.01% ~ 1.0% with element, and rare earth metal contains
Amount is calculated as 1.0% ~ 15.0% with element.
In catalyst of the present invention, described rare earth metal is the one or more in lanthanum, cerium, praseodymium, neodymium.
The catalyst of the present invention can be the powder catalyst or preformed catalyst for being not required to shaping.It is powdered
The granularity of catalyst is generally 0.05 ~ 0.2mm.Preformed catalyst can determine the size of granularity as needed, generally 0.5 ~
8.0mm。
The property of preformed catalyst of the present invention is as follows：Specific surface area is 200 ~ 1000m2/ g, pore volume 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) the mesh activated carbon of 150 mesh ~ 300 is beaten；
(2) step is introduced during amorphous silica-alumina plastic（1）Obtained activated carbon slurries；
(3) step（2）Material after obtained plastic carries out aging, filtering, washing, drying, obtains carrier material；
(4) by step（3）Catalyst carrier is made in the carrier material of gained, 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 inertia
It is calcined under gas shield, 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
One or more in carbon alcohol are beaten, and wherein low-carbon alcohols are the one or more in the monohydric alcohol that carbon number is 1 ~ 5.
In the inventive method, step（1）It is preferred that activated carbon is first handled using carbohydrate, then it is beaten.Described carbohydrate
For the one or more in monosaccharide and disaccharide, polysaccharide, preferably carbon number is 3 ~ 20 carbohydrate, for example：Triose, tetrose, penta
One or more in one or more in sugar, hexose, maltose, sucrose, more preferably glucose, sucrose.Described sugar
Class consumption accounts for the 2% ~ 50% of activated carbon weight, preferably 5% ~ 20%.Carbohydrate processing activated carbon can be by carbohydrate directly and activated carbon
Carbohydrate, can also be dissolved in solvent and add activated carbon by mixing, and solvent therein is water, low-carbon alcohols（I.e. carbon number is 1 ~ 5
Monohydric alcohol）In one or more.When carbohydrate handles activated carbon, the solid volume ratio of its liquid is below 10, preferably 1 ~ 5.Carbohydrate
Handle after 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, during wherein low-carbon alcohols are the monohydric alcohol that carbon number is 1 ~ 5
It is one or more.
Step of the present invention（2）In, amorphous silica-alumina plastic process can be carried out by process well known to those skilled in the art.
Amorphous silica-alumina plastic process is generally the neutralization reaction process of acid material and alkaline material, and plastic process typically uses two kinds
Material cocurrent plastic mode of operation, or a kind of material are placed on the operation side that another material in plastic cans is continuously added to plastic
Formula.Plastic material generally comprises silicon source（Al2(SO4)3、AlCl3、Al(NO3)3And NaAlO2One or more in）, silicon source
（One or more in waterglass, Ludox and organic silicon-containing compound etc.）, precipitating reagent（NaOH、NH4OH or CO2Deng）, according to
The different choice of plastic process is used, and conventional mode of operation mainly has：（1）Acid aluminium salt（Al2(SO4)3、AlCl3、Al
(NO3)3）With basic aluminium salt（NaAlO2）Or alkaline precipitating agent（NaOH、NH4OH）Neutralize plastic,（2）Basic aluminium salt（NaAlO2）With
Acidic precipitation agent（CO2）Neutralize plastic.Silicon source typically introduces plastic cans during plastic, can also be mixed with silicon source or precipitating reagent
Plastic is neutralized after conjunction again, such as waterglass adds and neutralization plastic is carried out in basic aluminium salt or alkaline precipitating agent, and Ludox adds acid
Carry out neutralizing plastic etc. in aluminium salt.Silicon source can also be added after silicon source precipitation in material.Can also be by two kinds of aforesaid way or two
Kind above in association with using.The above method is well-known to those skilled in the art.Described plastic process is general in room temperature ~ 85
Carried out at DEG C, be relatively suitably for 40 ~ 80 DEG C, preferably 50 ~ 70 DEG C.Described plastic process is typically entered under certain pH value condition
OK, typical pH is 6.0 ~ 10.0, is relatively suitably for 7.0 ~ 9.5, preferably 7.5 ~ 9.0.Step（4）Described aging, condition is such as
Under：PH is 6.0 ~ 10.0, preferably 7.0 ~ 9.5, and ageing time 0.25 ~ 8 hour is relatively adapted to 0.5 ~ 5 hour, preferably 1 ~ 3
Hour, aging temperature is room temperature ~ 85 DEG C, preferably 40 ~ 80 DEG C.Temperature and pH when temperature and pH during aging are with neutralizing is best
It is identical.
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 plastic neutralization reaction, the mixture is continuously added in plastic cans；（2）The mixture is charged first to
In plastic cans, then by the acid material and alkaline material that prepare amorphous silica-alumina and plastic；（3）By the mixture and plastic
One or more of mixing of 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
Washing, the lower alcohols of being added water when mashing washing, filtering such as wash at the mode, the temperature of washing should room temperature ~ 90 DEG C temperature model
In enclosing, preferably 50 ~ 70 DEG C.The washing of the material is general to be carried out in the range of pH is 1.0 ~ 9.0, and preferably pH is 4.0 ~ 8.5.
Step of the present invention（3）Described in material washing, filtering after should be free of or containing minimal amount of heteroion, heteroion includes
Na+、Cl-、SO4 2-、NO3 -、K+One or more in.
Step of the present invention（3）In, described material is after washing, filtering, and filter cake is dried, and drying mode can be used
Natural drying, oven drying, spray drying, microwave drying or infra-red drying, the drying condition typically used are as follows：50 ~
Dried 1 ~ 15 hour at 150 DEG C.
Step of the present invention（4）In, method A is to obtain pelleted substrate 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, method B and the shaping described in method C can be carried out as needed, generally strip, circle
Column, spherical, irregular strip, special-shaped ball etc., granularity can determine as needed, generally 0.5 ~ 8.0mm.Described forming process
In, the one or more that can be added as needed 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 dried 1 ~ 15 hour generally at 80 ~ 200 DEG C, roasting
Temperature is generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.
Step of the present invention（4）In, in method C, by step（3）The 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 and auxiliary agent can be sprayed or saturation dipping,
It can be supersaturated dipping.
Step of the present invention（5）In, after catalyst dipping, drying condition is dried 1 ~ 15 hour generally at 80 ~ 200 DEG C, roasting
Burn temperature and be generally 450 ~ 700 DEG C, roasting time is generally 1 ~ 10 hour.
Step of the present invention（5）In, when carrier impregnation active metal component and auxiliary agent, generally using containing active metal and auxiliary agent
Maceration extract impregnated.Maceration extract is prepared using conventional method, i.e., by noble metal（One kind or many in platinum, palladium, ruthenium and rhodium
Kind）It is dissolved in solvent and is formulated with the predecessor of rare earth metal.
The carrier that catalyst of the present invention is used is made up of the compound using activated carbon as core, using amorphous silica-alumina as shell
, so make reactant first with as the amorphous silica-alumina haptoreaction of shell after, then contact with the activated carbon as stratum nucleare into
Row reaction, make full use of that amorphous silica-alumina aperture is big, pore volume is high and activated carbon specific surface area is big, high adsorption capacity the characteristics of and
The synergy of active component and auxiliary agent, makes catalyst have higher reactivity and stability in use, improves catalyst
Service life.The carrier is particularly useful as the CWO of catalytic wet oxidation catalyst carrier, especially Love psychology
Catalyst carrier, with the stability for improving the activity of catalyst and using.
In the preparation process of catalyst of the present invention, activated carbon is introduced during the plastic of amorphous silica-alumina, so makes nothing
Amorphous silicon-alumina colloid wraps up activated carbon, is formed using activated carbon as core, using amorphous silica-alumina as the compound of shell, so comprehensively utilizes
Activated carbon specific surface area is big, the strong advantage of absorption affinity and amorphous silica-alumina high mechanical strength, and aperture is big, pore distribution concentration it is excellent
Point, amorphous silica-alumina parcel activated carbon, makes activated carbon be evenly distributed in amorphous silica-alumina, amorphous silica-alumina provides good
Mechanical support and intensity so that catalyst has good mechanical strength and anti-wear performance, while raw material is amorphous by shell
The duct of sial is diffused into the inner surface of activated carbon, and activated carbon provides powerful specific surface area, activated carbon for catalyst
Fine dispersion in amorphous silica-alumina causes the utilization rate of activated carbon to be improved, and the surface of activated carbon has obtained more abundant
Utilization, to improve catalyst performance and stability there is good facilitation.
In the preparation process of catalyst carrier of the present invention, it is beaten again after handling activated carbon in particular by carbohydrate, then
Introduced during the plastic of amorphous silica-alumina, carbohydrate is uniformly adsorbed on the surfaces externally and internally of activated carbon, passes through follow-up roasting
Burning process makes to be mixed in the carbohydrate breakdown charing in the middle of amorphous silica-alumina and activated carbon, the activated carbon connection amorphous silicon newly formed
Aluminium and activated carbon so that the combination of activated carbon and amorphous silica-alumina is even closer, the carbohydrate on activated carbon inner surface is through decomposing shape
Into the former activated carbon of new Activated Carbon Modification inner surface, add the adsorption activity position of activated carbon inner surface.It is therefore preferable that increase
Carbohydrate handles activated carbon, amorphous silica-alumina can be promoted closely to wrap up activated carbon, is conducive to improving the machinery of catalyst
Intensity and attrition resistance energy, and improve the utilization rate of the inner surface of activated carbon, are conducive to improving the active of catalyst and stably
Property.
Catalyst preparation process of the present invention is simply, conveniently, it is easy to operates, is adapted to industrial production.
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.
The preparation method of the present invention is further illustrated with reference to specific embodiment, but the scope of the present invention is not only
It is limited to the scope of these embodiments.
Commercially available powdery coconut husk charcoal specific surface area 928m used in the present invention2/ g, pore volume 1.0cm3/ g, average pore size
1.1nm, iodine sorption value 700mg/g, the mesh of granularity 200.Waterglass raw material is technical grade, and modulus is 3.0.
Embodiment 1
Solid aluminum chloride is added in distilled water, heats and stirs to dissolving, obtain liquor alumini chloridi (a).By dense ammonia
Water adds appropriate distilled water diluting into about 10% weak aqua ammonia (b).Powdery coconut husk charcoal is added in D/W and is well mixed, liquid
Gu volume ratio is 3：1, then add water mashing, obtains slurries (c).Waterglass is according to 1:2 dilution proportion in deionized water, is matched somebody with somebody
It is set to solution (d).(a) is added in plastic cans and is heated with stirring to after 65 DEG C, the valve for the container for having (b), control is opened
System in tank is added drop-wise to pH=4.5 within 10 minutes, continues that (b) is added dropwise, opens the valve for the container for having (c), control 30 points
System in tank is added drop-wise to pH=8.0 in clock, the valve of the container of (c) is controlled, it is ensured that be now added dropwise to complete.Keeping temperature is 65
DEG C, pH=8.0 after stopping 20 minutes, solution (d) are added into system, is according to the content of silica in amorphous silica-alumina
45wt% is calculated and added in 10 minutes.Aging 1 hour, material in tank is filtered, and washing is to without chlorion, and filtering will be filtered
Cake is dried 10 hours at 110 DEG C, obtains carrier material A-1.Then it is calcined 5 hours under the conditions of 550 DEG C under nitrogen protection,
Pulverize and sieve and obtain powder carrier J-1.The amount of plastic 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
Dry 10 hours, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Pt-Ce, so at 110 DEG C
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, heats and stirs to dissolving, obtain aluminum sulfate solution (a).By dense ammonia
Water adds appropriate distilled water diluting into about 10% weak aqua ammonia (b).Powdery coconut husk charcoal is added in D/W and is well mixed, liquid
Gu volume ratio is 3：1, then add water mashing, obtains activated carbon slurries (c).Waterglass is according to 1:2 dilution proportion is in deionized water
In, it is configured to solution (d).(a) is added in plastic cans and is heated with stirring to after 65 DEG C, the valve for the container for having (b) is opened,
System in tank is added drop-wise to pH=4.5 by control within 10 minutes, continues that (b) is added dropwise, and opens the valve for the container for having (c), control
System in tank is added drop-wise to pH=8.0 in 30 minutes, the valve of the container of (c) is controlled, it is ensured that be now added dropwise to complete.Keeping temperature
For 65 DEG C, pH=8.0 after stopping 20 minutes, solution (d) are added into system, according to the content of silica in amorphous silica-alumina
Calculate and added in 10 minutes for 50wt%.Aging 1 hour, material in tank is filtered, washing to sulfate radical-free ion, mistake
Filter, filter cake is dried 10 hours at 110 DEG C, carrier material A-2 is obtained.Then roasted under nitrogen protection under the conditions of 550 DEG C
Burn 5 hours, pulverize and sieve 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
Dry 10 hours, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Ru-Ce, then at DEG C
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, aluminum sulfate solution (a) is obtained.Will
Solid sodium metaaluminate is configured to concentration for 250g Al2O3/ l sodium aluminate solutions (b).Powdery coconut husk charcoal is added into aqueous sucrose solution
In be well mixed, the solid volume ratio of liquid is 3：1, then add water mashing, obtains slurries（c）.A plastic cans is taken, 2L deionized waters are inserted
It is heated with stirring to after 60 DEG C and adds slurries (c).Waterglass is according to 1:2 dilution proportion in deionized water, is configured to solution
(d).A retort is taken, 2L deionized waters is inserted and is heated with stirring to after 65 DEG C, while opening the container for having (a), (b), (c)
Valve, pH=8.0 of control system, control drips off (a) and (c) in 45 minutes simultaneously.Keeping temperature is 65 DEG C, pH=
8.0, after stopping 20 minutes, solution (d) is added into system, is calculated according to the content 55wt% of silica in amorphous silica-alumina
Added in 10 minutes.Aging 1 hour, material in tank is filtered, washing to sulfate radical-free ion, and filtering exists filter cake
Dried 10 hours at 110 DEG C, obtain carrier material A-3.Then it is calcined 5 hours, crushes under the conditions of 550 DEG C under nitrogen protection
Sieving obtains 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
Dry 10 hours, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Ru-Ce, then at DEG C
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, heats and stirs to dissolving, obtain liquor alumini chloridi (a).By dense ammonia
Water adds appropriate distilled water diluting into about 10% weak aqua ammonia (b), and powdery coconut husk charcoal is added in D/W and is well mixed, liquid
Gu volume ratio is 3：1, then add water mashing, obtains activated carbon slurries (c).Waterglass is according to 1:2 dilution proportion is in deionized water
In, it is configured to solution (d).(a) is added in plastic cans and is heated with stirring to after 65 DEG C, the valve for the container for having (b) is opened,
System in tank is added drop-wise to pH=4.5 by control within 10 minutes, continues that (b) is added dropwise, and opens the valve for the container for having (c), control
System in tank is added drop-wise to pH=8.0 in 30 minutes, the valve of the container of (c) is controlled, it is ensured that be now added dropwise to complete.Keeping temperature
For 65 DEG C, pH=8.0 after stopping 20 minutes, solution (d) are added into system, according to the content of silica in amorphous silica-alumina
Calculate and added in 10 minutes for 45wt%.Aging 1 hour, material in tank is filtered, and washing is filtered to without chlorion, will
Filter cake is dried 10 hours at 110 DEG C, obtains carrier material A-4.Then roasting 5 is small under the conditions of 550 DEG C under nitrogen protection
When, pulverize and sieve and obtain 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
Dry 10 hours, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Ru-Ce, then at DEG C
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, heats and stirs to dissolving, obtain aluminum sulfate solution (a).By dense ammonia
Water adds appropriate distilled water diluting into about 10% weak aqua ammonia (b).Powdery coconut husk charcoal is added in D/W and is well mixed, liquid
Gu volume ratio is 3：1, then add water mashing, obtains activated carbon slurries (c).Waterglass is according to 1:2 dilution proportion is in deionized water
In, it is configured to solution (d).(a) is added in plastic cans and is heated with stirring to after 65 DEG C, the valve for the container for having (b) is opened,
System in tank is added drop-wise to pH=4.5 by control within 10 minutes, continues that (b) is added dropwise, and opens the valve for the container for having (c), control
System in tank is added drop-wise to pH=8.0 in 30 minutes, the valve of the container of (c) is controlled, it is ensured that be now added dropwise to complete.Keeping temperature
For 65 DEG C, pH=8.0 after stopping 20 minutes, solution (d) are added into system, according to the content of silica in amorphous silica-alumina
Calculate and added in 10 minutes for 55wt%.Aging 1 hour, material in tank is filtered, washing to sulfate radical-free ion, mistake
Filter, filter cake is dried 10 hours at 110 DEG C, carrier material A-5 is obtained.Then roasted under nitrogen protection under the conditions of 550 DEG C
Burn 5 hours, pulverize and sieve 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
Dry 10 hours, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Pt-La, then at DEG C
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 made
Shape carrier J-6.
Preformed catalyst carrier prepares be the same as Example 2, obtains catalyst carrier Z-6.Active metal and carrying method are with real
Example 2 is applied, catalyst F is obtained, its composition is shown in Table 3.
Embodiment 7
The synthesis of embodiment 3 is repeated, without carbohydrate during plastic, catalyst carrier material A-7 and powder is made
Shape carrier J-7.
Preformed catalyst carrier prepares be the same as Example 3, obtains catalyst carrier Z-7, its property is shown in Table 2.Active metal and
Carrying method be the same as Example 3, obtains catalyst G, and its composition is shown in Table 3.
Comparative example 1
The synthesis of embodiment 2 is repeated, without activated carbon and carbohydrate during plastic, comparative catalyst's carrier material is made
Expect PA-1 and powder carrier DF-1, its appearance white.
The preparation be the same as Example 2 of preformed catalyst carrier and catalyst, obtains catalyst carrier DZ-A and catalyst DA.
Comparative example 2
Activated carbon 100g used in embodiment 2 is contacted to form paste with the peptization liquid containing nitric acid, extruded moulding, so
Dried 10 hours at 110 DEG C afterwards, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst carrier DZ-B,
Its outward appearance is black, then using the method dipping active metal component of embodiment 2, obtains catalyst DB.
Comparative example 3
By activated carbon used in embodiment 2 with carrier material PA-1 physical mixeds, with the peptization liquid contact containing nitric acid
Paste is formed, then extruded moulding is dried 10 hours at 110 DEG C, after being calcined 5 hours under the conditions of 550 DEG C under nitrogen protection,
Catalyst carrier DZ-C is obtained, wherein activated carbon content is 50wt%, and amorphous silicon aluminium content is 50wt%, and its outward appearance is black.
Then using the method dipping active metal component of embodiment 2, catalyst DC is obtained.
The plastic agents useful for same quality of table 1
The composition and property of the catalyst of table 2
The catalyst bulk property obtained after activated carbon is handled using carbohydrate it can be seen from catalyst property in table 2 to obtain
Improvement is arrived.
It is canescence as the carrier material and the outward appearance of carrier obtained by the embodiment of the present invention, 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 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 further illustrates that carrier material of the invention is using activated carbon as core, with nothing
Amorphous silicon-alumina dry glue is shell.
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, % | 97.4 | 95.2 | 95.4 | 83.9 | 98.0 | 93.0 |
From evaluation result as can be seen that the waste water COD after processing has obvious reduction, the COD of phenol wastewater is removed
Rate is all more than 90%.Continuously run after 1000h, evaluation result is listed in table 4.
The estimation of stability result of table 4
Used by catalyst it can be seen from the result of table 4 after 1000h, the catalyst activity base prepared using the inventive method
This does not change, 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, adds 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 kinds in Rh, Ru are active metal component, and rare earth metal is auxiliary agent, and carrier is with the activity of the mesh of 150 mesh ~ 300
Charcoal is core, using amorphous silica-alumina as shell, and wherein activated carbon accounts for the 10% ~ 70% of vehicle weight, and amorphous silica-alumina accounts for vehicle weight
30%~90%。
2. according to the catalyst described in claim 1, it is characterised in that described rare earth metal is one kind in lanthanum, cerium, praseodymium, neodymium
Or it is a variety of.
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%, amorphous silica-alumina 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, using the weight of catalyst 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 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 either 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
For 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 the mesh of 150 mesh ~ 300 is beaten；
(2) step is introduced during amorphous silica-alumina plastic（1）Obtained activated carbon slurries；
(3) step（2）Material after obtained plastic carries out aging, filtering, washing, drying, obtains carrier material；
(4) by step（3）Carrier is made in the carrier material of gained,
(5) step（4）Active metal component and auxiliary agent are impregnated in the catalyst carrier of gained, is then dried, in inert gas
Protection is lower to be calcined, and 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 at least uses following sides
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
One or more in alcohol are beaten, and wherein low-carbon alcohols are the one or more in the monohydric alcohol that carbon number is 1 ~ 5.
12. in accordance with the method for claim 8, it is characterised in that step（1）Described activated carbon is first handled using carbohydrate, so
It is beaten afterwards, described carbohydrate is the carbohydrate that carbon number is 3 ~ 20；Carbohydrate processing activated carbon be by carbohydrate directly with activity
Charcoal is mixed, or carbohydrate is dissolved in solvent adds activated carbon, and solvent therein is the monohydric alcohol that water, carbon number are 1 ~ 5
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 one kind or many in glucose, sucrose
Kind.
17. in accordance with the method for claim 12, it is characterised in that：When carbohydrate handles 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 silica-alumina plastic process
It is the neutralization reaction process of acid material and alkaline material, plastic process is by the way of the continuous acid-base titration of soda acid, or adopts
The mode neutralized with two kinds of material cocurrents.
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
It is continuous to add in plastic cans；（2）The activated carbon slurries are charged first in plastic cans, the acid of amorphous silica-alumina then will be prepared
Material and alkaline material in and plastic；（3）The activated carbon slurries are mixed with the one or more of plastic material, then plastic material
Neutralize 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 is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, and drying condition described in method B is at 80 ~ 200 DEG C, dry 1 ~
15 hours, sintering temperature was 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, in method C, by step（3）The 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, obtains catalyst carrier, 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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| CN103041810B (en) * | 2011-10-17 | 2014-10-15 | 中国石油化工股份有限公司 | Cellulosic ethanol wastewater treatment catalyst, preparation method thereof and wastewater treatment method |
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| CN102125842A (en) * | 2010-01-19 | 2011-07-20 | 华东理工大学 | Multiphase wet oxidation catalyst and preparation method thereof |
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