CN104667923B - Method for preparing noble metal catalyst for catalytic wet oxidation - Google Patents
Method for preparing noble metal catalyst for catalytic wet oxidation Download PDFInfo
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- CN104667923B CN104667923B CN201310621103.5A CN201310621103A CN104667923B CN 104667923 B CN104667923 B CN 104667923B CN 201310621103 A CN201310621103 A CN 201310621103A CN 104667923 B CN104667923 B CN 104667923B
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Abstract
The invention discloses a method for preparing a noble metal catalyst for catalytic wet oxidation. The catalyst comprises a carrier, an active metal ingredient and an auxiliary. The preparation method comprises the following steps: introducing amino acid treated activated carbon slurry into the process of gelling amorphous alumina; preparing a carrier material by means of aging and other steps; preparing the carrier from the carrier material, and loading the active metal ingredient and auxiliary. 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 the preparation method of a kind of catalytic wet oxidation catalyst, expensive especially for CWO
The preparation method of metallic catalyst.
Background technology
Along with the increasingly stringent of global environmental regulation, the Con trolling index of sewage qualified discharge requires more and more higher, at this
Under form, waste water treatment by catalytic oxidation the most increasingly obtains attention and the employing 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, for obtaining preferably place
Reason effect and by reducing reaction temperature, reaction pressure to keep relatively low waste water processing cost, preparation have high-activity component,
High intensity, the cheap catalyst of high stability become the key of waste water catalytic oxidation technologies application undoubtedly.
The catalyst of useless water catalytic oxidizing is broadly divided into homogeneous catalyst and heterogeneous solid catalyst two class.
Homogeneous catalyst mainly includes producing the Fenton reagent of oxygen radical, Fe3+、Cu2+, the metal such as cobalt and manganese
Ion, by means of the effect of these homogeneous catalysts, organic component in waste water, sulfide, ammonia nitrogen etc. are by air, oxygen, smelly
The oxide isolation such as oxygen, hydrogen peroxide is 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 preparation and the process of use are relatively
For simply, the slaines such as ferrum, copper, cobalt, manganese typically can be directly selected to be made into aqueous solution or be directly thrown in handled waste water,
And used by the water outlet after processing being discharged or regenerating Posterior circle.Use homogeneous catalytic oxidation, owing to metal active constituent is useless
Water can fully dissolve and disperse, typically can reach relatively stable water treatment effect, but also exist that reagent consumption is big, fortune
Row costly, the serious problems such as metal loss and secondary pollution, cause its application to be limited by bigger.
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.Live
Property charcoal be made up of carbonaceous material black, hole is flourishing, specific surface area big, a class microcrystalline carbon of high adsorption capacity.Activity
Charcoal stable in properties, acidproof, alkaline-resisting, heat-resisting, water insoluble or organic solvent, easily regenerate, be a kind of environmentally friendly adsorbent, extensively
General it is applied to the fields such as Industrial " three Waste " improvement, food, medicine, carrier, quasiconductor, battery and power storage.It is currently used for giving up
The heterogeneous solid catalyst that water processes mostly select activated carbon as carrier, but select catalysis prepared by activated carbon supported metal
Agent anti-wear performance is poor, and mechanical strength is the highest, 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, has certain acidity, pore size distribution$ is concentrated, machine
The advantages such as tool intensity is big, corrosion-resistant, are widely used at catalytic field, but amorphous alumina to there is specific surface little
Shortcoming, relatively small to organic absorption and conversion capability.
CN201110225789.7 discloses a kind of side utilizing discarded active amorphous aluminium oxide to prepare benzene adsorption material
Method, it be by cleaned for useless active amorphous aluminium oxide, filter, dried, use cryogenic seal heat treatment mode preparation one
Active amorphous aluminium 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, the most not only can block aluminium oxide
Duct, and the activated carbon so generated skewness in aluminium oxide.
CN201110255525.6 discloses the preparation method of a kind of active amorphous aluminium oxide/absorbent charcoal composite material,
Be by waste aluminum sludge, activated carbon, binding agent through mixing, pelletize, old, molding, dry, sinter, rinse, dry
Active amorphous aluminium oxide/absorbent charcoal composite material is made etc. step.The method belongs to salic species and activated carbon thing
Reason mixed process, aluminium oxide and activated carbon dispersion are uneven；And the mud impurity content height used, the amorphous of gained
Aluminum character is unstable, it is impossible to repeat, and structure is complicated.
CN201010267074.3 discloses the preparation method of a kind of activated alumina composite reactive Carbon Materials, with hydroxide
Aluminum, activated carbon and binding agent are raw material, through mixing, pelletize, old, molding, dry, sinter, rinse, drying and other steps, so
The composite obtained is still the physical mixture of aluminium oxide and activated carbon, and aluminium oxide is uneven with activated carbon dispersion, and it is comprehensive
Performance also needs to improve further.
Summary of the invention
For the deficiencies in the prior art, the invention provides one and have that catalytic performance is good, anti-wear performance strong, it is steady to use
The preparation method of the qualitative good noble metal catalyst for CWO.
The preparation process of catalytic wet oxidation catalyst of the present invention, this catalyst includes carrier, active metal component and helps
Agent, wherein with one or several in Pt, Pd, Rh, Ru as active metal component, rare earth metal is auxiliary agent, preparation process bag
Include:
(1) use aminoacid to process 150 mesh ~ 300 mesh activated carbons, then pull an oar；
(2) during amorphous alumina plastic, the activated carbon serosity that step (1) obtains is introduced；
(3) material after the plastic that step (2) obtains carry out aging, filter, wash, be dried, obtain carrier material；
(4) carrier material of step (3) gained is made catalyst carrier, preferably at least uses one of following method:
A, by the carrier material of step (3) gained, roasting under inert gas shielding, obtain catalyst carrier；
B, by the carrier material molding of step (3) gained, after drying, roasting under inert gas shielding, be catalyzed
Agent carrier；
C, by carrier material roasting under inert gas shielding of step (3) gained, the most again through molding, after drying,
Roasting under inert gas shielding, obtains catalyst carrier；
(5) impregnate active metal component and auxiliary agent in the catalyst carrier of step (4) gained, be then dried, at indifferent gas
The lower roasting of body protection, obtains catalytic wet oxidation catalyst.
The catalytic wet oxidation catalyst of the present invention, this 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%,
Aluminium oxide accounts for the 30% ~ 90% of vehicle weight, and preferably 30% ~ 70%.
In catalyst of the present invention, with one or several in precious metals pt, Pd, Rh, Ru as active metal component, rare earth
Metal is auxiliary agent, and on the basis of the weight of catalyst, the content of noble metal is calculated as 0.01% ~ 1.0% with element, containing of rare earth metal
Amount is calculated as 1.0% ~ 15.0% with element.
In catalyst of the present invention, described rare earth metal is one or more in lanthanum, cerium, praseodymium, neodymium.
The catalyst of the present invention can be the powder catalyst being not required to molding, it is also possible to be preformed catalyst.Powder
The granularity of catalyst is generally 0.05 ~ 0.2mm.Preformed catalyst can determine the size of granularity as required, generally 0.5 ~
8.0mm。
The character 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, < 3wt%, side pressure strength is 100 ~ 250N/cm to rate of wear.
Step of the present invention (1) described activated carbon can be selected for the Powdered Activated Carbon commodity of routine, such as all kinds of wood activated charcoals, really
Shell activated carbon, active carbon from coal；Can also select with wooden material, mineral material, plastics and garbage, as timber, wood flour, Linesless charcoal,
Coconut husk, pit, shell, coal, gangue, petroleum coke, asphalt, polrvinyl chloride, polypropylene, organic resin, damaged tire, surplus
The various activated carbon products that remaining mud etc. obtain through traditional preparation methods.Activated carbon used in the present invention is powder activated
Charcoal, granularity 150 ~ 300 mesh, specific surface area 500 ~ 3000m2/ g, pore volume 0.5 ~ 1.8cm3/ g, average pore radius 1 ~ 10nm.
In the inventive method, the making beating of activated carbon described in step (1) uses conventional method to carry out, general use add water, low
One or more in carbon alcohol are pulled an oar, wherein low-carbon alcohols be carbon number be one or more in the monohydric alcohol of 1 ~ 5.
In the inventive method, step (1) activated carbon first uses aminoacid to process, and then pulls an oar.Described aminoacid
For the carbon number aminoacid less than 20.Described aminoacid is hydrophilic amino acid, such as glycine, serine, threonine,
In cysteine, tyrosine, agedoite, glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid one
Plant or multiple, the hydrophilic amino acid of the preferably C number long-chain less than 10.Such as aspartic acid, glutamic acid, lysine etc..Institute
The aminoacid consumption stated accounts for the 2% ~ 50% of activated carbon weight, preferably 5% ~ 20%.Aminoacid processes activated carbon can be by aminoacid
Directly mixing with activated carbon, it is also possible to be dissolved in solvent by aminoacid and add activated carbon, solvent therein is water, low-carbon alcohols
One or more in (i.e. carbon number is the monohydric alcohol of 1 ~ 5).Aminoacid process activated carbon time, its liquid-solid volume ratio 10 with
Under, preferably 1 ~ 5.After aminoacid processes activated carbon, the liquid phase of excess is preferably filtered to remove, and pulls an oar the most again.Making beating can
Employing conventional method is carried out, general use add water, one or more in low-carbon alcohols are pulled an oar, wherein low-carbon alcohols is carbon atom
Number is one or more in the monohydric alcohol of 1 ~ 5.
The plastic process of the amorphous alumina described in step of the present invention (2) can be by well known to those skilled in the art
Process is carried out.The plastic process of amorphous alumina is usually acid material and the neutralization course of reaction of alkaline material.Plastic mistake
Journey can be to use in the way of the continuous acid-base titration of soda acid, it would however also be possible to employ two kinds of materials also flow the mode of neutralization.
In step of the present invention (2), aluminium oxide plastic is to use aluminum soluble salt to enter with acidic precipitation agent or alkaline precipitating agent
Row neutralizes the process of reaction, and aluminum soluble salt wherein used is one or more in aluminum chloride, aluminum sulfate, aluminum nitrate, institute
Acidic precipitation agent be usually in hydrochloric acid, sulphuric acid, nitric acid, oxalic acid, carbon dioxide etc. one or several, alkalescence used
Precipitant is usually one or several in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia etc..Aluminium oxide becomes
Glue can also use meta-aluminate (such as sodium metaaluminate and/or potassium metaaluminate) and acid aluminium salt (such as aluminum chloride, aluminum nitrate,
One or more in aluminum sulfate) method that is neutralized 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, typically under certain pH value condition
PH is 6.0 ~ 10.0, is relatively suitably for 7.0 ~ 9.5, preferably 7.5 ~ 9.0.Aging described in step (3), condition is as follows: pH is 6.0
~ 10.0, preferably 7.0 ~ 9.5, ageing time 0.25 ~ 8 hour, relatively it is suitable at 0.5 ~ 5 hour, preferably 1 ~ 3 hour, aging temperature
Degree is room temperature ~ 85 DEG C, preferably 40 ~ 80 DEG C.Temperature and pH time aging are preferably identical with temperature during neutralization and pH.
In step of the present invention (2), the incorporation way of the mixture of step (1) gained uses one or more of following manner
Combination: this mixture, in plastic and in course of reaction, is continuously added in plastic cans by (1)；(2) this mixture is charged first to
In plastic cans, then will prepare in the acid material of amorphous alumina and alkaline material and plastic；(3) by this mixture with become
One or more mixing of glue material, then in plastic material and plastic.
In step of the present invention (3), the mode of washing of described material is known in those skilled in the art, can select
Add water when making beating washing, filtration the mode such as washing, lower alcohols washing, and the temperature of washing should be at the temperature model of room temperature ~ 90 DEG C
In enclosing, preferably 50 ~ 70 DEG C.The washing of described material is typically to carry out in the range of 1.0 ~ 9.0 at pH, and preferably pH is 4.0 ~ 8.5.
Material described in step of the present invention (3) should not contain after washing, filtration or containing minimal amount of heteroion, heteroion includes
Na+、Cl-、SO4 2-、NO3 -、K+One or more in Deng.
In step of the present invention (3), described material is after washing, filtering, and filter cake is dried, and drying mode can use
Natural drying, oven drying, spray drying, microwave drying or infrared drying, the general drying condition used is as follows: 50 ~
It is dried 1 ~ 15 hour at 150 DEG C.
In step of the present invention (4), method A is to obtain powdered catalytic agent carrier without molding roasting direct.Described in method A
Roasting condition as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
In step of the present invention (4), the molding described in method B and method C can be carried out as required, generally strip, circle
Column, spherical, irregular strip, special-shaped ball etc., granularity can determine as required, generally 0.5 ~ 8.0mm.Described forming process
In, one or more in shaping assistant such as binding agent, peptization acid, extrusion aid etc. can be added as required.
In step of the present invention (4), 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.
In step of the present invention (4), in method C, by carrier material roasting under inert gas shielding of step (3) gained,
Described roasting condition is as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.The most again through molding, it is dried
After, roasting under inert gas shielding, obtain catalyst carrier, the drying condition after molding is as follows: at 80 ~ 200 DEG C, be dried 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, carrying out roasting under inert gas shielding, selected noble gas is generally nitrogen or argon.
In step of the present invention (5), carrier impregnation metal component and auxiliary agent can be to spray, it is also possible to be saturated dipping, also
It can be supersaturation dipping.
In step of the present invention (5), after catalyst dipping, drying condition is generally at 80 ~ 200 DEG C, is dried 1 ~ 15 hour, roasting
Burning temperature and be generally 450 ~ 700 DEG C, roasting time is generally 1 ~ 10 hour.
In step of the present invention (5), when carrier impregnation active metal component and auxiliary agent, generally use containing active metal and auxiliary agent
Impregnation liquid impregnate.Impregnation liquid uses conventional method preparation, will the noble metal (one or many in platinum, palladium, ruthenium and rhodium
Kind) and the predecessor of rare earth metal be dissolved in solvent formulated.
In the preparation process of catalyst carrier of the present invention, it is to use aminoacid to pull an oar again after processing activated carbon, then exists
Introducing during the plastic of amorphous alumina, such aminoacid adsorbs uniformly on the surfaces externally and internally of activated carbon, by rear
Continuous roasting process makes to be mixed in the aminoacid in the middle of aluminium oxide and activated carbon and decomposes carbonization, and the activated carbon being newly formed connects oxidation
Aluminum and activated carbon so that the combination of activated carbon and aluminium oxide is more tight, and the aminoacid on activated carbon inner surface is through being decomposed to form
The inner surface of the former activated carbon of new Activated Carbon Modification, add the adsorption activity position of activated carbon inner surface.Therefore, aminoacid processes
Activated carbon, can promote aluminium oxide closely coating active charcoal, is conducive to improving mechanical strength and the abrasion resisting of catalyst
Performance, and improve the utilization rate of the inner surface of activated carbon, be conducive to improving activity and the stability of catalyst.
Catalyst preparation process of the present invention is simple, convenient, it is easy to operation, is suitable for commercial production.
Detailed description of the invention
The specific surface area of product of the present invention and pore volume are to use low temperature liquid nitrogen physisorphtion to measure.Rate of wear is to use to turn
Cartridge type abrasion instrument measures and (is specifically shown in " catalyst carrier preparation and application technology " (petroleum industry publishing house, in May, 2002, Zhu Hong
Method is write, and 4.5.4 saves).Powder carrier and catalyst grain size use laser particle size analyzer to measure；Shaping carrier and catalysis
Agent granularity uses sieve method to record.In the present invention, wt% is mass fraction.
Further illustrate the preparation method of the present invention below in conjunction with 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, granularity 200 mesh.
Embodiment 1
Solid aluminum chloride is joined in distilled water, heat simultaneously and stir to dissolving, obtaining solution (a).By strong aqua ammonia
Add appropriate distilled water diluting and become about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in glutamic acid aqueous solution, liquid
Gu volume ratio is 3:1, then add water making beating, obtains serosity (c).After adding (a) in plastic cans and being heated with stirring to 60 DEG C,
Open the valve of the container having (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, now add in tank
C (), continues dropping (b), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0.Keeping temperature is 60 DEG C, and pH=8.0 is aging
1 hour, being filtered by material in tank, washing, to without chloride ion, is filtered, and is dried 10 hours by filter cake, is carried at 110 DEG C
Body materials A-1.Roasting 5 hours under the conditions of 550 DEG C, pulverize and sieve and obtain powder carrier J-1 the most under nitrogen protection.Become
The amount of glue agents useful for same is listed in table 1.
Take powder carrier J-1 100 grams, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then exist
It is dried 10 hours at 110 DEG C, after roasting 5 hours, impregnates with the impregnation liquid containing Pt-Ce, so under the conditions of 550 DEG C under nitrogen protection
After at 110 DEG C be dried 10 hours, nitrogen protection under under the conditions of 550 DEG C roasting 5 hours, obtain catalyst A, its composition is shown in Table
2。
Embodiment 2
Solid aluminum sulfate is joined in distilled water, heat simultaneously and stir to dissolving, obtaining solution (a).By strong aqua ammonia
Add appropriate distilled water diluting and become about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in glutamic acid aqueous solution, liquid
Gu volume ratio is 3:1, then add water making beating, obtains activated carbon serosity (c).Take a plastic cans, tank adds (a) and is heated with stirring to
After 60 DEG C, open the valve of the container having (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, open (c) and hold
The valve of device, continues dropping (b), and system in tank is added drop-wise in controlling 30 minutes pH=8.0, controls the valve of the container of (c),
Ensure now to be added dropwise to complete.Keeping temperature is 60 DEG C, and material in tank aging 1 hour, is filtered by pH=8.0, and washing is to nothing
Sulfate ion, filters, and is dried 10 hours by filter cake, obtains carrier material A-2 at 110 DEG C.Exist the most under nitrogen protection
Roasting 5 hours under the conditions of 550 DEG C, pulverize and sieve and obtain powder carrier J-2.The amount of plastic agents useful for same is listed in table 1.
Taking carrier material A-2 100 grams, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours, impregnates with the impregnation liquid containing Ru-Ce, then under the conditions of 550 DEG C under nitrogen protection
At 110 DEG C be dried 10 hours, nitrogen protection under under the conditions of 550 DEG C roasting 5 hours, obtain catalyst B, its composition is shown in Table 2.
Embodiment 3
Solid aluminum sulfate is joined in distilled water, heat simultaneously and stir to dissolving, obtaining solution (a).Solid is inclined
It is 250g Al that sodium aluminate is configured to concentration2O3/ L sodium aluminate solution (b).Powdery coconut husk charcoal is added in glutamic acid aqueous solution mixed
Closing uniformly, liquid-solid volume ratio is 3:1, and then add water making beating, obtains serosity (c).Take a plastic cans, insert the stirring of 2L deionized water
Add serosity (c) after being heated to 60 DEG C, open the valve of the container having (a), (b) simultaneously, control the pH=8.0 of system, control
In making 45 minutes, (a) is dripped off, close valve.Keeping temperature is 60 DEG C, and material in tank aging 1 hour, is carried out by pH=8.0
Filter, wash to sulfate radical-free ion, filter, filter cake is dried 10 hours at 110 DEG C, obtains carrier material A-3.Then exist
Nitrogen protection under under the conditions of 550 DEG C roasting 5 hours, pulverize and sieve and obtain powder carrier J-3.The amount row of plastic agents useful for same
In table 1.
Taking carrier material A-3 100 grams, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours, impregnates with the impregnation liquid containing Ru-Ce, then under the conditions of 550 DEG C under nitrogen protection
At 110 DEG C be dried 10 hours, nitrogen protection under under the conditions of 550 DEG C roasting 5 hours, obtain catalyst C, its composition is shown in Table 2.
Embodiment 4
Solid aluminum chloride is joined in distilled water, heat simultaneously and stir to dissolving, obtaining solution (a).By strong aqua ammonia
Add appropriate distilled water diluting and become about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in lysine solution, liquid
Gu volume ratio is 3:1, then add water making beating, obtains activated carbon serosity (c).In plastic cans, add (a) and be heated with stirring to 60 DEG C
After, open the valve of the container having (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, now adds in tank
Enter (c), continue dropping (b), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0.Keeping temperature is 60 DEG C, pH=8.0, always
Changing 1 hour, filtered by material in tank, washing, to without chloride ion, is filtered, and is dried 10 hours by filter cake, obtains at 110 DEG C
Carrier material A-4.Roasting 5 hours under the conditions of 550 DEG C, pulverize and sieve and obtain powder carrier J-4 the most under nitrogen protection.
The amount of plastic agents useful for same is listed in table 1.
Taking carrier material A-4 100 grams, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours, impregnates with the impregnation liquid containing Ru-Ce, then under the conditions of 550 DEG C under nitrogen protection
At 110 DEG C be dried 10 hours, nitrogen protection under under the conditions of 550 DEG C roasting 5 hours, obtain catalyst D, its composition is shown in Table 2.
Embodiment 5
Solid aluminum sulfate is joined in distilled water, heat simultaneously and stir to dissolving, obtaining solution (a).By strong aqua ammonia
Add appropriate distilled water diluting and become about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in lysine solution, liquid
Gu volume ratio is 3:1, then add water making beating, obtains activated carbon serosity (c).Take a plastic cans, tank adds (a) and is heated with stirring to
After 60 DEG C, open the valve of the container having (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, open (c) and hold
The valve of device, continues dropping (b), and system in tank is added drop-wise in controlling 30 minutes pH=8.0, controls the valve of the container of (c),
Ensure now to be added dropwise to complete.Keeping temperature is 60 DEG C, and material in tank aging 1 hour, is filtered by pH=8.0, and washing is to nothing
Sulfate ion, filters, and is dried 10 hours by filter cake, obtains carrier material A-5 at 110 DEG C.Exist the most under nitrogen protection
Roasting 5 hours under the conditions of 550 DEG C, pulverize and sieve and obtain powder carrier J-5.The amount of plastic agents useful for same is listed in table 1.
Taking carrier material A-5 100 grams, contact with the peptization liquid containing nitric acid and form paste, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours, impregnates with the impregnation liquid containing Pt-La, then under the conditions of 550 DEG C under nitrogen protection
At 110 DEG C be dried 10 hours, nitrogen protection under under the conditions of 550 DEG C roasting 5 hours, obtain catalyst E, its composition is shown in Table 2.
Comparative example 1
Repeat the synthesis of embodiment 2, without activated carbon and aminoacid during plastic, prepare comparative catalyst's carrier
Material PA-1 and powder carrier DF-1, its appearance white.
Preformed catalyst is prepared with embodiment 2, obtains catalyst DA, and its composition is shown in Table 2.
Comparative example 2
By activated carbon 100 grams used in embodiment 2, contact with the peptization liquid containing nitric acid and form paste, extruded moulding,
Then being dried 10 hours at 110 DEG C, after roasting 5 hours, obtain carrier under nitrogen protection under the conditions of 550 DEG C, its outward appearance is
Black.Then using the method dipping active metal component of embodiment 2, obtain catalyst DB, its composition is shown in Table 2.
Comparative example 3
By activated carbon used in embodiment 2 with carrier material PA-1 physical mixed, contact with the peptization liquid containing nitric acid
Form paste, extruded moulding, be then dried 10 hours at 110 DEG C, under nitrogen protection under the conditions of 550 DEG C after roasting 5 hours,
Obtaining carrier, wherein activated carbon content is 50wt%, and alumina content is 50wt%, and its outward appearance is black.Then embodiment 2 is used
Method dipping active metal component, obtain catalyst DC, its composition is shown in Table 2.
Comparative example 4
Repeat the synthesis of embodiment 2, without aminoacid during plastic, prepare catalyst carrier material PA-2 and powder
Powder carrier DF-2.
Preformed catalyst is prepared with embodiment 2, obtains catalyst DD, and its composition is shown in Table 2.
Table 1 plastic reagent quality
The composition of table 2 catalyst and character
By catalyst property in table 2 it can be seen that use the catalyst bulk property that aminoacid obtains after processing activated carbon
It is improved.
It is canescence, without obvious black, explanation by the carrier material of embodiment of the present invention gained and the outward appearance of carrier
Activated carbon becomes the core of carrier material and carrier.
In the present invention, use X-ray photoelectron spectroscopy (XPS) to embodiment and comparative example 1 resulting vehicle material surface
Element be analyzed.From analysis result, the elementary composition and PA-1 group on embodiment resulting vehicle materials A-1 ~ A-5 surface
Become essentially identical, all have the elemental carbon of trace.This further illustrates, and the carrier material of the present invention is with activated carbon as core, with oxygen
Changing aluminum dry glue is shell.
Simulated wastewater is used to carry out evaluating catalyst.
Preparation sodium sulfite waste water, COD be 12000mg/L pH value of solution be 6～7, comment in small-sized flow reactor
Valency.At treatment temperature 45 DEG C, volume space velocity 2.0h-1, it is wet that the reaction condition of gas-liquid volume ratio 200 carries out continuous catalysis to this waste water
Formula airoxidation.Result is listed in table 3.
Table 3 evaluation result
| Catalyst is numbered | B | DA | DB | DC | DD |
| COD clearance, % | 97.9 | 84.8 | 96.7 | 93.4 | 94.4 |
From table 3 evaluation result it can be seen that waste water COD after treatment has had obvious reduction, the COD of phenol wastewater is gone
Except rate all more than 90%.After continuously running 1000h, evaluation result is listed in table 4.
Table 4 estimation of stability result
By table 4 result it can be seen that after catalyst use 1000h, use catalyst activity base prepared by the inventive method
Originally it is not changed in, there is good stability.
The present invention uses has the noble metal of excellent catalytic activity as active component, adds rare earth metal as auxiliary agent,
Rare earth metal and noble metal have good coordinative role, add the stability of catalyst and activity and reduce cost, tool
There is good application prospect.
Claims (19)
1. a preparation method for catalytic wet oxidation catalyst, this catalyst includes carrier, active metal component and auxiliary agent, its
In with one or several in Pt, Pd, Rh, Ru as active metal component, rare earth metal is auxiliary agent, and preparation process includes:
(1) use aminoacid to process 150 mesh ~ 300 mesh activated carbons, then pull an oar；It is by ammonia that aminoacid processes activated carbon
Base acid directly mixes with activated carbon, or is dissolved in solvent by aminoacid and adds activated carbon；Described aminoacid is carbon atom
The number aminoacid less than 20；
(2) during amorphous alumina plastic, the activated carbon serosity that step (1) obtains is introduced；
(3) material after the plastic that step (2) obtains carry out aging, filter, wash, be dried, obtain catalyst carrier material；
(4) carrier material of step (3) gained is made catalyst carrier；
(5) impregnate active metal component and auxiliary agent in the catalyst carrier of step (4) gained, be then dried, protect at noble gas
Protect lower roasting, obtain catalytic wet oxidation catalyst.
The most in accordance with the method for claim 1, it is characterised in that the preparation of step (4) catalyst carrier at least uses following side
One of method:
A, by the carrier material of step (3) gained, roasting under inert gas shielding, obtain catalyst carrier；
B, by the carrier material molding of step (3) gained, after drying, roasting under inert gas shielding, obtain catalyst carry
Body；
C, by carrier material roasting under inert gas shielding of step (3) gained, the most again through molding, after drying, in inertia
Roasting under gas shield, obtains catalyst carrier.
The most in accordance with the method for claim 1, it is characterised in that described catalyst carrier is with the activity of 150 mesh ~ 300 mesh
Charcoal is core, with amorphous alumina as shell, wherein activated carbon accounts for the 10% ~ 70% of vehicle weight, and aluminium oxide accounts for the 30% of vehicle weight
~90%。
The most in accordance with the method for claim 1, it is characterised in that described rare earth metal be the one in lanthanum, cerium, praseodymium, neodymium or
Multiple.
The most in accordance with the method for claim 1, it is characterised in that in described catalyst carrier, activated carbon accounts for vehicle weight
30% ~ 70%, aluminium oxide accounts for the 30% ~ 70% of vehicle weight.
The most in accordance with the method for claim 1, it is characterised in that in described catalyst, on the basis of the weight of catalyst,
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.
The most in accordance with the method for claim 1, it is characterised in that described catalyst or powder catalyst, or
Preformed catalyst, the granularity of powder catalyst is 0.05 ~ 0.2mm, and preformed catalyst granularity is 0.5 ~ 8.0mm.
The most in accordance with the method for claim 1, it is characterised in that the character of step (1) described activated carbon is as follows: specific surface area
500~3000m2/ g, pore volume 0.5 ~ 1.8cm3/ g, average pore radius 1 ~ 10nm.
The most in accordance with the method for claim 1, it is characterised in that the activated carbon making beating employing described in step (1) adds water and low-carbon (LC)
One or more in alcohol are pulled an oar, wherein low-carbon alcohols be carbon number be one or more in the monohydric alcohol of 1 ~ 5.
The most in accordance with the method for claim 1, it is characterised in that described aminoacid consumption account for activated carbon weight 2% ~
50%。
11. in accordance with the method for claim 1, it is characterised in that described aminoacid consumption account for activated carbon weight 5% ~
20%。
12. in accordance with the method for claim 1, it is characterised in that described aminoacid be glycine, serine, threonine,
In cysteine, tyrosine, agedoite, glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid one
Plant or multiple.
13. in accordance with the method for claim 1, it is characterised in that the aminoacid described in step (1) is that carbon number is less than 10
The hydrophilic amino acid of long-chain.
14. in accordance with the method for claim 1, it is characterised in that: it is directly with alive by aminoacid that aminoacid processes activated carbon
Property charcoal mixing, or aminoacid be dissolved in solvent add activated carbon, solvent therein is water and carbon number is the one of 1 ~ 5
One or more in unit's alcohol；When aminoacid processes activated carbon, liquid-solid volume ratio is below 10.
15. in accordance with the method for claim 1, it is characterised in that: the plastic mistake of the amorphous alumina described in step (2)
Journey is acid material and the neutralization course of reaction of alkaline material, and plastic process uses the mode of the continuous acid-base titration of soda acid, or
Use two kinds of materials and flow the mode of neutralization.
16. in accordance with the method for claim 1, it is characterised in that: in step (2), the activated carbon serosity of step (1) gained
Incorporation way uses the one or more combination of following manner: this activated carbon serosity, in plastic and in course of reaction, is connected by (1)
In continuous addition plastic cans；(2) this activated carbon serosity is charged first in plastic cans, then will prepare the acidity of amorphous alumina
In material and alkaline material and plastic；(3) this activated carbon serosity is mixed with one or more of plastic material, then plastic thing
Material neutralizes plastic.
17. in accordance with the method for claim 1, it is characterised in that: in step (3), described drying condition is as follows: 50 ~
It is dried 1 ~ 15 hour at 150 DEG C.
18. in accordance with the method for claim 2, it is characterised in that: in step (4), 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 the drying condition described in method B is at 80 ~ 200 DEG C, be dried 1 ~
15 hours, sintering temperature was 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, in method C, by the carrier material of step (3) gained
Roasting under inert gas shielding, described roasting condition is as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 little
Time, the most again through molding, after drying, roasting under inert gas shielding, obtain catalyst carrier, the drying condition after molding is such as
Under: at 80 ~ 200 DEG C, being dried 1 ~ 15 hour, roasting condition is as follows: sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 little
Time.
19. in accordance with the method for claim 1, it is characterised in that: in step (5), catalyst carrier impregnates active metal
After component and auxiliary agent, drying condition is to be dried 1 ~ 15 hour at 80 ~ 200 DEG C, and sintering temperature condition is 450 ~ 700 DEG C of roastings 1 ~ 10
Hour.
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