CN104667973B - Catalyst carrier material and preparation method thereof - Google Patents
Catalyst carrier material and preparation method thereof Download PDFInfo
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- CN104667973B CN104667973B CN201310621077.6A CN201310621077A CN104667973B CN 104667973 B CN104667973 B CN 104667973B CN 201310621077 A CN201310621077 A CN 201310621077A CN 104667973 B CN104667973 B CN 104667973B
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Abstract
The invention discloses a catalyst carrier material and a preparation method thereof. The carrier material uses activated carbon with particle size of 150-300 meshes as a core and amorphous silica-alumina dried gum as a shell, wherein the activated carbon is 10-70 percent of the dry base of the carrier material, and the amorphous silica-alumina dried gum is 30-90 percent of the weight of silica and alumina; the carrier material comprises amino acid which is 2-50 percent of the weight of activated carbon. The method comprises the following steps: introducing amino acid treated activated carbon slurry into the process of gelling amorphous silica-alumina, and preparing the catalyst carrier material by means of aging, drying and other steps. The carrier material is especially suitable for a catalytic wet oxidation catalyst, so that 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 catalyst carrier material and preparation method thereof, especially for the catalysis of CWO
Agent carrier material and preparation method thereof.
Background technology
With the increasingly stringent of global environmental regulation, the Con trolling index of sewage qualified discharge requires more and more higher, here
Under form, waste water treatment by catalytic oxidation has increasingly obtained attention and the employing 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, preferably locate for obtaining
Reason effect and keep relatively low wastewater treatment expense by reducing reaction temperature, reaction pressure, preparation have high-activity component,
High intensity, the cheap catalyst of high stability undoubtedly become the key of waste water catalytic oxidation technologies application.
The catalyst of waste water catalysis oxidation is broadly divided into homogeneous catalyst and heterogeneous solid catalyst two class.
Homogeneous catalyst mainly include with produce oxygen radical Fenton reagent, 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 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 is prepared and is used process relatively
For simple, typically directly can be made into aqueous solution from slaines such as ferrum, copper, cobalt, manganese or be directly thrown in handled waste water,
And used by discharging in the water outlet after processing or regenerating Posterior circle.Using homogeneous catalytic oxidation, because metal active constituent is useless
Can fully dissolve in water and disperse, typically can reach relatively stable water treatment effect, but exist that reagent consumption is big, fortune
Row costly, the serious problems such as metal loss and secondary pollution, cause its application to be subject to larger limiting.
Heterogeneous solid catalyst is mainly with activated carbon, molecular sieve, amorphous alumina, titanium dioxide etc. as carrier, with
One or more of alkali metal, alkaline-earth metal, transition metal or Pt, Pd noble metal make the catalyst of active component composition.Live
Property charcoal be made up of carbonaceous material black, hole is flourishing, specific surface area is 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.Currently used for useless
The heterogeneous solid catalyst of water process selects activated carbon mostly as carrier, but selects merely activated carbon supported metal preparation
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 beaten
Discount., because having good chemical stability, pore volume is big for amorphous silica-alumina, has stronger acidity, pore size distribution$ is concentrated, machine
Tool intensity is big, corrosion-resistant the advantages of, be widely used in catalytic field, but amorphous silica-alumina have little the lacking of specific surface
Point, absorption and conversion capability to Organic substance are relatively weak.
CN201110225789.7 discloses a kind of side preparing benzene adsorption material using discarded active amorphous aluminium oxide
Method, it be will cleaned for useless active amorphous aluminium oxide, filter, be dried after, prepared a kind of using cryogenic seal heat treatment mode
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, so not only can block aluminium oxide
Duct, and the activated carbon so being generated skewness in aluminium oxide.
CN201110255525.6 discloses a kind of preparation method of active amorphous aluminium oxide/absorbent charcoal composite material,
Be by waste aluminum sludge, activated carbon, binding agent through mixings, pelletize, old, molding, dry, sinter, rinsing, drying
Make active amorphous aluminium oxide/absorbent charcoal composite material 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 being used, the amorphous of gained
Aluminum property 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
Aluminum, activated carbon and binding agent are raw material, through mixing, pelletize, old, molding, dry, sinter, rinsing, drying and other steps, so
The composite obtaining is still the physical mixture of aluminium oxide and activated carbon, and aluminium oxide and activated carbon dispersion are uneven, and it is comprehensive
Performance also needs to improve further.
Content of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of catalyst carrier material.Urged using this
What agent carrier material was made has good catalytic performance in catalytic wet oxidation catalyst, and anti-wear performance is strong, uses
Good stability.
The catalyst carrier material of the present invention, with the activated carbon of 150 mesh ~ 300 mesh as core, with contained amorphous silica-alumina dry glue be
Shell, wherein on the basis of the butt weight of catalyst carrier material, the content of activated carbon is 10% ~ 70%, preferably 30% ~ 70%,
The content that contained amorphous silica-alumina dry glue is counted with silicon oxide and aluminium oxide for 30% ~ 90%, preferably 30% ~ 70%, described carrier material
In contain aminoacid, described aminoacid accounts for the 2% ~ 50% of activated carbon weight.
Described aminoacid is hydrophilic amino acid, such as glycine, serine, threonine, cysteine, tyrosine, sky
One of winter amide, L-Glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid or multiple, preferably carbon is former
Subnumber is less than the hydrophilic amino acid of 20 long-chain.Such as one of aspartic acid, glutamic acid, lysine etc. or multiple.
Aminoacid described in the carrier material of the present invention is mainly distributed between the inner surface of activated carbon and nucleocapsid i.e.
Between activated carbon and contained amorphous silica-alumina dry glue.
The granularity of the catalyst carrier material of the present invention is generally 0.05 ~ 0.2mm.
The preparation process of catalyst carrier material of the present invention is as follows：
(1) 150 mesh ~ 300 mesh activated carbons are adopted amino acid treatment, then pulled an oar；
(2) introduce step during amorphous silica-alumina plastic（1）The activated carbon serosity obtaining；
(3) step（2）Material after the plastic obtaining carry out aging, filter, washing, be dried, obtain catalyst carrier material
Material.
The described activated carbon of step (1) of the present invention 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 from wooden material, mineral material, plastics and garbage, such 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. obtains 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, step（1）Described activated carbon making beating is carried out using conventional method, typically using adding water, low
One or more of carbon alcohol is pulled an oar, one or more of monohydric alcohol that wherein low-carbon alcohols are 1 ~ 5 for carbon number.
In the inventive method, step（1）Activated carbon first adopts amino acid treatment, is then pulled an oar.Described aminoacid
For hydrophilic amino acid, such as glycine, serine, threonine, cysteine, tyrosine, agedoite, L-Glutamine, bad ammonia
One of acid, arginine, histidine, aspartic acid, glutamic acid or multiple, preferably carbon number are less than the parent of 20 long-chain
Aqueouss aminoacid.Such as aspartic acid, glutamic acid, lysine etc..Described aminoacid consumption accounts for the 2% ~ 50% of activated carbon weight,
It is preferably 5% ~ 20%.Aminoacid can directly be mixed it is also possible to be dissolved in aminoacid by amino acid treatment activated carbon with activated carbon
Activated carbon is added, solvent therein is water, low-carbon alcohols in solvent（I.e. carbon number is 1 ~ 5 monohydric alcohol）One of or many
Kind.During amino acid treatment activated carbon, its liquid consolidates volume ratio below 10, preferably 1 ~ 5.After amino acid treatment activated carbon, excessive
Liquid phase be preferably filtered to remove, then pulled an oar again.Making beating can be carried out using conventional method, typically using adding water, low-carbon alcohols
One or more of pulled an oar, wherein low-carbon alcohols are 1 ~ 5 one or more of monohydric alcohol for carbon number.
Step of the present invention（2）Described in the plastic process of amorphous silica-alumina can be by mistake well known to those skilled in the art
Cheng Jinhang.The plastic process of amorphous silica-alumina is usually the neutralization reaction process of acid material and alkaline material.Plastic process can
In the way of using the continuous acid-base titration of soda acid, it would however also be possible to employ the mode of two kinds of material cocurrent neutralizations.
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 is general to adopt two kinds
Material cocurrent plastic mode of operation, or a kind of material is placed in plastic cans the operation side that another kind of material is continuously added to plastic
Formula.Plastic material generally comprises silicon source（Al2(SO4)3、AlCl3、Al(NO3)3And NaAlO2One or more of Deng）, silicon source
（One or more of waterglass, Ludox and organic silicon-containing compound etc.）, precipitant（NaOH、NH4OH or CO2Deng）, according to
The different choice of plastic process uses, 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）Neutralization plastic,（2）Basic aluminium salt（NaAlO2）With
Acidic precipitation agent（CO2）Neutralization plastic.Silicon source introduces plastic cans it is also possible to mix with silicon source or precipitant typically during plastic
Neutralize plastic again after conjunction, be such as neutralized plastic in waterglass addition basic aluminium salt or alkaline precipitating agent, Ludox adds acid
It is neutralized plastic etc. in aluminium salt.Silicon source can also add after silicon source precipitation in material.Can also be by two kinds of aforesaid way or two
Plant above in association with use.Said method is all well-known to those skilled in the art.Described plastic process is typically in room temperature ~ 85
Carry 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 is aging, and 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 suitable at 0.5 ~ 5 hour, preferably 1 ~ 3
Hour, aging temperature is room temperature ~ 85 DEG C, preferably 40 ~ 80 DEG C.Temperature when aging and pH are best with temperature during neutralization and pH
Identical.
Step of the present invention（2）In, step（1）The incorporation way of the mixture of gained adopts one or more of following manner
Combination：（1）During plastic neutralization reaction, this mixture is continuously added in plastic cans；（2）This mixture is charged first to
In plastic cans, then will prepare in the acid material of amorphous silica-alumina and alkaline material and plastic；（3）By this mixture and plastic
One or more 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 select
Add water when making beating washing, filtration the modes such as washing, lower alcohols washing, and the temperature of washing should be in the temperature model of room temperature ~ 90 DEG C
In enclosing, preferably 50 ~ 70 DEG C.The washing of described material is to carry out in the range of 1.0 ~ 9.0 typically in pH, and preferably pH is 4.0 ~ 8.5.
Step of the present invention（3）Described in material in washing, filter after should without or contain minimal amount of heteroion, heteroion includes
Na+、Cl-、SO4 2-、NO3 -、K+One or more of Deng.
Step of the present invention（3）In, after washing, filtering, filter cake is dried described material, and drying mode can adopt
Natural drying, oven drying, spray drying, microwave drying or infrared drying, the general drying condition adopting is as follows：50 ~
It is dried 1 ~ 15 hour at 150 DEG C.
In the present invention, carry out roasting under inert gas shielding, selected noble gases are generally nitrogen or argon.
Catalyst carrier material of the present invention is with activated carbon as core, with amorphous silica-alumina as shell, so make reactant first with
After the amorphous silica-alumina haptoreaction of shell, then contact with the activated carbon as stratum nucleare and reacted, it is no fixed to make full use of
Shape sial aperture is big, pore volume is high and activated carbon specific surface area big, the feature of high adsorption capacity, makes catalyst have higher reaction
Activity and stability in use, improve the service life of catalyst.This carrier is particularly useful as catalytic wet oxidation catalyst carrier,
The catalytic wet oxidation catalyst carrier of especially Love psychology, to improve the activity of catalyst and the stability of use.
In the preparation process of catalyst carrier material of the present invention, beat again in particular by after amino acid treatment activated carbon
Slurry, then introduces, such aminoacid uniformly adsorbs on the surfaces externally and internally of activated carbon during the plastic of amorphous silica-alumina,
The aminoacid being mixed in the middle of amorphous silica-alumina and activated carbon is made to decompose carbonization, the new activity being formed by follow-up roasting process
Charcoal connects amorphous silica-alumina and activated carbon so that the combination of activated carbon and amorphous silica-alumina is even closer, on activated carbon inner surface
The former activated carbon of new Activated Carbon Modification through being decomposed to form for the aminoacid inner surface, increased the adsorption activity of activated carbon inner surface
Position.Therefore, amino acid treatment activated carbon, can promote amorphous silica-alumina closely to wrap up activated carbon, be conducive to raising to urge
The mechanical strength of agent and abrasion resisting performance, and improve the utilization rate of the inner surface of activated carbon, be conducive to improving catalyst
Activity and stability.
Catalyst carrier preparation process of the present invention is simple, conveniently it is easy to operate, suitable commercial production.
Specific embodiment
The specific surface area of product of the present invention and pore volume are to be measured using low temperature liquid nitrogen physisorphtion.Rate of wear is to adopt to turn
Cartridge type abrasion instrument measures（It 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 granularity adopts laser particle size analyzer to measure；Shaping carrier and catalyst grain size are adopted
Recorded with sieve method.In the present invention, wt% is mass fraction.
To further illustrate the preparation method of the present invention with reference to specific embodiment, but the scope of the present invention is not only
It is limited to the scope of these embodiments.
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, granularity 200 mesh.Waterglass raw material is technical grade, and modulus is 3.0.
Embodiment 1
Solid aluminum chloride is added in distilled water, heats and stir to dissolving, obtain liquor alumini chloridi (a).By dense ammonia
Water adds appropriate distilled water diluting to become about 10% 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).Waterglass is according to 1:2 dilution proportion in deionized water, is joined
It is set to solution (d).After adding (a) in plastic cans and being heated with stirring to 65 DEG C, open the valve of the container having (b), control
Within 10 minutes, system in tank is added drop-wise to pH=4.5, continues Deca (b), open the valve of the container having (c), control 30 points
In clock, system in tank is added drop-wise to pH=8.0, the valve of container controlling (c) is it is ensured that be now added dropwise to complete.Keeping temperature is 65
DEG C, pH=8.0, after stopping 20 minutes, add solution (d) in system, the content according to silicon dioxide in amorphous silica-alumina is
45wt% calculates and added in 10 minutes.Aging 1 hour, material in tank is filtered, wash to no chloride ion, filter, will filter
Cake is dried 10 hours at 110 DEG C, obtains carrier material A-1.The amount of plastic agents useful for same is listed in table 1.
Take 100 grams of carrier material A-1, form paste with the peptization liquid contact containing nitric acid, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst carrier Z-1, its property is shown in
Table 2.
Embodiment 2
Solid aluminum sulfate is added in distilled water, heats and stir to dissolving, obtain aluminum sulfate solution (a).By dense ammonia
Water adds appropriate distilled water diluting to become about 10% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in glutamic acid aqueous solution, liquid
Gu volume ratio is 5：1, then add water making beating, obtains activated carbon serosity (c).Waterglass is according to 1:2 dilution proportion is in deionized water
In, it is configured to solution (d).After adding (a) in plastic cans and being heated with stirring to 65 DEG C, open the valve of the container having (b),
Control, within 10 minutes, system in tank is added drop-wise to pH=4.5, continue Deca (b), open the valve of the container having (c), control
In 30 minutes, system in tank is added drop-wise to pH=8.0, the valve of container controlling (c) is it is ensured that be now added dropwise to complete.Keeping temperature
For 65 DEG C, pH=8.0, after stopping 20 minutes, add solution (d) in system, according to the content of silicon dioxide in amorphous silica-alumina
Calculate for 50wt% and added in 10 minutes.Aging 1 hour, material in tank is filtered, washed to sulfate radical-free ion, mistake
Filter, filter cake is dried 10 hours at 110 DEG C, obtains carrier material A-2.The amount of plastic agents useful for same is listed in table 1.
Take 100 grams of carrier material A-2, form paste with the peptization liquid contact containing nitric acid, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst carrier Z-2, its property is shown in
Table 2.Then impregnated with the impregnation liquid containing Ce-Cu, be then dried 10 hours at 110 DEG C, under nitrogen protection under the conditions of 550 DEG C
Roasting 5 hours, obtains catalyst B, and its composition is shown in Table 3.
Embodiment 3
Solid aluminum sulfate is added in distilled water, heats simultaneously and stir to dissolving, obtain aluminum sulfate solution (a).Will
It is 250g Al that solid sodium metaaluminate is configured to concentration2O3/ l sodium aluminate solution (b).Powdery coconut husk charcoal is added glutamic acid water-soluble
Mix homogeneously in liquid, the solid volume ratio of liquid is 3：1, then add water making beating, obtains serosity（c）.Take a plastic cans, insert 2L deionization
Water adds serosity (c) after being heated with stirring to 60 DEG C.Waterglass is according to 1:2 dilution proportion in deionized water, is configured to solution
(d).Take a retort, insert after 2L deionized water is heated with stirring to 65 DEG C, open the container having (a), (b), (c) simultaneously
Valve, the pH=8.0 of control system, control in 45 minutes and (a) and (c) dripped off simultaneously.Keeping temperature is 65 DEG C, pH=
8.0, after stopping 20 minutes, add solution (d) in system, content 55wt% according to silicon dioxide in amorphous silica-alumina calculates
Added in 10 minutes.Aging 1 hour, material in tank is filtered, wash to sulfate radical-free ion, filter, filter cake is existed
It is dried 10 hours at 110 DEG C, obtain carrier material A-3.The amount of plastic agents useful for same is listed in table 1.
Take 100 grams of carrier material A-3, form paste with the peptization liquid contact containing nitric acid, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst carrier Z-3, its property is shown in
Table 2.
Embodiment 4
Solid aluminum chloride is added in distilled water, heats and stir to dissolving, obtain liquor alumini chloridi (a).By dense ammonia
Water adds appropriate distilled water diluting to become about 10% weak ammonia (b), and 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).Waterglass is according to 1:2 dilution proportion is in deionized water
In, it is configured to solution (d).After adding (a) in plastic cans and being heated with stirring to 65 DEG C, open the valve of the container having (b),
Control, within 10 minutes, system in tank is added drop-wise to pH=4.5, continue Deca (b), open the valve of the container having (c), control
In 30 minutes, system in tank is added drop-wise to pH=8.0, the valve of container controlling (c) is it is ensured that be now added dropwise to complete.Keeping temperature
For 65 DEG C, pH=8.0, after stopping 20 minutes, add solution (d) in system, according to the content of silicon dioxide in amorphous silica-alumina
Calculate for 45wt% and added in 10 minutes.Aging 1 hour, material in tank is filtered, wash to no chloride ion, filter, will
Filter cake is dried 10 hours at 110 DEG C, obtains carrier material A-4.The amount of plastic agents useful for same is listed in table 1.
Take 100 grams of carrier material A-4, form paste with the peptization liquid contact containing nitric acid, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst carrier Z-4, its property is shown in
Table 2.
Embodiment 5
Solid aluminum sulfate is added in distilled water, heats and stir to dissolving, obtain aluminum sulfate solution (a).By dense ammonia
Water adds appropriate distilled water diluting to become about 10% 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).Waterglass is according to 1:2 dilution proportion is in deionized water
In, it is configured to solution (d).After adding (a) in plastic cans and being heated with stirring to 65 DEG C, open the valve of the container having (b),
Control, within 10 minutes, system in tank is added drop-wise to pH=4.5, continue Deca (b), open the valve of the container having (c), control
In 30 minutes, system in tank is added drop-wise to pH=8.0, the valve of container controlling (c) is it is ensured that be now added dropwise to complete.Keeping temperature
For 65 DEG C, pH=8.0, after stopping 20 minutes, add solution (d) in system, according to the content of silicon dioxide in amorphous silica-alumina
Calculate for 55wt% and added in 10 minutes.Aging 1 hour, material in tank is filtered, washed to sulfate radical-free ion, mistake
Filter, filter cake is dried 10 hours at 110 DEG C, obtains carrier material A-5.The amount of plastic agents useful for same is listed in table 1.
Take 100 grams of carrier material A-5, form paste with the peptization liquid contact containing nitric acid, extruded moulding, then 110
It is dried 10 hours at DEG C, after roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst carrier Z-5, its property is shown in
Table 2.
Comparative example 1
Solid aluminum sulfate is added in distilled water, heats and stir to dissolving, obtain aluminum sulfate solution (a).By dense ammonia
Water adds appropriate distilled water diluting to become about 10% weak ammonia (b).Waterglass is according to 1:2 dilution proportion in deionized water, configures
Become solution (c).After adding (a) in plastic cans and being heated with stirring to 65 DEG C, open the valve of the container having (b), control 30
In minute, system in tank is added drop-wise to pH=8.0.Keeping temperature is 65 DEG C, pH=8.0, after stopping 20 minutes, adds in system
Solution (c), the content according to silicon dioxide in amorphous silica-alumina calculates for 50wt% and added in 10 minutes.Aging 1 hour, will
In tank, material is filtered, and washs to sulfate radical-free ion, filters, filter cake is dried 10 hours at 110 DEG C, obtains carrier material
Material PA-1, its appearance white.
Take 100 grams of carrier material PA-1, form paste, extruded moulding, Ran Hou with the peptization liquid contact containing nitric acid
It is dried 10 hours at 110 DEG C, after roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst carrier DZ- of molding
A, its appearance white, its property is shown in Table 2.Then impregnated with the impregnation liquid containing Ce-Cu, be then dried 10 hours at 110 DEG C, nitrogen
Under gas shielded under the conditions of 550 DEG C roasting 5 hours, obtain catalyst DA, its composition is shown in Table 3.
Comparative example 2
By 100 grams of activated carbon used in embodiment 2, contact with the peptization liquid containing nitric acid and form paste, extruded moulding,
Then it is dried 10 hours at 110 DEG C, after roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, obtain catalyst carrier DZ-
B, its outward appearance is black, then adopts the method for embodiment 2 to impregnate active metal component, obtains catalyst DB.
Comparative example 3
By activated carbon used in embodiment 2 with carrier material PA-1 physical mixed, with the peptization liquid contact containing nitric acid
Form paste, extruded moulding, be then dried 10 hours at 110 DEG C, after roasting 5 hours under the conditions of 550 DEG C under nitrogen protection,
Obtain catalyst carrier DZ-C, wherein activated carbon content is 50wt%, and amorphous silicon aluminium content is 50wt%, its outward appearance black.So
The method adopting embodiment 2 afterwards impregnates active metal component, obtains catalyst DC.
Comparative example 4
Repeat the synthesis of embodiment 2, without aminoacid during plastic, prepared catalyst carrier material PA-2.
Preformed catalyst carrier is prepared with embodiment 2, obtains catalyst carrier DZ-D.Active metal and carrying method are with real
Apply example 2, obtain catalyst DD, its composition is shown in Table 3.
Table 1 plastic agents useful for same quality
The property of table 2 catalyst carrier
The composition of table 3 catalyst
Be can be seen that by the property of catalyst carrier in table 2 and carried using the catalyst obtaining after amino acid treatment activated carbon
Compared with the catalyst carrier obtaining without aminoacid, bulk property is improved body.
Canescence is by the carrier material of embodiment of the present invention gained and the outward appearance of carrier, no obvious black, explanation
Activated carbon becomes the core of carrier material and carrier.
In the present invention, using 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 micro elemental carbon.This further illustrates, and the carrier material of the present invention is with activated carbon as core, with no
Amorphous silicon-alumina dry glue is shell.
The catalyst of the catalyst of the invention described above catalyst carrier preparation and its comparison vehicle preparation is evaluated.
Catalyst packing, in bubbling bed reactor, with ozone as oxide isolation, contains phenol to certain oil plant, sulfur-containing waste water enters
Row batch (-type) is processed.
Major pollutants COD in waste water：1500mg/L、S2-：280mg/L, volatile phenol：180mg/L.
Treatment conditions are normal temperature and pressure, catalyst amount 100g, waste water 200ml, ozone amount 35mg/L, the time of staying
30min.Catalyst is listed in table 4 using the result of handled waste water after 4 times.
Table 4 evaluation result
The waste water that can be seen that after treatment from table 4 evaluation result can meet qualified discharge Two-stage control index request.Make
With the catalyst of the inventive method preparation, there is preferable activity.
After catalyst uses 100 times, evaluation result is listed in table 5.
Table 5 estimation of stability result
Be can be seen that by table 5 result, using the catalyst of this method preparation, there is good stability.
Claims (15)
1. a kind of catalyst carrier material, with the activated carbon of 150 mesh ~ 300 mesh as core, with contained amorphous silica-alumina dry glue as shell, to carry
On the basis of the weight of body material butt, the content of activated carbon is 10% ~ 70%, and contained amorphous silica-alumina dry glue is in terms of silicon oxide and aluminium oxide
Content be 30% ~ 90%；Aminoacid is contained, described aminoacid accounts for the 2% ~ 50% of activated carbon weight in described carrier material；
Wherein, described aminoacid is less than 20 hydrophilic amino acid for carbon number.
2. according to the carrier material described in claim 1 it is characterised in that：On the basis of the weight of carrier material butt, activity
The content of charcoal is 30% ~ 70%, and the content that contained amorphous silica-alumina dry glue is counted with silicon oxide and aluminium oxide is for 30% ~ 70%.
3. according to the carrier material described in claim 1 it is characterised in that：Described aminoacid account for activated carbon weight 5% ~
20%.
4. according to the carrier material described in claim 1 it is characterised in that：Described aminoacid is glycine, serine, Soviet Union's ammonia
Acid, cysteine, tyrosine, agedoite, L-Glutamine, lysine, arginine, histidine, aspartic acid, in glutamic acid
One or more.
5. according to the carrier material described in claim 1 it is characterised in that：Described aminoacid be aspartic acid, glutamic acid, rely
One of propylhomoserin or multiple.
6. according to the carrier material described in claim 1 it is characterised in that：Described aminoacid is mainly distributed on the interior of activated carbon
It is between activated carbon and contained amorphous silica-alumina dry glue between surface and nucleocapsid.
7. according to the carrier material described in claim 1 it is characterised in that：The granularity of described catalyst carrier material is 0.05
~0.2mm.
8. according to the carrier material described in claim 1 it is characterised in that：The property of described activated carbon is as follows：Specific surface area 500
~3000m2/ g, pore volume 0.5 ~ 1.8cm3/ g, average pore radius 1 ~ 10nm.
9. the preparation method of the arbitrary described carrier material of claim 1 ~ 8, including：
(1) by the activated carbon of 150 mesh ~ 300 mesh with after amino acid treatment, then pull an oar；
(2) introduce step during amorphous silica-alumina plastic（1）The activated carbon serosity obtaining；
(3) step（2）Material after the plastic obtaining carry out aging, filter, washing, be dried, obtain catalyst carrier material；
Wherein, amino acid treatment activated carbon is directly to mix aminoacid with activated carbon, or aminoacid is dissolved in solvent again
Add activated carbon, solvent therein is one or more of water or carbon number monohydric alcohol for 1 ~ 5.
10. in accordance with the method for claim 9 it is characterised in that the property of the described activated carbon of step (1) is as follows：Specific surface area
500~3000m2/ g, pore volume 0.5 ~ 1.8cm3/ g, average pore radius 1 ~ 10nm.
11. in accordance with the method for claim 9 it is characterised in that step（1）Described activated carbon making beating is using adding water or low
One or more of carbon alcohol is pulled an oar, one or more of monohydric alcohol that wherein low-carbon alcohols are 1 ~ 5 for carbon number.
12. in accordance with the method for claim 9 it is characterised in that：During amino acid treatment activated carbon, the solid volume ratio of liquid 10 with
Under.
13. in accordance with the method for claim 9 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
Mode with two kinds of material cocurrent neutralizations.
14. in accordance with the method for claim 9 it is characterised in that：Step（2）In, step（1）The activated carbon serosity of gained
Incorporation way adopts the one or more combination of following manner：（1）During plastic neutralization reaction, by this activated carbon serosity even
In continuous addition plastic cans；（2）This activated carbon serosity is charged first in plastic cans, then will prepare the acid of amorphous silica-alumina
Material and alkaline material in and plastic；（3）This activated carbon serosity is mixed with one or more of plastic material, then plastic material
Neutralization plastic.
15. in accordance with the method for claim 9 it is characterised in that：Step（3）In, described drying condition is as follows：50 ~
It is dried 1 ~ 15 hour at 150 DEG C.
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| CN105521829A (en) * | 2015-12-16 | 2016-04-27 | 钟俊超 | Preparation method of wear-resistant large-pore-volume microspherical silica carrier |
| CN105536796A (en) * | 2015-12-16 | 2016-05-04 | 钟俊超 | Wear-resistant microspheric Fe2O3/SiO2 catalyst preparation method |
| CN105536881A (en) * | 2015-12-16 | 2016-05-04 | 钟俊超 | Preparation method of wear-resistant microspheroidal silica carrier |
| CN105396569A (en) * | 2015-12-16 | 2016-03-16 | 钟俊超 | Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier |
| CN105435858A (en) * | 2015-12-16 | 2016-03-30 | 钟俊超 | Preparation method of wear-resistant large-pore-volume microspherical silica carrier |
| CN105498853A (en) * | 2015-12-16 | 2016-04-20 | 钟俊超 | Method for preparing wear-resisting large-pore-volume micro-spherical silicon dioxide carrier |
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