CN104667994B - Method for preparing catalytic wet oxidation catalyst carrier - Google Patents
Method for preparing catalytic wet oxidation catalyst carrier Download PDFInfo
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- CN104667994B CN104667994B CN201310621076.1A CN201310621076A CN104667994B CN 104667994 B CN104667994 B CN 104667994B CN 201310621076 A CN201310621076 A CN 201310621076A CN 104667994 B CN104667994 B CN 104667994B
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Abstract
The invention discloses a method for preparing a catalytic wet oxidation catalyst carrier. The catalyst carrier takes activated carbon as a core and amorphous silica-alumina as a shell. The preparation method comprises the following steps: introducing slurry of saccharide treated activated carbon into the process of gelling amorphous silica-alumina, aging after gelling, and carrying out hydrothermal treatment; filtering, washing and drying to obtain a carrier material; and preparing the catalyst carrier. The catalyst prepared from the catalyst carrier 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 preparation method of catalytic wet oxidation catalyst carrier, particularly contain activated carbon and amorphous
The preparation method of the catalytic wet oxidation catalyst carrier of aluminium oxide.
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 the catalysis from activated carbon supported metal preparation
Agent anti-wear performance is poor, and mechanical strength is not high, and the metal of load is easy to run off so that the application effect of activated-carbon catalyst has beaten folding
Button., because having good chemical stability, pore volume is big for amorphous alumina, has certain acidity, pore size distribution$ is concentrated, machine
Tool intensity is big, corrosion-resistant the advantages of, be widely used in catalytic field, but amorphous alumina to there is specific surface little
Shortcoming, absorption and conversion capability to Organic substance are relatively small.
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 catalytic wet oxidation catalyst carrier.
Good catalytic performance is had using the catalyst that this catalyst carrier is made, and anti-wear performance is strong, stability in use is good.
The preparation method of catalytic wet oxidation catalyst carrier of the present invention, including：
(1) 150 mesh ~ 300 mesh activated carbons are adopted saccharide to process, then pulled an oar；
(2) introduce step during amorphous alumina plastic（1）The activated carbon serosity obtaining；
(3) step（2）Material after the plastic obtaining carries out aging, after hydrothermal treatment, refilters, washs, being dried, obtaining
To catalyst carrier material；
(4) by step（3）The catalyst carrier material of gained makes catalyst carrier.
In the present invention, step（4）At least adopt one of following methods：
A, by step（3）The carrier material of gained, roasting under inert gas shielding, obtain catalyst carrier；
B, by step（3）The carrier material molding of gained, after drying, roasting under inert gas shielding, it is catalyzed
Agent carrier；
C, by step（3）The roasting under inert gas shielding of the carrier material of gained, then again through molding, after being dried,
Roasting under inert gas shielding, obtains catalyst carrier.
The catalytic wet oxidation catalyst carrier of the present invention, with the activated carbon of 150 mesh ~ 300 mesh as core, with amorphous
Aluminum is shell, and wherein activated carbon accounts for the 10% ~ 70% of vehicle weight, preferably 30% ~ 70%, aluminium oxide accounts for the 30% ~ 90% of vehicle weight,
It is preferably 30% ~ 70%.
The catalyst carrier of the present invention can be to be not required to powdered catalytic agent carrier or the preformed catalyst of molding
Carrier.The granularity of powdered catalytic agent carrier is generally 0.05 ~ 0.2mm.Preformed catalyst carrier can determine grain as needed
The size of degree, generally 0.5 ~ 8.0mm.
The property of shaping of catalyst carrier of the present invention is as follows：Specific surface area is 200 ~ 1000m2/ g, pore volume be 0.5 ~
2.0cm3/ g, rate of wear<3wt%, side pressure strength is 100 ~ 300N/cm.
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 saccharide to process, and is then pulled an oar.Described saccharide is single
One of sugar, disaccharidase, polysaccharide or multiple, the preferably saccharide for 3 ~ 20 for the carbon number, for example：Triose, tetrose, pentose, oneself
One or more of one or more of sugar, maltose, sucrose, more preferably glucose, sucrose.Described saccharide consumption
Account for the 2% ~ 50% of activated carbon weight, preferably 5% ~ 20%.Saccharide is processed activated carbon and directly can be mixed saccharide with activated carbon,
Saccharide can be dissolved in solvent and add activated carbon, solvent therein is water, low-carbon alcohols（I.e. carbon number is 1 ~ 5 unitary
Alcohol）One or more of.When saccharide processes activated carbon, its liquid consolidates volume ratio below 10, preferably 1 ~ 5.Saccharide is processed lives
Property charcoal after, excessive liquid phase is preferably filtered to remove, and is then pulled an oar again.Making beating can be carried out using conventional method, general employing
Add water, one or more of low-carbon alcohols are pulled an oar, one of monohydric alcohol that wherein low-carbon alcohols are 1 ~ 5 for carbon number or
Multiple.
Step of the present invention（2）Described in the plastic process of amorphous alumina can be by well known to those skilled in the art
Process is carried out.The plastic process of amorphous alumina is usually the neutralization reaction process of acid material and alkaline material.Plastic mistake
Journey can be 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, aluminium oxide plastic is to be entered with acidic precipitation agent or alkaline precipitating agent using aluminum soluble salt
The process of row neutralization reaction, aluminum soluble salt wherein used is one or more of aluminum chloride, aluminum sulfate, aluminum nitrate, institute
Acidic precipitation agent is usually one of hydrochloric acid, sulphuric acid, nitric acid, oxalic acid, carbon dioxide etc. or several, used alkalescence
Precipitant is usually one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia etc. or several.Aluminium oxide becomes
Glue can also adopt meta-aluminate（Such as sodium metaaluminate and/or potassium metaaluminate）With acid aluminium salt（Such as aluminum chloride, aluminum nitrate,
One or more of aluminum sulfate）The method being 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.Step（3）Described is aging, and condition is as follows：PH is 6.0
~ 10.0, preferably 7.0 ~ 9.5, ageing time 0.25 ~ 8 hour, relatively it is suitable at 0.5 ~ 5 hour, preferably 1 ~ 3 hour, aging temperature
Spend for room temperature ~ 85 DEG C, preferably 40 ~ 80 DEG C.Temperature when aging and pH are preferably identical with temperature during neutralization and pH.
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 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.
Step of the present invention（3）In, before hydrothermal treatment consists, preferably through filtering or heating concentration, remove excessive moisture
And soluble species.It is heating stepses at 90 ~ 110 DEG C that wherein said heating concentrates（2）Products obtained therefrom, preferable temperature is
95 ~ 105 DEG C, preferably 98 ~ 100 DEG C, it is heated to immobilising paste shape.
Step of the present invention（3）In, described hydrothermal treatment consists are carried out in hermetic container, and the temperature of hydrothermal treatment consists is 90 ~ 300
DEG C, preferably 100 ~ 250 DEG C, preferably 150 ~ 210 DEG C, described hydrothermal treatment consists be in material treatment temperature produced from
Carry out under the pressure condition of body.Described hydrothermal conditions are 0.5 ~ 48h, preferably for 1 ~ 36h, preferably 2 ~ 24h.
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.
Step of the present invention（4）In, 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.
Step of the present invention（4）In, the molding described in method B and method C can be carried out as needed, generally strip, circle
Column, spherical, irregular strip, special-shaped ball etc., granularity can determine as needed, generally 0.5 ~ 8.0mm.Described forming process
In, shaping assistant such as one or more of the acid of binding agent, peptization, extrusion aid etc. can be added as needed.
Step of the present invention（4）In, the drying condition described in method B is generally at 80 ~ 200 DEG C, is dried 1 ~ 15 hour, roasting
Generally 450 ~ 700 DEG C of temperature, roasting time generally 1 ~ 10 hour.
Step of the present invention（4）In, in method C, by step（3）The roasting under inert gas shielding of the carrier material of gained,
Described roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.Then again through molding, it is dried
Afterwards, roasting under inert gas shielding, obtains catalyst carrier, and the drying condition after molding is as follows：At 80 ~ 200 DEG C, dry 1 ~
15 hours, roasting condition was as follows：Generally 450 ~ 700 DEG C of sintering temperature, roasting time generally 1 ~ 10 hour.
In the present invention, carry out roasting under inert gas shielding, selected noble gases are generally nitrogen or argon.
In the preparation process of catalyst carrier of the present invention, pull an oar again after processing activated carbon in particular by saccharide, then
Introduce during the plastic of amorphous alumina, saccharide uniformly adsorbs on the surfaces externally and internally of activated carbon, by follow-up
Roasting process makes to be mixed in the carbohydrate breakdown carbonization in the middle of aluminium oxide and activated carbon, and the new activated carbon being formed connects aluminium oxide and work
Property charcoal so that the combination of activated carbon and aluminium oxide is even closer, saccharide on the activated carbon inner surface new activity through being decomposed to form
Charcoal modifies the inner surface of former activated carbon, increased the adsorption activity position of activated carbon inner surface.Therefore, saccharide processes activated carbon, can
To promote aluminium oxide closely to wrap up activated carbon, be conducive to improving mechanical strength and the abrasion resisting performance of catalyst, and carry
The high utilization rate of the inner surface of activated carbon, is conducive to improving activity and the stability of catalyst.In use, reactant
Kind not tolerant first pass through shell and enter back into stratum nucleare, the insoluble float in reactant is first adsorbed and is deposited in shell, hydro-thermal
Process the mesopore contributing to aluminium oxide formation rule, be favorably improved the appearance dirt ability of shell aluminium oxide, so that catalyst is had more
High reactivity and stability in use, improve the service life of catalyst.
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 radius
1.1nm, iodine sorption value 700mg/g, granularity 200 mesh.
Embodiment 1
Solid aluminum chloride is added in distilled water, heats simultaneously and stir to dissolving, obtain solution (a).By strong aqua ammonia
Appropriate distilled water diluting is added to become about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in D/W, liquid
Gu volume ratio is 3：1, then add water making beating, obtains serosity (c).After adding (a) and be heated with stirring to 60 DEG C in plastic cans,
Open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, now add in tank
C (), continues Deca (b), control in 30 minutes and for system in tank to be added drop-wise to pH=8.0.Keeping temperature is 60 DEG C, and pH=8.0 is aging
1 hour, material in tank is dried to contents on dry basis 15wt% at 100 DEG C in baking oven, material is transferred in autoclave, 180
Process 4h under the conditions of DEG C, filtered, wash to no chloride ion, filter, filter cake is dried 10 hours at 110 DEG C, is urged
Agent carrier material A-1.Then roasting 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.
Take 100 grams of powder carrier J-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 Z-1, its property
It is shown in Table 2.
Embodiment 2
Solid aluminum sulfate is added in distilled water, heats simultaneously and stir to dissolving, obtain solution (a).By strong aqua ammonia
Appropriate distilled water diluting is added to become about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in D/W, liquid
Gu volume ratio is 3：1, then add water making beating, obtains activated carbon serosity (c).Take a plastic cans, add (a) in tank and be heated with stirring to
After 60 DEG C, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, open (c) and hold
The valve of device, continues Deca (b), controls in 30 minutes and for system in tank to be added drop-wise to 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, pH=8.0, aging 1 hour, by material filtering in tank to contents on dry basis
15wt%, material is transferred in autoclave, processes 4h, filtered, wash to sulfate radical-free ion, mistake under the conditions of 180 DEG C
Filter, filter cake is dried 10 hours at 110 DEG C, obtains catalyst carrier material A-2.Then under nitrogen protection in 550 DEG C of bars
Roasting 5 hours under part, pulverize and sieve and obtain powder carrier J-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 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 aqueous sucrose solution and mixes
Uniformly, the solid volume ratio of liquid is 3：1, then add water making beating, obtains serosity（c）.Take a plastic cans, insert the stirring of 2L deionized water and add
Heat adds serosity to after 60 DEG C（c）, open the valve of the container having (a), (b), the pH=8.0 of control system simultaneously, control
In 45 minutes, (a) is dripped off, close valve.Keeping temperature is 60 DEG C, pH=8.0, aging 1 hour, by material filtering in tank extremely
Contents on dry basis 15wt%, material is transferred in autoclave, processes 4h, filtered, wash to sulfate radical-free under the conditions of 180 DEG C
Ion, filters, and filter cake is dried 10 hours at 110 DEG C, obtains catalyst carrier material A-3.Then exist under nitrogen protection
Roasting 5 hours under the conditions of 550 DEG C, pulverize and sieve and obtain powder carrier J-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 simultaneously and stir to dissolving, obtain solution (a).By strong aqua ammonia
Appropriate distilled water diluting is added to become about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in D/W, liquid
Gu volume ratio is 3：1, then add water making beating, obtains activated carbon serosity (c).Add (a) and be heated with stirring to 60 DEG C in plastic cans
Afterwards, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, now add in tank
Enter (c), continue Deca (b), control in 30 minutes and system in tank is added drop-wise to pH=8.0.Keeping temperature is 60 DEG C, pH=8.0, always
Change 1 hour, material in tank be dried to contents on dry basis 15wt% at 100 DEG C in baking oven, material is transferred in autoclave,
Process 4h under the conditions of 180 DEG C, filtered, wash to no chloride ion, filter, filter cake is dried 10 hours at 110 DEG C, obtains
Catalyst carrier material A-4.Then roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, pulverize and sieve and obtain powder and carry
Body J-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 simultaneously and stir to dissolving, obtain solution (a).By strong aqua ammonia
Appropriate distilled water diluting is added to become about 10wt% weak ammonia (b).Powdery coconut husk charcoal adds mix homogeneously in D/W, liquid
Gu volume ratio is 3：1, then add water making beating, obtains activated carbon serosity (c).Take a plastic cans, add (a) in tank and be heated with stirring to
After 60 DEG C, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, open (c) and hold
The valve of device, continues Deca (b), controls in 30 minutes and for system in tank to be added drop-wise to pH=8.0, controls the valve of the container of (c),
Ensure now to be added dropwise to complete.Keeping temperature be 60 DEG C, pH=8.0, aging 1 hour, by material in tank at 100 DEG C in baking oven
It is dried to contents on dry basis 15wt%, material is transferred in autoclave, process 4h under the conditions of 180 DEG C, filtered, wash to no
Sulfate ion, filters, and filter cake is dried 10 hours at 110 DEG C, obtains catalyst carrier material A-5.Then protect in nitrogen
Under shield under the conditions of 550 DEG C roasting 5 hours, pulverize and sieve and obtain powder carrier J-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 simultaneously and stir to dissolving, obtain solution (a).By strong aqua ammonia
Appropriate distilled water diluting is added to become about 10wt% weak ammonia (b).Take a plastic cans, add (a) in tank and be heated with stirring to 60 DEG C
Afterwards, open the valve of the container having (b), control in 30 minutes and system in tank is added drop-wise to pH=8.0.Keeping temperature is 60 DEG C,
PH=8.0, aging 1 hour, material in tank is filtered, and washs to sulfate radical-free ion, filters, and filter cake is dry at 110 DEG C
Dry 10 hours, obtain carrier 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, obtain catalyst carrier DZ-A, its appearance white, its property
Matter is shown in Table 2.Then impregnated with the impregnation liquid containing Ce-Cu, be then dried 10 hours at 110 DEG C, roasting 5 under the conditions of 550 DEG C
Hour, obtain catalyst DA, its composition is shown in Table 3.
Comparative example 2
Activated carbon 100g used in embodiment 2 is contacted with the peptization liquid containing nitric acid and forms paste, extruded moulding, so
It is dried 10 hours at 110 DEG C afterwards, 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 alumina content is 50wt%, its outward appearance black.Then adopt
Impregnate active metal component with the method for embodiment 2, obtain catalyst DC.
Comparative example 4
Repeat the synthesis of embodiment 2, do not carry out hydrothermal treatment consists, prepared comparative catalyst's carrier material during plastic
PA-2 and powder carrier DF-2.
The preparation of preformed catalyst carrier and catalyst, with embodiment 2, obtains catalyst carrier DZ-D and catalyst DD, its
Composition is shown in Table 2.
Comparative example 5
Repeat the synthesis of embodiment 2, without saccharide during plastic, and do not carry out at hydro-thermal during plastic
Reason, prepared catalyst carrier material PA-3 and powder carrier DF-3.
Preformed catalyst carrier is prepared with embodiment 2, obtains catalyst carrier DZ-E.Active metal and carrying method are with real
Apply example 2, obtain catalyst DE, its composition is shown in Table 3.
Table 1 plastic reagent 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 the catalyst carrier obtaining after activated carbon is processed using saccharide
Compared with the catalyst carrier obtaining without saccharide, bulk property is improved.
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 oxygen
Change aluminum 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
Can be seen that from table 5 estimation of stability result, using the catalyst of this method preparation, there is more excellent stablizing
Property.
Claims (17)
1. a kind of preparation method of catalytic wet oxidation catalyst carrier, including：
(1) 150 mesh ~ 300 mesh activated carbons are adopted saccharide to process, then pulled an oar；
(2) introduce step during amorphous alumina plastic（1）The activated carbon serosity obtaining；
(3) step（2）Material after the plastic obtaining carries out aging, after hydrothermal treatment, refilters, washs, being dried, being urged
Agent carrier material；
(4) by step（3）The catalyst carrier material of gained makes catalyst carrier；
Wherein, step（1）Described saccharide is 3 ~ 20 saccharide for carbon number, saccharide process activated carbon be by saccharide directly with
Activated carbon mixes, or saccharide is dissolved in solvent adds activated carbon, and solvent therein is water or carbon number is the one of 1 ~ 5
One or more of first alcohol.
2. in accordance with the method for claim 1 it is characterised in that：Step（4）Catalyst carrier material is made catalyst carry
Body at least adopt one of following methods：
A, by step（3）The carrier material of gained, roasting under inert gas shielding, obtain catalyst carrier；
B, by step（3）The carrier material molding of gained, after drying, roasting under inert gas shielding, obtain catalyst and carry
Body；
C, by step（3）The roasting under inert gas shielding of the carrier material of gained, then again through molding, after being dried, in inertia
Roasting under gas shield, obtains catalyst carrier.
3. in accordance with the method for claim 1 it is characterised in that described catalyst carrier, with the activity of 150 mesh ~ 300 mesh
Charcoal be core, with amorphous alumina as shell, wherein activated carbon accounts for the 10% ~ 70% of vehicle weight, and aluminium oxide accounts for the 30% of vehicle weight
~90%.
4. 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.
5. in accordance with the method for claim 1 it is characterised in that described catalyst carrier or powder catalyst carry
Body, or preformed catalyst carrier, the granularity of powdered catalytic agent carrier is 0.05 ~ 0.2mm, preformed catalyst carrier granularity
For 0.5 ~ 8.0mm.
6. in accordance with the method for claim 1 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.
7. in accordance with the method for claim 1 it is characterised in that step（1）Described activated carbon making beating is using adding water or low-carbon (LC)
One or more of alcohol is pulled an oar, one or more of monohydric alcohol that wherein low-carbon alcohols are 1 ~ 5 for carbon number.
8. in accordance with the method for claim 1 it is characterised in that described saccharide consumption accounts for the 2% ~ 50% of activated carbon weight.
9. in accordance with the method for claim 1 it is characterised in that described saccharide consumption accounts for the 5% ~ 20% of activated carbon weight.
10. in accordance with the method for claim 1 it is characterised in that described saccharide is triose, tetrose, pentose, hexose, Fructus Hordei Germinatus
One or more of sugar, sucrose.
11. in accordance with the method for claim 1 it is characterised in that：When saccharide processes activated carbon, the solid volume ratio of liquid 10 with
Under.
12. in accordance with the method for claim 1 it is characterised in that：Step（2）Described in amorphous alumina plastic mistake
Journey is the neutralization reaction process of acid material and alkaline material, plastic process by the way of the continuous acid-base titration of soda acid, or
By the way of two kinds of material cocurrent neutralizations.
13. in accordance with the method for claim 1 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 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 neutralization plastic.
14. in accordance with the method for claim 1 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.
15. in accordance with the method for claim 1 it is characterised in that step（3）In, before hydrothermal treatment consists, through filtering or heating
Concentrate；Described heating concentrates and is heated to immobilising paste shape, and it is in step that described heating concentrates（2）Products obtained therefrom is aging
After the completion of, then heat at 90 ~ 110 DEG C.
16. in accordance with the method for claim 1 it is characterised in that step（3）In, described hydrothermal treatment consists are in hermetic container
Carry out, the temperature of hydrothermal treatment consists is 90 ~ 300 DEG C, described hydrothermal treatment consists be in material treatment temperature produced itself
Pressure condition under carry out, described hydrothermal conditions are 0.5 ~ 48h.
17. in accordance with the method for claim 2 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 the 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
Roasting under inert gas shielding, described roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is little for 1 ~ 10
When, then again through molding, after being dried, roasting under inert gas shielding, obtain catalyst carrier, the drying condition after molding is such as
Under：At 80 ~ 200 DEG C, it is dried 1 ~ 15 hour, roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is little for 1 ~ 10
When.
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