CN104667933B - Method for preparing wet oxidation catalyst - Google Patents
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- CN104667933B CN104667933B CN201310620830.XA CN201310620830A CN104667933B CN 104667933 B CN104667933 B CN 104667933B CN 201310620830 A CN201310620830 A CN 201310620830A CN 104667933 B CN104667933 B CN 104667933B
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Abstract
The invention discloses a method for preparing a catalytic wet oxidation catalyst. The catalyst comprises a carrier and an active metal ingredient loaded on the carrier, wherein the active metal ingredient comprises transitional metal and rare-earth metal; the carrier uses activated carbon as a core and amorphous silica-alumina as a shell. The preparation method comprises the following steps: introducing saccharide treated activated carbon slurry in the process of gelling amorphous silica-alumina, aging after gelling, and carrying out hydrothermal treatment; filtering, washing and drying to obtain a carrier material; preparing the carrier from the carrier material, and loading the active metal ingredient. 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 preparation method of catalytic wet oxidation catalyst, particularly contain activated carbon and amorphous silica-alumina
Catalytic wet oxidation catalyst preparation method.
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 be mainly with activated carbon, molecular sieve, aluminium oxide, titanium dioxide etc. as carrier, with alkali metal,
One or more of alkaline-earth metal, transition metal or Pt, Pd noble metal make the catalyst of active component composition.Activated carbon is
The black being made up of carbonaceous material, hole are flourishing, specific surface area is big, a class microcrystalline carbon of high adsorption capacity.Activated carbon property
Stable, acidproof, alkaline-resisting, heat-resisting, water insoluble or organic solvent, easily regenerate, be a kind of environmentally friendly adsorbent, extensively apply
In fields such as Industrial " three Waste " improvement, food, medicine, carrier, quasiconductor, battery and power storage.Currently used for wastewater treatment
Heterogeneous solid catalyst mostly select activated carbon as carrier, but select merely the catalyst of activated carbon supported metal preparation
Anti-wear performance is poor, and mechanical strength is not high, and the metal of load is easy to run off so that the application effect of activated-carbon catalyst is made a discount.
, because having good chemical stability, pore volume is big for amorphous silica-alumina, has stronger acidity, pore size distribution$ is concentrated, machinery is strong
The advantages of degree is big, corrosion-resistant, is widely used in catalytic field, but amorphous silica-alumina haves the shortcomings that specific surface is little,
Select merely the catalytic mechanical intensity height of amorphous silica-alumina preparation, pore size distribution is more concentrated, and pore volume is big, but specific surface is little,
Absorption and conversion capability to Organic substance are relatively weak.
CN201110225789.7 discloses a kind of method preparing benzene adsorption material using discarded activated alumina, and it is
After cleaned for waste activated alumina, filtration, being dried, a kind of activated alumina/work is prepared using cryogenic seal heat treatment mode
Property carbon composite, has good adsorption effect to benzene.The method is by the organic matter carbonizing within aluminium oxide, activated carbon master
In the duct of aluminium oxide to be distributed in, so not only can block the duct of aluminium oxide, and the activated carbon so being generated is in oxygen
Change skewness in aluminum.
CN201110255525.6 discloses a kind of preparation method of active alumina/active carbon composite material, is by aluminum
Section bar factory industrial sludge, activated carbon, binding agent through mixing, pelletize, old, molding, dry, sinter, rinsing, drying and other steps
Make active alumina/active carbon composite material.The method belongs to salic species and activated carbon physical mixing processes,
Aluminium oxide and activated carbon dispersion are uneven；And the mud impurity content that used is high, the Properties of Alumina of gained 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 one kind has, catalytic performance is good, anti-wear performance is strong, using steady
The preparation method of qualitative good catalytic wet oxidation catalyst.
The preparation process of catalytic wet oxidation catalyst of the present invention, this catalyst is with transition metal and rare earth metal as activity
Metal component, wherein transition metal are the base metal in the 4th and 5 cycles in the periodic table of elements, and carrier is with the work of 150 mesh ~ 300 mesh
Property charcoal be core, with amorphous silica-alumina as shell, preparation process includes：
(1) 150 mesh ~ 300 mesh activated carbons are adopted saccharide to process, 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 carries out aging, after hydrothermal treatment, refilters, washs, being dried, obtaining
To carrier material；
(4) by step（3）The carrier material of gained makes catalyst carrier, preferably at least adopts 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；
(5) step（4）Impregnate active metal component in the catalyst carrier of gained, be then dried, in inert gas shielding
Lower roasting, obtains catalytic wet oxidation catalyst.
The catalytic wet oxidation catalyst of the present invention, including carrier and the active metal component that is supported on carrier, wherein
With transition metal and rare earth metal as active metal component, wherein transition metal is the non-noble in the 4th and 5 cycles in the periodic table of elements
Metal, carrier is that wherein activated carbon accounts for vehicle weight as core, with amorphous silica-alumina as shell with the activated carbon of 150 mesh ~ 300 mesh
10% ~ 70%, preferably 30% ~ 70%, amorphous silica-alumina accounts for the 30% ~ 90% of vehicle weight, and preferably 30% ~ 70%.
In catalyst of the present invention, described transition metal is selected from one or more of vanadium, chromium, manganese, ferrum, cobalt, copper and titanium.
In catalyst of the present invention, with transition metal and rare earth metal as active metal component, with the weight of catalyst as base
Standard, the content of transition metal oxide is 1% ~ 15%, and the content of rare-earth oxide is 1% ~ 15%.
In catalyst of the present invention, described rare earth metal is one or more of lanthanum, cerium.
The catalyst of the present invention can be powder catalyst or the preformed catalyst being not required to molding.Powder
The granularity of catalyst is generally 0.05 ~ 0.2mm.Preformed catalyst can determine the size of granularity as needed, generally 0.5 ~
8.0mm.
The property of preformed catalyst of the present invention is as follows：Specific surface area is 200 ~ 1000m2/ g, pore volume is 0.3 ~ 1.8cm3/
G, rate<3wt%, side pressure strength is 100 ~ 250N/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）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, 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.
Step of the present invention（5）In, carrier impregnation active metal component can be sprayed or saturation dipping, also may be used
To be supersaturation dipping.
Step of the present invention（5）In, after catalyst dipping, drying condition is generally at 80 ~ 200 DEG C, is dried 1 ~ 15 hour, roasting
Burn generally 450 ~ 700 DEG C of temperature, roasting time generally 1 ~ 10 hour.
Step of the present invention（5）In, during carrier impregnation active metal component, generally carried out using the impregnation liquid containing active metal
Dipping.Impregnation liquid adopts conventional method to prepare, will transition metal（As vanadium, chromium, manganese, ferrum, cobalt, copper and titanium）, rare earth metal（As
Lanthanum, cerium）Predecessor on metal is dissolved in solvent and is formulated.
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 silica-alumina, saccharide uniformly adsorbs on the surfaces externally and internally of activated carbon, by follow-up roasting
Burning process makes to be mixed in the carbohydrate breakdown carbonization in the middle of amorphous silica-alumina and activated carbon, and the new activated carbon being formed connects amorphous silicon
, so that the combination of activated carbon and amorphous silica-alumina is even closer, the saccharide on activated carbon inner surface is through decomposing shape for aluminum and activated carbon
The inner surface of the former activated carbon of new Activated Carbon Modification becoming, increased the adsorption activity position of activated carbon inner surface.Therefore, saccharide is processed
Activated carbon, can promote amorphous silica-alumina closely to wrap up activated carbon, be conducive to improving the mechanical strength of catalyst and resist
Wear hardness, and improve the utilization rate of the inner surface of activated carbon, be conducive to improving activity and the stability of catalyst.Using
During, the insoluble matter of reaction species first passes through shell and enters back into stratum nucleare, and the insoluble float in reactant first adsorbs deposition
In shell, hydrothermal treatment consists contribute to the mesopore of amorphous silica-alumina formation rule, are favorably improved the appearance of shell amorphous silica-alumina
Dirty ability, makes catalyst have higher reactivity and stability in use, improves the service life of catalyst.
Catalyst 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 and catalyst grain size adopt laser particle size analyzer to measure；Shaping carrier and catalysis
Agent granularity is recorded using 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 D/W, 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 dried to contents on dry basis at 100 DEG C in baking oven
15wt%, material is transferred in autoclave, processes 4h, filtered under the conditions of 180 DEG C, washs to no chloride ion, filters, will
Filter cake is dried 10 hours at 110 DEG C, obtains carrier material A-1, then roasting 5 is little under the conditions of 550 DEG C under nitrogen protection
When, 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, with the impregnation liquid dipping containing Ce-Cu, so
Afterwards 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 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 D/W, 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 50wt% and added in 10 minutes.Aging 1 hour, material is shifted by material filtering in tank to contents on dry basis 15wt%
To in autoclave, process 4h under the conditions of 180 DEG C, filtered, wash to sulfate radical-free ion, filter, by filter cake at 110 DEG C
It is dried 10 hours, obtains carrier material A-2, then roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, pulverize and sieve
To 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, with the impregnation liquid dipping containing Ce-Cu, then
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 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 aqueous sucrose solution
Middle mix homogeneously, the solid volume ratio of liquid is 3：1, then add water making beating, obtains serosity（c）.Take a plastic cans, insert 2L deionized water
Serosity (c) is added 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 is transferred in autoclave by material filtering in tank to contents on dry basis 15wt%,
Process 4h under the conditions of 180 DEG C, filtered, wash to sulfate radical-free ion, filter, filter cake is dried 10 hours at 110 DEG C,
Obtain carrier material A-3, then roasting 5 hours under the conditions of 550 DEG C under nitrogen protection, 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, with the impregnation liquid dipping containing Ce-Fe, then
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 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 D/W, 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 dried to contents on dry basis at 100 DEG C in baking oven
15wt%, material is transferred in autoclave, processes 4h, filtered under the conditions of 180 DEG C, washs to no chloride ion, filters, will
Filter cake is dried 10 hours at 110 DEG C, obtains carrier material A-4, then roasting 5 is little under the conditions of 550 DEG C under nitrogen protection
When, pulverize and sieve and obtain powder carrier J-4.The amount of plastic agents useful for same is listed in table 1.
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, with the impregnation liquid dipping containing Ce-Mn, then
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 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 D/W, 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 dried to contents on dry basis at 100 DEG C in baking oven
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 carrier material A-5, then roasts under the conditions of 550 DEG C under nitrogen protection
Burn 5 hours, pulverize and sieve and obtain powder carrier J-5.The amount of plastic agents useful for same is listed in table 1.
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, with the impregnation liquid dipping containing La-Cu, then
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 saccharide during plastic, prepared comparative catalyst's carrier material
Material carrier material PA-1 and powder carrier DF-1, its appearance white.
The preparation of preformed catalyst carrier and catalyst, with embodiment 2, obtains catalyst carrier DZ-A and catalyst DA.
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 50 wt %, the content of amorphous silica-alumina is 50 wt %, and its outward appearance is black
Color.Then the method adopting embodiment 2 impregnates active metal component, obtains 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 agents useful for same quality
The composition of table 2 catalyst and property
Be can be seen that by catalyst property in table 2 and the catalyst obtaining after activated carbon is processed and without sugar using saccharide
The catalyst that class obtains is compared, and 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 no
Amorphous silicon-alumina dry glue is shell.
The invention described above catalyst and its comparative catalyst are 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 3 using the result of handled waste water after 4 times.
Table 3 evaluation result
The waste water that can be seen that after treatment from table 3 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 4.
Table 4 estimation of stability result
Can be seen that from table 4 estimation of stability result, using the catalyst of this method preparation, there is more excellent stablizing
Property.
Claims (20)
1. a kind of preparation method of catalytic wet oxidation catalyst, this catalyst is with transition metal and rare earth metal as active metal
Component, wherein transition metal are the base metal in the 4th and 5 cycles in the periodic table of elements, and carrier is with the activated carbon of 150 mesh ~ 300 mesh
For core, with amorphous silica-alumina as shell, preparation process includes：
(1) 150 mesh ~ 300 mesh activated carbons are adopted saccharide to process, 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 carries out aging, after hydrothermal treatment, refilters, washs, being dried, being carried
Body material；
(4) by step（3）The carrier material of gained makes catalyst carrier；
(5) step（4）Impregnate active metal component in the catalyst carrier of gained, be then dried, roast under inert gas shielding
Burn, obtain catalytic wet oxidation catalyst；
Wherein, step（1）It is directly to mix saccharide with activated carbon that saccharide processes activated carbon, or saccharide is dissolved in solvent again
Add activated carbon, solvent therein is water, carbon number is one or more of 1 ~ 5 monohydric alcohol；Step（1）Described sugar
Class is 3 ~ 20 saccharide for carbon number.
2. in accordance with the method for claim 1 it is characterised in that：Step（4）The preparation of catalyst carrier at least adopts following
One of method：
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 in described catalyst, activated carbon account for vehicle weight 10% ~
70%, amorphous silica-alumina accounts for the 30% ~ 90% of vehicle weight.
4. in accordance with the method for claim 1 it is characterised in that described transition metal be selected from vanadium, chromium, manganese, ferrum, cobalt, copper and
One or more of titanium；Described rare earth metal is one or more of lanthanum, cerium.
5. in accordance with the method for claim 1 it is characterised in that in described catalyst, activated carbon account for vehicle weight 30% ~
70%, amorphous silica-alumina accounts for the 30% ~ 70% of vehicle weight.
6. 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 transition metal oxide is 1% ~ 15%, and the content of rare-earth oxide is 1% ~ 15%.
7. 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.
8. 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.
9. in accordance with the method for claim 1 it is characterised in that step（1）Described activated carbon making beating is using adding water, 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.
10. in accordance with the method for claim 1 it is characterised in that step（1）Described saccharide consumption accounts for activated carbon weight
2%~50%.
11. in accordance with the method for claim 1 it is characterised in that step（1）Described saccharide consumption accounts for activated carbon weight
5%~20%.
12. in accordance with the method for claim 1 it is characterised in that step（1）Described saccharide be triose, tetrose, pentose, oneself
One or more of sugar, maltose, sucrose.
13. 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.
14. in accordance with the method for claim 1 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.
15. 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 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.
16. 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.
17. 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.
18. 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.
19. 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.
20. in accordance with the method for claim 1 it is characterised in that：Step（5）In, drying condition is at 80 ~ 200 DEG C, is dried
1 ~ 15 hour, sintering temperature condition was 450 ~ 700 DEG C of roastings 1 ~ 10 hour.
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| CN109603833A (en) * | 2018-12-12 | 2019-04-12 | 佛山科学技术学院 | A kind of composite catalyst for dye wastewater treatment |
| CN115920873B (en) * | 2022-10-31 | 2024-10-08 | 中国科学院福建物质结构研究所 | Preparation method and application of saccharide-modified active carbon carrier and catalyst |
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