CN104667986B - Method for preparing catalytic wet oxidation catalyst carrier - Google Patents
Method for preparing catalytic wet oxidation catalyst carrier Download PDFInfo
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- CN104667986B CN104667986B CN201310620827.8A CN201310620827A CN104667986B CN 104667986 B CN104667986 B CN 104667986B CN 201310620827 A CN201310620827 A CN 201310620827A CN 104667986 B CN104667986 B CN 104667986B
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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 alumina as a shell. The preparation method comprises the following steps: introducing slurry of amino acid treated activated carbon into the process of gelling amorphous-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 containing activated carbon and amorphous
The preparation method of the catalytic wet oxidation catalyst carrier of aluminum oxide.
Background technology
With increasingly strict, the Con trolling index requirement more and more higher of sewage qualified discharge of global environmental regulation, here
Under form, waste water treatment by catalytic oxidation has increasingly obtained the attention and 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, it is to obtain preferably to locate
Reason effect and by reducing reaction temperature, reaction pressure to keep relatively low wastewater treatment expense, prepare with high-activity component,
High intensity, the cheap catalyst of high stability undoubtedly become the key of waste water catalytic oxidation technologies application.
The catalyst of waste water catalysis oxidation is broadly divided into two class of homogeneous catalyst and heterogeneous solid catalyst.
Homogeneous catalyst mainly includes producing Fenton reagent, the Fe of oxygen radical3+、Cu2+, the metal such as cobalt and manganese
Ion, by means of the effect of these homogeneous catalysts, organic component, sulfide, ammonia nitrogen in waste water etc. by air, oxygen, smelly
The oxide isolations such as oxygen, hydrogen peroxide are oxidized into low molecular acid (low mass molecule alcohol or carbon dioxide), sulfate or thiosulfuric acid
Salt, nitrogen etc., make waste water reach the processing intent of decarburization, desulfurization and denitrogenation.Homogeneous oxidation catalyst prepare and using process compared with
For simple, typically directly the aqueous solution can be made into from slaines such as iron, 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, as 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
The row serious problems such as costly, metal loss and secondary pollution, cause its application to be limited by larger.
Heterogeneous solid catalyst is mainly with activated carbon, molecular sieve, amorphous alumina, titanium dioxide etc. as carrier, with
One or more in alkali metal, alkaline-earth metal, transition metal or Pt, Pd noble metal make the catalyst of active component composition.It is living
Property charcoal be that black, hole by made by carbonaceous material is flourishing, specific surface area is big, a class microcrystalline carbon of high adsorption capacity.Activity
Charcoal is stable in properties, acidproof, alkaline-resisting, heat-resisting, water insoluble or organic solvent, easily regenerates, is a kind of environmentally friendly adsorbent, extensively
It is general to be applied to the fields such as Industrial " three Waste " improvement, food, medicine, carrier, semiconductor, battery and power storage.Currently used for useless
The heterogeneous solid catalyst of water process selects activated carbon mostly as carrier, but from catalysis prepared by activated carbon supported metal
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, with certain acidity, pore size distribution$ concentration, machine
Tool intensity is big, it is corrosion-resistant the advantages of, be widely used in catalytic field, but amorphous alumina to there is specific surface little
Shortcoming, the absorption and conversion capability to organic matter are relatively small.
CN201110225789.7 discloses a kind of side for preparing benzene adsorption material using discarded active amorphous aluminum oxide
Method, it be will it is useless active amorphous aluminum oxide cleaned, filter, be dried after, prepared using cryogenic seal heat treatment mode a kind of
Active amorphous aluminum oxide/absorbent charcoal composite material, has good adsorption effect to benzene.The method is by amorphous alumina
Internal organic matter carbonizing, activated carbon are mainly distributed in the duct of amorphous alumina, so can not only block aluminum oxide
Duct, and the activated carbon for so being generated skewness in aluminum oxide.
CN201110255525.6 discloses a kind of preparation method of active amorphous aluminum oxide/absorbent charcoal composite material,
Be by waste aluminum sludge, activated carbon, binding agent through mixing, granulation, it is old, be molded, dry, sintering, rinsing, be dried
Active amorphous aluminum oxide/absorbent charcoal composite material is made etc. step.The method belongs to salic species and activated carbon thing
Reason mixed process, aluminum oxide and activated carbon disperse uneven；And the sludge impurity content height for being used, the amorphous of gained
Aluminium property is 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
Aluminium, activated carbon and binding agent be raw material, Jing mix, granulation, it is old, be molded, dry, sintering, rinsing, drying and other steps, so
The composite for obtaining is still the physical mixture of aluminum oxide and activated carbon, aluminum oxide and activated carbon uneven, its synthesis of dispersion
Performance also needs further to improve.
The 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.
There is good catalytic performance using catalyst made by the catalyst carrier, and anti-wear performance is strong, stability in use is good.
The preparation process of catalytic wet oxidation catalyst carrier of the present invention, including：
(1) 150 mesh ~ 300 mesh activated carbons are adopted into amino acid treatment, is then beaten；
(2) step is introduced during amorphous alumina plastic（1）The activated carbon slurries for obtaining；
(3) step（2）Material after the plastic for obtaining carries out aging, after hydro-thermal process, refilters, washs, being dried；
(4) by step（3）The catalyst carrier material of gained makes catalyst carrier.
In the present invention, step（4）Catalyst carrier material is made into catalyst carrier at least using one of following methods：
A, by step（3）The carrier material of gained, the roasting under inert gas shielding obtain catalyst carrier；
B, by step（3）The carrier material shaping of gained, after drying, the roasting under inert gas shielding is catalyzed
Agent carrier；
C, by step（3）Carrier material roasting under inert gas shielding of gained, then Jing shapings again, after being dried,
Roasting under inert gas shielding, obtains catalyst carrier.
The catalytic wet oxidation catalyst carrier of the present invention, the activated carbon with 150 mesh ~ 300 mesh is as core, with amorphous
Aluminium is shell, and wherein activated carbon accounts for the 10% ~ 70% of vehicle weight, preferably 30% ~ 70%, aluminum oxide accounts for the 30% ~ 90% of vehicle weight,
Preferably 30% ~ 70%.
The catalyst carrier of the present invention can be powdered catalytic agent carrier, or the preformed catalyst for being not required to be molded
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 are 100 ~ 300N/cm.
Step (1) of the present invention described activated carbon can select conventional Powdered Activated Carbon commodity, such as all kinds of wood activated charcoals, fruit
Shell activated carbon, active carbon from coal；Can also from wooden material, mineral material, plastics and discarded object, such as timber, wood chip, charcoal,
It is coconut husk, fruit stone, shell, coal, gangue, petroleum coke, asphalt, polyvinyl chloride, polypropylene, organic resin, damaged tire, surplus
The various activated carbon products that the Jing such as remaining sludge traditional preparation methods are obtained.Activated carbon used in the present invention is powder activated
Charcoal, 150 ~ 300 mesh of granularity, 500 ~ 3000m of specific surface area2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius.
In the inventive method, step（1）Described activated carbon beating is carried out using conventional method, it is general using adding water, it is low
One or more in carbon alcohol is beaten, and wherein low-carbon alcohols are that carbon number is one or more in 1 ~ 5 monohydric alcohol.
In the inventive method, step（1）Activated carbon first adopts amino acid treatment, is then beaten.Described amino acid
For hydrophilic amino acid, such as glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, bad ammonia
Acid, arginine, histidine, aspartic acid, one or more in glutamic acid, preferably hydrophily of the C numbers less than 20 long-chain
Amino acid.Such as aspartic acid, glutamic acid, lysine etc..Described amino acid consumption accounts for the 2% ~ 50% of activated carbon weight, preferably
For 5% ~ 20%.Amino acid directly can be mixed by amino acid treatment activated carbon with activated carbon, it is also possible to which amino acid is dissolved in solvent
In add activated carbon, solvent therein is water, low-carbon alcohols（I.e. carbon number is 1 ~ 5 monohydric alcohol）In one or more.
During amino acid treatment activated carbon, its liquid consolidates volume ratio below 10, preferably 1 ~ 5.After amino acid treatment activated carbon, excessive liquid
Mutually preferably it is filtered to remove, is then beaten again.Beating can be carried out using conventional method, general using adding water, in low-carbon alcohols
It is beaten for one or more, wherein low-carbon alcohols are that carbon number is one or more in 1 ~ 5 monohydric alcohol.
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 with by the way of 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, aluminum oxide plastic is 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 aluminium chloride, aluminum sulfate, one or more in aluminum nitrate, institute
Acidic precipitation agent is usually one or several in hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, carbon dioxide etc., alkalescence used
Precipitating reagent is usually one or several in sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor etc..Aluminum oxide into
Glue can also adopt meta-aluminate（Such as sodium metaaluminate and/or potassium metaaluminate）With acid aluminium salt（Such as aluminium chloride, aluminum nitrate,
One or more in aluminum sulfate）It is neutralized the method for plastic.Described plastic process is typically carried out at room temperature ~ 85 DEG C,
40 ~ 80 DEG C are suitably for relatively, preferably 50 ~ 70 DEG C.Described plastic process is typically carried out under certain pH value condition, typically
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 is relatively adapted at 0.5 ~ 5 hour, preferably 1 ~ 3 hour, aging temperature
Spend for room temperature ~ 85 DEG C, preferably 40 ~ 80 DEG C.Temperature and pH when aging is 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, the mixture is continuously added in plastic cans；（2）The mixture is charged first to
In plastic cans, in then preparing the acid material and alkaline material of amorphous alumina and plastic；（3）By the mixture with into
One or more mixing of glue material, then in plastic material and plastic.
Step of the present invention（3）In, before hydro-thermal process, best Jing filters or heats concentration, removes excessive moisture
And soluble species.Wherein described heating concentration is the heating stepses at 90 ~ 110 DEG C（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 hydro-thermal process is carried out in closed container, and the temperature of hydro-thermal process is 90 ~ 300
DEG C, preferably 100 ~ 250 DEG C, preferably 150 ~ 210 DEG C, described hydro-thermal process be in material treatment temperature it is produced from
Carry out under the pressure condition of body.Described hydrothermal conditions are 0.5 ~ 48h, are preferably 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 be selected
Add water when 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 the 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 should not contain in washing, after filtering or contain minimal amount of heteroion, heteroion includes
Na+、Cl-、SO4 2-、NO3 -、K+One or more in.
Step of the present invention（3）In, after washing, filtering, filter cake is dried described material, and drying mode can be adopted
Natural drying, oven drying, spray drying, microwave drying or infra-red drying, the general drying condition for adopting are 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 shaping roasting direct.Described in method A
Roasting condition it is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.
Step of the present invention（4）In, the shaping 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, one or more in shaping assistant such as adhesive, peptization acid, 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）Carrier material roasting under inert gas shielding of gained,
Described roasting condition is as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.Then Jing shapings again, are dried
Afterwards, the roasting under inert gas shielding, obtains catalyst carrier, and the drying condition after shaping 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, roasting is carried out under inert gas shielding, selected inert gas is generally nitrogen or argon gas.
In the preparation process of catalyst carrier of the present invention, it is the Ran Hou using being beaten after amino acid treatment activated carbon again
Introduce during the plastic of amorphous alumina, such amino acid uniformly adsorbs on the surfaces externally and internally of activated carbon, by rear
Continuous roasting process make to be mixed in aluminum oxide and activated carbon in the middle of amino acid decompose charing, the new activated carbon connection oxidation for being formed
Aluminium and activated carbon so that the combination of activated carbon and aluminum oxide is even closer, the amino acid Jing on activated carbon inner surface are decomposed to form
New Activated Carbon Modification original activated carbon inner surface, increased the adsorption activity position of activated carbon inner surface.Therefore, amino acid treatment
Activated carbon, can promote aluminum oxide closely to wrap up activated carbon, be conducive to improving mechanical strength and the abrasion resisting of catalyst
Performance, and the utilization rate of the inner surface of activated carbon is improve, be conducive to improving the activity of catalyst and stability.Using process
In, the not tolerant of reaction species first passes through shell and enters back into stratum nucleare, and the insoluble suspension in reactant first adsorbs and is deposited on shell
In layer, hydro-thermal process contributes to the mesopore of aluminum oxide formation rule, is favorably improved the appearance dirt ability of shell aluminum oxide, makes catalysis
Agent has higher reactivity and stability in use, improves the service life of catalyst.
Catalyst carrier preparation process of the present invention is simple, convenient, it is easy to operate, and is adapted to industrial production.
Specific embodiment
The specific surface area of product of the present invention and pore volume are determined using low temperature liquid nitrogen physisorphtion.Rate of wear is to adopt to turn
Cartridge type abrasion instrument is determined（It is specifically shown in《Catalyst carrier is prepared and application technology》（Petroleum industry publishing house, in May, 2002, Zhu Hong
Method is write, 4.5.4 sections）.Powder carrier granularity is determined using laser particle size analyzer；Shaping carrier and catalyst grain size are adopted
Measured with sieve method.In the present invention, wt% is mass fraction.
The preparation method of the present invention is further illustrated with reference to specific embodiment, but the scope of the present invention is not only
It is limited to the scope of these embodiments.
Commercially available powdery coconut husk charcoal specific surface area 928m used in the present invention2/ g, pore volume 1.0cm3/ g, average pore radius
1.1nm, iodine sorption value 700mg/g, 200 mesh of granularity.
Embodiment 1
Solid aluminum chloride is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is well mixed in adding glutamic acid aqueous solution, liquid
Gu volume ratio is 3：1, then add water beating, obtains slurries (c).After adding (a) in plastic cans and being heated with stirring to 60 DEG C,
Opening has the valve of the container of (b), and system in tank was added drop-wise to pH=4.0 within 10 minutes by control, was now added in tank
C (), continues (b) is added dropwise, system in tank was added drop-wise to pH=8.0 in 30 minutes by control.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
4h is processed under the conditions of DEG C, is filtered, wash to without chlorion, filter, filter cake is dried 10 hours at 110 DEG C, is carried
Body materials 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.Into
The amount of glue agents useful for same is listed in table 1.
100 grams of powder carrier J-1 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
Be dried 10 hours at 110 DEG C, under nitrogen protection, catalyst carrier Z-1 is obtained, its property after roasting 5 hours under the conditions of 550 DEG C
It is shown in Table 2.
Embodiment 2
Solid aluminum sulfate is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is well mixed in adding glutamic acid aqueous solution, liquid
Gu volume ratio is 3：1, then add water beating, obtains activated carbon slurries (c).A plastic cans is taken, (a) is added in tank and is heated with stirring to
After 60 DEG C, opening has the valve of the container of (b), and system in tank was added drop-wise to pH=4.0 within 10 minutes by control, is opened (c) and is held
The valve of device, continues (b) is added dropwise, and system in tank was added drop-wise to pH=8.0 in 30 minutes by control, controlled the valve of the container of (c),
Guarantee is now 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
Be dried to contents on dry basis 15wt%, material is transferred in autoclave, 4h is processed under the conditions of 180 DEG C, is filtered, washed to nothing
Sulfate ion, filters, and filter cake is dried 10 hours at 110 DEG C, carrier material A-2 is obtained, is then existed under nitrogen protection
Roasting 5 hours under the conditions of 550 DEG C, pulverize and sieve and obtain powder carrier J-2.The amount of plastic agents useful for same is listed in table 1.
100 grams of carrier material A-2 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then 110
Being dried 10 hours at DEG C, under nitrogen protection, catalyst carrier Z-2 being obtained after roasting 5 hours under the conditions of 550 DEG C, its property is shown in
Table 2.Then impregnated with the maceration extract 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, while heating and stirring to dissolving, solution (a) is obtained.Solid is inclined
Sodium aluminate is configured to concentration for 250g Al2O3/ L sodium aluminate solutions (b).Powdery coconut husk charcoal is added in glutamic acid aqueous solution and is mixed
Close uniform, the solid volume ratio of liquid is 3：1, then add water beating, obtains slurries（c）.A plastic cans is taken, the stirring of 2L deionized waters is inserted
Slurries are added after being heated to 60 DEG C（c）, while open have (a), the valve of the container of (b), and the pH=8.0 of control system, control
(a) was dripped off in 45 minutes by system, closed valve.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, 4h is processed under the conditions of 180 DEG C, filtered, wash to without sulfuric acid
Radical ion, filters, and filter cake is dried 10 hours at 110 DEG C, carrier material A-3 is obtained, then under nitrogen protection at 550 DEG C
Under the conditions of roasting 5 hours, pulverize and sieve and obtain powder carrier J-3.The amount of plastic agents useful for same is listed in table 1.
100 grams of carrier material A-3 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then 110
Being dried 10 hours at DEG C, under nitrogen protection, catalyst carrier Z-3 being obtained after roasting 5 hours under the conditions of 550 DEG C, its property is shown in
Table 2.
Embodiment 4
Solid aluminum chloride is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is well mixed in adding lysine solution, liquid
Gu volume ratio is 3：1, then add water beating, obtains activated carbon slurries (c).(a) is added in plastic cans and is heated with stirring to 60 DEG C
Afterwards, the valve of the container for having (b) is opened, system in tank was added drop-wise to pH=4.0 within 10 minutes by control, was now added in tank
Enter (c), continue (b) is added dropwise, system in tank was added drop-wise to pH=8.0 in 30 minutes by control.Keeping temperature is 60 DEG C, pH=8.0, always
Change 1 hour, material filtering in tank to contents on dry basis 15wt% be transferred to material in autoclave, under the conditions of 180 DEG C, 4h is processed,
Filtered, wash to without chlorion, filter, filter cake is dried 10 hours at 110 DEG C, carrier material A-4, Ran Hou is obtained
Nitrogen protection under under the conditions of 550 DEG C roasting 5 hours, pulverize and sieve and obtain powder carrier J-4.The amount row of plastic agents useful for same
In table 1.
100 grams of carrier material A-4 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then 110
Being dried 10 hours at DEG C, under nitrogen protection, catalyst carrier Z-4 being obtained after roasting 5 hours under the conditions of 550 DEG C, its property is shown in
Table 2.
Embodiment 5
Solid aluminum sulfate is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).Powdery coconut husk charcoal is well mixed in adding lysine solution, liquid
Gu volume ratio is 3：1, then add water beating, obtains activated carbon slurries (c).A plastic cans is taken, (a) is added in tank and is heated with stirring to
After 60 DEG C, opening has the valve of the container of (b), and system in tank was added drop-wise to pH=4.0 within 10 minutes by control, is opened (c) and is held
The valve of device, continues (b) is added dropwise, and system in tank was added drop-wise to pH=8.0 in 30 minutes by control, controlled the valve of the container of (c),
Guarantee is now 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
Be dried to contents on dry basis 15wt%, material is transferred in autoclave, 4h is processed under the conditions of 180 DEG C, is filtered, washed to nothing
Sulfate ion, filters, and filter cake is dried 10 hours at 110 DEG C, carrier material A-5 is obtained, is then existed under nitrogen protection
Roasting 5 hours under the conditions of 550 DEG C, pulverize and sieve and obtain powder carrier J-5.The amount of plastic agents useful for same is listed in table 1.
100 grams of carrier material A-5 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, then 110
Being dried 10 hours at DEG C, under nitrogen protection, catalyst carrier Z-5 being obtained after roasting 5 hours under the conditions of 550 DEG C, its property is shown in
Table 2.
Comparative example 1
Solid aluminum sulfate is added in distilled water, while heating and stirring to dissolving, solution (a) is obtained.By concentrated ammonia liquor
Appropriate distilled water diluting is added into about 10wt% weak aqua ammonias (b).A plastic cans is taken, (a) is added in tank and is heated with stirring to 60 DEG C
Afterwards, the valve of the container for having (b) is opened, system in tank was added drop-wise to pH=8.0 in 30 minutes by control.Keeping temperature is 60 DEG C,
PH=8.0, aging 1 hour, material in tank is filtered, and is washed to sulfate radical-free ion, is filtered, filter cake is done at 110 DEG C
Dry 10 hours, carrier material PA-1 is obtained, its appearance white.
100 grams of carrier material PA-1 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou
It is dried 10 hours at 110 DEG C, under the conditions of 550 DEG C after roasting 5 hours, obtains catalyst carrier DZ-A, its appearance white, its property
Matter is shown in Table 2.Then impregnated with the maceration extract containing Ce-Cu, be then dried 10 hours at 110 DEG C, the roasting 5 under the conditions of 550 DEG C
Hour, catalyst DA is obtained, its composition is shown in Table 3.
Comparative example 2
By 100 grams of activated carbon used in embodiment 2, contact to form paste with the peptization liquid containing nitric acid, extruded moulding,
Then be dried 10 hours at 110 DEG C, under nitrogen protection, catalyst carrier DZ- is obtained after roasting 5 hours under the conditions of 550 DEG C
B, its outward appearance are black, then using the method dipping active metal component of embodiment 2, obtain catalyst DB.
Comparative example 3
By activated carbon used in embodiment 2 with carrier material PA-1 physical mixeds, contact with the peptization liquid containing nitric acid
Paste is formed, then extruded moulding is dried 10 hours at 110 DEG C, under nitrogen protection under the conditions of 550 DEG C after roasting 5 hours,
Catalyst carrier DZ-C is obtained, wherein activated carbon content is 50wt%, and alumina content is 50wt%, its outward appearance black.Then adopt
With the method dipping active metal component of embodiment 2, catalyst DC is obtained.
Comparative example 4
Repeat the synthesis of embodiment 2, do not carry out hydro-thermal process during plastic, comparative catalyst's carrier material is obtained
PA-2 and powder carrier DF-2.
The preparation of preformed catalyst carrier and catalyst obtains catalyst carrier DZ-D and catalyst DD with embodiment 2, its
Composition is shown in Table 2.
Comparative example 5
Repeat the synthesis of embodiment 2, without amino acid during plastic, and do not carry out at hydro-thermal during plastic
Reason, is obtained 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
Example 2 is applied, catalyst DE is obtained, its composition is shown in Table 3.
1 plastic reagent quality of table
The property of 2 catalyst carrier of table
The composition of 3 catalyst of table
Can be seen that by the property of catalyst carrier in table 2 and carried using the catalyst obtained after amino acid treatment activated carbon
Compared with the catalyst carrier obtained without amino acid, bulk property is improved body.
The outward appearance of carrier material and carrier by obtained by the embodiment of the present invention is canescence, without obvious black, explanation
Activated carbon becomes the core of carrier material and carrier.
In the present invention, using X-ray photoelectron spectroscopy（XPS）To 1 resulting vehicle material surface of embodiment and comparative example
Element be analyzed.From analysis result, element composition and the PA-1 groups on embodiment resulting vehicle -1 ~ A-5 of materials A surfaces
Into essentially identical, there is micro elemental carbon.This further illustrates, and the carrier material of the present invention is with activated carbon as core, with oxygen
It is shell to change aluminium dry glue.
Catalyst prepared by catalyst prepared by the invention described above catalyst carrier and its comparison vehicle is evaluated.
Catalyst packing with ozone as oxide isolation, enters containing phenol, sulfur-containing waste water to certain oil plant in bubbling bed reactor
The process of row batch (-type).
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.
4 evaluation result of table
The waste water that can be seen that Jing after processing from 4 evaluation result of table can meet qualified discharge Two-stage control index request.Make
There is preferably activity with catalyst prepared by the inventive method.
Using after 100 times, evaluation result is listed in table 5 to catalyst.
5 estimation of stability result of table
Can be seen that from 5 estimation of stability result of table and there is more excellent stablizing using catalyst prepared by this method
Property.
Claims (18)
1. a kind of preparation method of catalytic wet oxidation catalyst carrier, including：
(1) 150 mesh ~ 300 mesh activated carbons are adopted into amino acid treatment, is then beaten；
(2) step is introduced during amorphous alumina plastic（1）The activated carbon slurries for obtaining；
(3) step（2）Material after the plastic for obtaining carries out aging, after hydro-thermal process, refilters, washs, being dried, obtaining
Catalyst carrier material；
(4) by step（3）The catalyst carrier material of gained makes catalyst carrier.
2. in accordance with the method for claim 1, it is characterised in that：Step（4）Catalyst carrier material is made into catalyst load
Body is at least using one of following methods：
A, by step（3）The carrier material of gained, the roasting under inert gas shielding obtain catalyst carrier；
B, by step（3）The carrier material shaping of gained, after drying, the roasting under inert gas shielding obtains catalyst load
Body；
C, by step（3）Carrier material roasting under inert gas shielding of gained, then Jing shapings again, 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 aluminum 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%, aluminum 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 are carried
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 step (1) activated carbon is as follows：Specific surface area
500~3000m2/ g, 0.5 ~ 1.8cm of pore volume3/ g, 1 ~ 10nm of average pore radius.
7. in accordance with the method for claim 1, it is characterised in that step（1）Described activated carbon beating employing adds water, low-carbon (LC)
One or more in alcohol is beaten, and wherein low-carbon alcohols are that carbon number is one or more in 1 ~ 5 monohydric alcohol.
8. in accordance with the method for claim 1, it is characterised in that step（1）Described activated carbon first adopts amino acid treatment,
Then it is beaten, described amino acid is amino acid that carbon number is less than 20.
9. in accordance with the method for claim 1, it is characterised in that described amino acid consumption accounts for the 2% ~ 50% of activated carbon weight.
10. in accordance with the method for claim 1, it is characterised in that described amino acid consumption account for activated carbon weight 5% ~
20%。
11. in accordance with the method for claim 1, it is characterised in that described amino acid be glycine, serine, threonine,
In cysteine, tyrosine, asparagine, glutamine, lysine, arginine, histidine, aspartic acid, glutamic acid one
Plant or various.
12. in accordance with the method for claim 1, it is characterised in that：Amino acid treatment activated carbon be by amino acid directly with work
Property charcoal mixing, or amino acid be dissolved in solvent add activated carbon, solvent therein be water, carbon number for 1 ~ 5 one
One or more in first alcohol；During amino acid treatment activated carbon, the solid volume ratio of its liquid is below 10.
13. 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.
14. in accordance with the method for claim 1, it is characterised in that：Step（2）In, step（1）The activated carbon slurries of gained
One or more combination of the incorporation way using following manner：（1）During plastic neutralization reaction, the activated carbon slurries are connected
In continuous addition plastic cans；（2）The activated carbon slurries are charged first in plastic cans, the acidity of amorphous alumina then will be prepared
In material and alkaline material and plastic；（3）One or more of the activated carbon slurries with plastic material are mixed, then plastic thing
Material neutralization plastic.
15. in accordance with the method for claim 1, it is characterised in that step（3）In, before hydro-thermal process, Jing is filtered or is heated
Concentration；Described heating concentration is heated to immobilising paste shape, and described heating concentration is in step（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 hydro-thermal process is in closed container
Carry out, the temperature of hydro-thermal process is 90 ~ 300 DEG C, described hydro-thermal process is produced itself in material treatment temperature
Pressure condition under carry out, described hydrothermal conditions are 0.5 ~ 48h.
17. 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.
18. 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 be 450 ~ 700 DEG C, roasting time be 1 ~ 10 hour, the drying condition described in method B be at 80 ~ 200 DEG C, be dried 1 ~
15 hours, sintering temperature was 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, in method C, by step（3）The carrier material of gained
The roasting under inert gas shielding, described roasting condition are as follows：Sintering temperature is 450 ~ 700 DEG C, and roasting time is 1 ~ 10 little
When, then Jing shapings again, after being dried, the roasting under inert gas shielding obtains catalyst carrier, and the drying condition after shaping 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 1 ~ 10 little
When.
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| KR100801443B1 (en) * | 2006-12-07 | 2008-02-11 | 재단법인서울대학교산학협력재단 | Heteropoly acid catalyst immobilized on nitrogen-containing mesoporous carbon, production method thereof and production method of methacrylic acid using said catalyst |
| CN102049256A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Waste water treatment catalyst and preparation method thereof |
| CN102921406A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Active carbon catalyst and preparation method and application thereof |
| CN103041818A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of catalytic wet oxidation catalyst and treatment method of organic wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100801443B1 (en) * | 2006-12-07 | 2008-02-11 | 재단법인서울대학교산학협력재단 | Heteropoly acid catalyst immobilized on nitrogen-containing mesoporous carbon, production method thereof and production method of methacrylic acid using said catalyst |
| CN102049256A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Waste water treatment catalyst and preparation method thereof |
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| CN103041818A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of catalytic wet oxidation catalyst and treatment method of organic wastewater |
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