CN110013859A - A kind of complex carrier ozone catalyst and its preparation method and application - Google Patents
A kind of complex carrier ozone catalyst and its preparation method and application Download PDFInfo
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- CN110013859A CN110013859A CN201910189343.XA CN201910189343A CN110013859A CN 110013859 A CN110013859 A CN 110013859A CN 201910189343 A CN201910189343 A CN 201910189343A CN 110013859 A CN110013859 A CN 110013859A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a kind of complex carrier ozone catalysts for belonging to water process and agricultural wastes application technology as the second resource field and its preparation method and application.Complex carrier ozone catalyst of the present invention includes complex carrier, active component and auxiliary agent；Complex carrier is obtained by agricultural wastes straw mixing, granulation, the charing of catalyst carrier and pretreatment, activation；Active component is Fe, Mn, auxiliary agent Ce, Ti.Complex carrier ozone catalyst provided by the invention has the characteristics that high catalytic efficiency, active component are environmental-friendly, is not easy to dissolve out, the problem of not only solving ozone catalyst in the prior art at high cost, processing waste water low efficiency, and the recycling for realizing agricultural wastes straw recycles.
Description
Technical field
The invention belongs to water process and agricultural wastes application technology as the second resource field, in particular to a kind of complex carrier is smelly
VPO catalysts and its preparation method and application.
Background technique
China is used as a large agricultural country, and the utilization and exploitation of stalk resource be both related to the effective use of agricultural resource.
The main Land use systems of stalk have: straw-returning, feed, the energy, producing methane and raw material of industry etc..
Catalytic ozonation technology is widely used in water treatment field, such as in drinking water, sanitary sewage, Industry Waste
In the processing of water.It is the hot spot of water treatment field research in recent years as a kind of effective high-level oxidation technology.In catalysis ozone
During oxidation technology degradation of contaminant, using the material of high-specific surface area as carrier, be conducive to the dispersion of catalyst activity component,
And be conducive to pollutant in the absorption degradation on surface.Catalyst can promote ozone in the freedom of catalyst surface generation oxidisability
Base etc., such as: OH, O2 -·、HO2, with pollutant reaction in sewage, reach the purpose of degradation.But the catalysis prepared at present
Agent, it is generally existing it is at high cost, stability is poor, processing waste water low efficiency etc. limits the main problem of the technical application.
Summary of the invention
The purpose of the present invention is to provide a kind of complex carrier ozone catalyst and its preparation method and application, particular techniques
Scheme is as follows:
A kind of complex carrier ozone catalyst includes complex carrier, active component and auxiliary agent；
The complex carrier is mixed by the agricultural wastes straw of catalyst carrier and pretreatment, activation, be granulated, carbonized
It arrives；
The active component is Fe, Mn, and the auxiliary agent is Ce, Ti.
The agricultural wastes straw is that one of corn, wheat, rice, eggplant, cotton, grape stalk are a variety of.
The catalyst carrier is the common carriers such as alumina support.
The pretreatment of the agricultural wastes straw is to crush, cleaning, drying, be ground up, sieved；The activation is with reagent
Ammonium hydroxide.
The preparation method of the complex carrier ozone catalyst the following steps are included:
(1) by agricultural wastes straw first through crushing, cleaning, drying, be ground up, sieved, be then soaked in ammonium hydroxide and live
Stalk after processing is made after dry in change processing；
(2) catalyst carrier is uniformly mixed with stalk after processing obtained by step (1), after binder, deionized water is added,
Through granulation, drying, charing, complex carrier is made；
(3) complex carrier obtained by step (1) is impregnated in active component salt solution under room temperature (20-30 DEG C), dry,
Roasting；Then it is impregnated in auxiliary agent salting liquid under room temperature (20-30 DEG C), dry, roasting；Complex carrier ozone catalytic is made
Agent.
In the step (1), agricultural wastes straw is crushed, drying temperature is 80-120 DEG C after cleaning, and drying time is
6-12h；The grit number of crossing is 80-100 mesh；Soaking time is 3-4h, ammonia concn 0.1-0.3mol/L in ammonium hydroxide.
In the step (2), stalk quality is the 2- of stalk mixture quality after catalyst carrier and processing after processing
8wt.%；Binder additional amount is the 20-30wt.% of stalk quality sum after catalyst carrier and processing.
In the step (2), binder is methylcellulose and/or sodium cellulose glycolate；The partial size of granulation is 2-
8mm；Drying temperature is 80-120 DEG C, drying time 6-12h；Carbonization temperature is 200-350 DEG C, carbonization time 1-3h.
Further, the carbonization temperature is preferably 300 DEG C, and the carbonization time is preferably 1h.
In the step (3), active component salt solution is nitrate solution, chlorination salting liquid；The auxiliary agent salting liquid is
Cerous nitrate, butyl titanate.
Active component Fe, the Mn quality sum is the 10-30wt.% of complex carrier, and Fe, Mn molar ratio are (1~2):
1；Adjuvant component Ce, Ti quality sum is the 5-10wt.% of complex carrier, and Ce, Ti molar ratio are 1:1.
Further, active component Fe, the Mn quality sum is preferably the 20wt.% of complex carrier, the auxiliary agent group
Dividing Ce, Ti quality sum is preferably the 10wt.% of complex carrier.
In the step (3), dip time is 12-24h；Drying temperature is 80-120 DEG C, drying time 6-12h；
Maturing temperature is 400-600 DEG C, and calcining time is 3-8h.
Further, in the step (3), drying temperature is preferably 105 DEG C, drying time 12h；Maturing temperature is
450 DEG C, calcining time is 5h.
The complex carrier ozone catalyst catalytic ozonation degradation sanitary sewage, Industry Waste water pollutant, it is described
Pollutant is organic pollutant.
Further, organic pollutant of the present invention is hardly degraded organic substance, (difficult for biological degradation) organic matter difficult to degrade
Refer to the organic matter that microorganism cannot be degraded in any condition with sufficiently fast speed, including phenolic compound, polycyclic
Arene compounds, heterocycle compound, organic cyanogen compound, synthetic detergent, Polychlorinated biphenyls etc..Some organic matters, which have, to be caused
, there is huge harm in the effects of cancer, teratogenesis, mutagenesis to environment and the mankind.
The invention has the benefit that
(1) using agricultural wastes straw and custom catalysts carrier as mixed carrier, what is formed after carbonizing answers the present invention
Carrier is closed, there is porous structure and specific surface area is significantly improved, using the suction-operated of complex carrier, so that stalk obtains
High added value resource utilization, reduces preparation cost.
(2) for the present invention using iron, manganese as activity component metal element, cerium, titanium are assistant metal element, are roasted using impregnation drying
Activity component metal element, assistant metal element are carried on complex carrier by burning method, so that active component, auxiliary agent equably divide
It is dispersed in the surface of complex carrier, preparation process is simple and active component is environmental-friendly；The complex carrier ozone catalyst of preparation is steady
Qualitative strong, active metal component is not easy dissolution and the efficiency of O3 catalytic oxidation is significantly improved, high catalytic efficiency；Wherein urge
The efficiency for changing ozone oxidation degradation of phenol reaches 65% or more.
Detailed description of the invention
Attached drawing 1 and attached drawing 2 are cotton stalk-alumina composite carrier ozone catalyst O3 catalytic oxidation in embodiment 1
Performance comparison；
Attached drawing 3 is cotton stalk-alumina composite carrier ozone catalyst O3 catalytic oxidation performance pair in embodiment 2
Than；
Attached drawing 4 is corn stover-alumina composite carrier ozone catalyst O3 catalytic oxidation performance pair in embodiment 3
Than；
Attached drawing 5 is wheat stalk-alumina composite carrier ozone catalyst O3 catalytic oxidation performance pair in embodiment 4
Than；
Attached drawing 6 is grape branch stalk-alumina composite carrier ozone catalyst O3 catalytic oxidation performance pair in embodiment 5
Than；
Attached drawing 7 is grape branch stalk-alumina composite carrier ozone catalyst O3 catalytic oxidation performance pair in embodiment 6
Than.
Specific embodiment
The present invention provides a kind of complex carrier ozone catalysts and its preparation method and application, with reference to the accompanying drawing and real
Applying example, the present invention is described further.
Embodiment 1: cotton stalk-nano aluminium oxide complex carrier ozone catalyst preparation and its ozone oxidation performance
Cotton stalk-nano aluminium oxide complex carrier ozone catalyst is prepared as steps described below:
(1) stalk pretreatment: the cotton stalk of agriculture waste is crushed, cleaning, removal surface impurity, is 100 in temperature
It is dry in DEG C baking oven, it is ground to 80 mesh, drying for standby；
(2) stalk activates: powder stalk obtained by step (1) being added in 0.1mol/L ammonia spirit, 3h is impregnated, is completed
Stalk powder after activation processing is dried 12h by the activation processing of stalk in 100 DEG C of baking ovens；
(3) it is granulated, is dry: by stalk powder made from 0.5g step (2), 9.5g alumina powder, 3g carboxymethyl cellulose
Plain sodium, deionized water are ground after evenly mixing, prepare carrier master batch, partial size 2-8mm, dry 12h, standby in 100 DEG C of baking ovens
With；
(4) it carbonizes: step (3) resulting vehicle master batch is put into 300 DEG C of Muffle furnace, in air atmosphere, carbonize 1h, it is complete
At the charing of carrier master batch, stalk particle carbonizes to form activated carbon from activated sludge particle, forms porous compound load with nano aluminium oxide
Body；It is cooled to room temperature, obtains 8.190g complex carrier.
(5) it impregnates active component: being 1:1 according to Fe, Mn molar ratio, active component Fe, Mn quality sum is step (4) institute
The ratio for obtaining complex carrier quality 20wt.%, weighs nine water ferric nitrate of 5.962g, 1.859g manganese chloride, is dissolved in deionization respectively
It in water, mixes after mixing evenly, obtains the first maceration extract；Complex carrier obtained by step (4) is immersed in the first maceration extract,
12h is impregnated at room temperature, places into the oven drying 12h that temperature is 100 DEG C；Finally there is the carrier of iron, manganese to put dry back loading
Entering temperature is to roast 5h in 450 DEG C of Muffle furnaces；It is cooled to room temperature.
(6) impregnation aids: being 1:1 according to Ce, Ti molar ratio, and auxiliary agent Ce, Ti quality sum is compound load obtained by step (4)
The ratio of weight 10wt.% weighs 1.891g cerium nitrate hexahydrate and is dissolved in deionized water, and 1.481g butyl titanate is dissolved in anhydrous
It in ethyl alcohol, mixes after mixing evenly, obtains the second maceration extract；There is the carrier impregnation of iron, manganese the load obtained by step (5) again
In two maceration extracts, 12h is impregnated at room temperature, and placing into temperature is 100 DEG C of oven drying 12h；Finally will dry back loading have cerium,
Titanium, iron, manganese carrier to be put into temperature be to roast 5h in 450 DEG C of Muffle furnace, it is smelly that cotton stalk-alumina composite carrier is made
VPO catalysts.
Ozone catalyst obtained is spheric granules, passes through N2Adsorption/desorption characterization, measuring its specific surface area is
159.89m2/g。
Cotton stalk-alumina composite carrier ozone catalyst dosage 10g/L of above-mentioned preparation method preparation, ozone are thrown
Dosage is 3.5mg/L, takes 500mg/L phenolic waste water, and catalytic ozonation reacts 35min, and phenol removal rate reaches 93%, relative to
Independent ozone catalytic phenol removal rate improves 47%, specific as shown in Figure 1.
Under equal conditions, COD is taken0The sanitary sewage that (COD initial value) is about 79mg/L, catalysis ozone react 60min,
COD removal rate reaches 82%, improves 31% relative to independent ozone catalytic COD removal rate, specific as shown in Figure 2.
Embodiment 2: cotton stalk-nano aluminium oxide complex carrier ozone catalyst preparation and its ozone oxidation performance
Cotton stalk-nano aluminium oxide complex carrier ozone catalyst is prepared as steps described below:
(1) stalk pretreatment: the cotton stalk of agriculture waste is crushed, cleaning, removal surface impurity, is 105 in temperature
It is dry in DEG C baking oven, it is ground to 80 mesh, drying for standby；
(2) stalk activates: powder stalk obtained by step (1) being added in 0.2mol/L ammonia spirit, 3h is impregnated, is completed
Stalk powder after activation processing is dried 12h by the activation processing of stalk in 105 DEG C of baking ovens；
(3) it is granulated, is dry: by stalk powder made from 0.2g step (2), 9.8g alumina powder, 2g carboxymethyl cellulose
Plain sodium, deionized water are ground after evenly mixing, prepare carrier master batch, partial size 2-8mm, dry 12h, standby in 105 DEG C of baking ovens
With；
(4) it carbonizes: step (3) resulting vehicle master batch is put into 300 DEG C of Muffle furnace, in air atmosphere, carbonize 1h, it is complete
At the charing of carrier master batch, stalk particle carbonizes to form activated carbon from activated sludge particle, forms porous compound load with nano aluminium oxide
Body；It is cooled to room temperature, obtains 7.290g complex carrier.
(5) it impregnates active component: being 2:1 according to Fe, Mn molar ratio, active component Fe, Mn quality sum is step (4) institute
The ratio for obtaining complex carrier quality 10wt.%, weighs nine water ferric nitrate of 3.527g, 0.550g manganese chloride, is dissolved in deionization respectively
It in water, mixes after mixing evenly, obtains the first maceration extract；Complex carrier obtained by step (4) is immersed in the first maceration extract,
12h is impregnated at room temperature, places into the oven drying 12h that temperature is 100 DEG C；Finally there is the carrier of iron, manganese to put dry back loading
Entering temperature is to roast 5h in 450 DEG C of Muffle furnaces；It is cooled to room temperature.
(6) impregnation aids: being 1:1 according to Ce, Ti molar ratio, and auxiliary agent Ce, Ti quality sum is compound load obtained by step (4)
The ratio of weight 10wt.% weighs 1.683g cerium nitrate hexahydrate and is dissolved in deionized water, and 1.318g butyl titanate is dissolved in anhydrous
It in ethyl alcohol, mixes after mixing evenly, obtains the second maceration extract；There is the carrier impregnation of iron, manganese the load obtained by step (5) again
In two maceration extracts, 12h is impregnated at room temperature, and placing into temperature is 105 DEG C of oven drying 12h；Finally will dry back loading have cerium,
Titanium, iron, manganese carrier to be put into temperature be to roast 6h in 450 DEG C of Muffle furnace, it is smelly that cotton stalk-alumina composite carrier is made
VPO catalysts.
Cotton stalk-alumina composite carrier ozone catalyst dosage 10g/L of above-mentioned preparation method preparation, ozone are thrown
Dosage is 3.5mg/L, takes 500mg/L phenolic waste water, and catalytic ozonation reacts 35min, and phenol removal rate reaches 67%, relative to
Independent ozone catalytic phenol removal rate improves 21%, specific as shown in Figure 3.
Embodiment 3: corn stover-nano aluminium oxide complex carrier ozone catalyst preparation and its ozone oxidation performance
Corn stover-nano aluminium oxide complex carrier ozone catalyst is prepared as steps described below:
(1) stalk pretreatment: being 105 in temperature by the corn straw smashing of agriculture waste, cleaning, removal surface impurity
Dry 12h, is ground to 100 mesh, drying for standby in DEG C baking oven.
(2) stalk activates: powder stalk obtained by step (1) being added in 0.3mol/L ammonium hydroxide, 4h is impregnated, completes stalk
Activation processing；Stalk powder after activation processing is dried into 12h in 105 DEG C of baking ovens；
(3) be granulated, be dry: by stalk powder made from 0.2g step (2), 9.8g alumina powder, 3g methylcellulose,
Deionized water is ground after evenly mixing, prepares carrier master batch, partial size 2-8mm, dry 12h, spare in 105 DEG C of baking ovens.
(4) it carbonizes: step (3) resulting vehicle master batch is put into 250 DEG C of Muffle furnace, in air atmosphere, carbonize 2h, it is complete
At the charing of carrier master batch, stalk particle carbonizes to form activated carbon from activated sludge particle, forms porous compound load with nano aluminium oxide
Body；It is cooled to room temperature, obtains 7.231g complex carrier.
(5) it impregnates active component: being 1:1 according to Fe, Mn molar ratio, active component Fe, Mn quality sum is step (4) institute
The ratio for obtaining complex carrier quality 20wt.%, takes nine water ferric nitrate of 5.266g, 1.642g manganese chloride is dissolved in deionized water respectively
In, it mixes after mixing evenly, obtains the first maceration extract；Complex carrier obtained by step (4) is immersed in the first maceration extract, in room
Temperature is lower to impregnate 12h, and placing into temperature is 105 DEG C of oven drying 12h；Finally there is the carrier master batch of iron, manganese to be put into temperature load
To roast 5h in 500 DEG C of Muffle furnaces；It is cooled to room temperature.
(6) impregnation aids: being 1:1 according to Ce, Ti molar ratio, and auxiliary agent Ce, Ti quality sum is compound load obtained by step (4)
The ratio of weight 10wt.% weighs 1.669g cerium nitrate hexahydrate and is dissolved in deionized water, and 1.308g butyl titanate is dissolved in anhydrous
It in ethyl alcohol, mixes after mixing evenly, obtains the second maceration extract；There is the carrier impregnation of iron, manganese the load obtained by step (5) again
In two maceration extracts, 12h is impregnated at room temperature, and placing into temperature is 105 DEG C of oven drying 12h；Finally by load have cerium, titanium, iron,
The carrier of manganese is put into the Muffle furnace that temperature is 500 DEG C, roasts 5h, and corn stover-alumina composite carrier ozone catalytic is made
Agent.
The corn stover of above-mentioned preparation method preparation-nano aluminium oxide complex carrier ozone catalyst dosage 10g/L is smelly
Oxygen dosage is 3.5mg/L, takes 500mg/L phenolic waste water, and catalytic ozonation reacts 35min, and phenol removal rate reaches 74%, phase
28% is improved for independent ozone catalytic phenol removal rate, as shown in Figure 4.
Embodiment 4: wheat stalk-nano aluminium oxide complex carrier ozone catalyst preparation and its ozone oxidation performance
Wheat stalk-nano aluminium oxide complex carrier ozone catalyst is prepared as steps described below:
(1) stalk pretreatment: the wheat stalk of agriculture waste is crushed, cleaning, removal surface impurity, is 100 in temperature
Dry 12h, is ground to 100 mesh, drying for standby in DEG C baking oven.
(2) stalk activates: powder stalk obtained by step (1) being added in 0.1mol/L ammonia spirit, 3h is impregnated, is completed
The activation processing of stalk；Stalk powder after activation processing is dried into 12h in 100 DEG C of baking ovens；
(3) it is granulated, is dry: by stalk powder made from 0.8g step (2), 9.2g nano aluminium oxide, 3g carboxymethyl cellulose
Plain sodium, deionized water are ground after evenly mixing, prepare carrier master batch, partial size 2-8mm, dry 12h, standby in 100 DEG C of baking ovens
With.
(4) it carbonizes: step (3) resulting vehicle master batch is put into 300 DEG C of Muffle furnace, in air atmosphere, carbonize 1h, it is complete
At the charing of carrier master batch, stalk particle carbonizes to form activated carbon from activated sludge particle, forms porous compound load with nano aluminium oxide
Body；It is cooled to room temperature, obtains 5.942g complex carrier.
(5) it impregnates active component: being 1:1 according to Fe, Mn molar ratio, active component Fe, Mn quality sum is step (4) institute
The ratio for obtaining complex carrier quality 20wt.%, weighs nine water ferric nitrate of 4.325g, 1.349g manganese chloride is dissolved in deionization respectively
It in water, mixes after mixing evenly, obtains the first maceration extract；Complex carrier obtained by step (4) is immersed in the first maceration extract,
12h is impregnated at room temperature, and placing into temperature is 105 DEG C of oven drying 12h；Finally by load has iron, the carrier of manganese is put into temperature and is
In 450 DEG C of Muffle furnaces, 5h is roasted；It is cooled to room temperature.
(6) impregnation aids: being 1:1 according to Ce, Ti molar ratio, and auxiliary agent Ce, Ti quality sum is compound load obtained by step (4)
The ratio of weight 10wt.% weighs 1.372g cerium nitrate hexahydrate and is dissolved in deionized water, and 1.075g butyl titanate is dissolved in anhydrous
It in ethyl alcohol, mixes after mixing evenly, obtains the second maceration extract；There is the carrier impregnation of iron, manganese the load obtained by step (5) again
In two maceration extracts, 12h is impregnated at room temperature, and placing into temperature is 105 DEG C of oven drying 12h；Finally by load have cerium, titanium, iron,
The carrier of manganese is put into the Muffle furnace that temperature is 450 DEG C, is roasted 5h, is obtained wheat stalk-nano aluminium oxide complex carrier ozone
Catalyst.
The wheat stalk of above-mentioned preparation method preparation-nano aluminium oxide complex carrier ozone catalyst dosage 10g/L is smelly
Oxygen dosage is 3.5mg/L, takes 500mg/L phenolic waste water, and catalytic ozonation reacts 35min, and phenol removal rate reaches 82%, phase
36% is improved for independent ozone catalytic phenol removal rate, as shown in Figure 5.
Embodiment 5: the preparation of grape branch stalk-nano aluminium oxide composite carried catalyst and its ozone oxidation performance
Grape branch stalk-nano aluminium oxide complex carrier ozone catalyst is prepared as steps described below:
(1) stalk pretreatment: agriculture waste grape branch being crushed, cleaning, removal surface impurity, is 120 DEG C of bakings in temperature
Dry 12h, is ground to 100 mesh, drying for standby in case.
(2) stalk activates: powder stalk obtained by step (1) being added in 0.2mol/L ammonia spirit, 4h is impregnated, is completed
The activation processing of stalk；Stalk powder after activation processing is dried into 12h in 110 DEG C of baking ovens；
(3) it is granulated, is dry: by stalk powder made from 0.8g step (2), 9.2g nano aluminium oxide, 3g carboxymethyl cellulose
Plain sodium, deionized water are ground after evenly mixing, prepare carrier master batch, partial size 2-8mm, dry 12h, standby in 120 DEG C of baking ovens
With.
(4) it carbonizes: step (3) resulting vehicle master batch is put into 300 DEG C of Muffle furnace, in air atmosphere, carbonize 1h, it is complete
At the charing of carrier master batch, stalk particle carbonizes to form activated carbon from activated sludge particle, forms porous compound load with nano aluminium oxide
Body；It is cooled to room temperature, obtains 6.265g complex carrier.
(5) it impregnates active component: being 1:1 according to Fe, Mn molar ratio, active component Fe, Mn quality sum is step (4) institute
The ratio for obtaining complex carrier quality 20wt.%, weighs nine water ferric nitrate of 4.560g, 1.422g manganese chloride, is dissolved in deionization respectively
It in water, mixes after mixing evenly, obtains the first maceration extract；Complex carrier obtained by 6.265g step (4) is immersed in the first dipping
In liquid, 12h is impregnated at room temperature, and placing into temperature is 105 DEG C of oven drying 12h；Finally there is the carrier of iron, manganese to be put into load
Temperature is to roast 5h in 450 DEG C of Muffle furnaces；It is cooled to room temperature.
(6) impregnation aids: being 1:1 according to Ce, Ti molar ratio, and auxiliary agent Ce, Ti quality sum is compound load obtained by step (4)
The ratio of weight 10wt.% weighs 1.446g cerium nitrate hexahydrate and is dissolved in deionized water, and 1.133g butyl titanate is dissolved in anhydrous
It in ethyl alcohol, mixes after mixing evenly, obtains the second maceration extract；There is the carrier impregnation of iron, manganese the load obtained by step (5) again
In two maceration extracts, 12h is impregnated at room temperature, and placing into temperature is 105 DEG C of oven drying 12h；Finally by load have cerium, titanium, iron,
The carrier of manganese is put into the Muffle furnace that temperature is 450 DEG C, roasts 6h, it is smelly to obtain grape branch stalk-nano aluminium oxide complex carrier
VPO catalysts.
Grape branch stalk-nano aluminium oxide complex carrier ozone catalyst dosage 10g/L of above-mentioned preparation method preparation,
Ozone dosage is 3.5mg/L, takes 500mg/L phenolic waste water, and catalytic ozonation reacts 35min, and phenol removal rate reaches 90%,
44% is improved relative to independent ozone catalytic phenol removal rate, as shown in Figure 6.
Embodiment 6: the preparation of grape branch stalk-nano aluminium oxide composite carried catalyst and its ozone oxidation performance
Grape branch stalk-nano aluminium oxide complex carrier ozone catalyst is prepared as steps described below:
(1) stalk pretreatment: agriculture waste grape branch being crushed, cleaning, removal surface impurity, is 108 DEG C of bakings in temperature
Dry 12h, is ground to 100 mesh, drying for standby in case.
(2) stalk activates: powder stalk obtained by step (1) being added in 0.2mol/L ammonia spirit, 4h is impregnated, is completed
The activation processing of stalk；Stalk powder after activation processing is dried into 12h in 108 DEG C of baking ovens；
(3) it is granulated, is dry: by stalk powder made from 0.5g step (2), 9.5g nano aluminium oxide, 3g carboxymethyl cellulose
Plain sodium, deionized water are ground after evenly mixing, prepare carrier master batch, partial size 2-8mm, dry 12h, standby in 108 DEG C of baking ovens
With.
(4) it carbonizes: step (3) resulting vehicle master batch is put into 350 DEG C of Muffle furnace, in air atmosphere, carbonize 1.5h,
The charing of carrier master batch is completed, stalk particle is carbonized to form activated carbon from activated sludge particle, be formed with nano aluminium oxide porous compound
Carrier；It is cooled to room temperature, obtains 6.640g complex carrier.
(5) it impregnates active component: being 1:1 according to Fe, Mn molar ratio, active component Fe, Mn quality sum is step (4) institute
The ratio for obtaining complex carrier quality 30wt.%, weighs nine water ferric nitrate of 7.250g, 6.425g manganese nitrate (mass fraction
50wt.%), it is dissolved in deionized water, mixes after mixing evenly respectively, obtain the first maceration extract；By compound load obtained by step (4)
Body is immersed in the first maceration extract, impregnates 12h at room temperature, and placing into temperature is 105 DEG C of oven drying 12h；It finally will load
There is iron, the carrier of manganese is put into temperature to roast 5h in 450 DEG C of Muffle furnaces；It is cooled to room temperature.
(6) impregnation aids: being 1:1 according to Ce, Ti molar ratio, and auxiliary agent Ce, Ti quality sum is compound load obtained by step (4)
The ratio of weight 5wt.% weighs 0.766g cerium nitrate hexahydrate and is dissolved in deionized water, and 0.600g butyl titanate is dissolved in anhydrous
It in ethyl alcohol, mixes after mixing evenly, obtains the second maceration extract；There is the carrier impregnation of iron, manganese the load obtained by step (5) again
In two maceration extracts, 12h is impregnated at room temperature, and placing into temperature is 108 DEG C of oven drying 12h；Finally by load have cerium, titanium, iron,
The carrier of manganese is put into the Muffle furnace that temperature is 450 DEG C, roasts 6h, it is smelly to obtain grape branch stalk-nano aluminium oxide complex carrier
VPO catalysts.
Grape branch stalk-nano aluminium oxide complex carrier ozone catalyst dosage 10g/L of above-mentioned preparation method preparation,
Ozone dosage is 3.5mg/L, takes 500mg/L phenolic waste water, and catalytic ozonation reacts 35min, and phenol removal rate reaches 83%,
37% is improved relative to independent ozone catalytic phenol removal rate, as shown in Figure 7.
Claims (10)
1. a kind of complex carrier ozone catalyst, which is characterized in that including complex carrier, active component and auxiliary agent；
The complex carrier is obtained by agricultural wastes straw mixing, granulation, the charing of catalyst carrier and pretreatment, activation；
The active component is Fe, Mn, and the auxiliary agent is Ce, Ti.
2. complex carrier ozone catalyst according to claim 1, which is characterized in that the catalyst carrier is aluminium oxide
Carrier.
3. complex carrier ozone catalyst according to claim 1, which is characterized in that the agricultural wastes straw it is pre-
Processing is crushing, cleaning, drying, is ground up, sieved；The activation is ammonium hydroxide with reagent.
4. the preparation method of any one of the claim 1-3 complex carrier ozone catalyst, which is characterized in that including following step
It is rapid:
(1) by agricultural wastes straw first through crushing, cleaning, drying, be ground up, sieved, be then soaked in ammonium hydroxide, be made after dry
Stalk after processing；
(2) catalyst carrier is uniformly mixed with stalk after processing obtained by step (1), after binder, deionized water is added, through making
Grain, dry, charing, are made complex carrier；
(3) complex carrier obtained by step (1) is impregnated in active component salt solution at room temperature, dry, roasting；Then in room
It is impregnated under temperature in auxiliary agent salting liquid, dry, roasting；Complex carrier ozone catalyst is made.
5. the preparation method according to claim 4, which is characterized in that in the step (1), agricultural wastes straw powder
Drying temperature is 80-120 DEG C after broken, cleaning, drying time 6-12h；The grit number of crossing is 80-100 mesh；It is soaked in ammonium hydroxide
The bubble time is 3-4h, ammonia concn 0.1-0.3mol/L.
6. the preparation method according to claim 4, which is characterized in that in the step (2), stalk quality is to urge after processing
The 2-8wt.% of stalk mixture quality after agent carrier and processing；Binder additional amount is stalk after catalyst carrier and processing
The 20-30wt.% of mixture quality.
7. the preparation method according to claim 4, which is characterized in that in the step (2), binder is carboxymethyl cellulose
Plain sodium and/or methylcellulose；The partial size of granulation is 2-8mm；Drying temperature is 80-120 DEG C, drying time 6-12h；Charing temperature
Degree is 200-350 DEG C, carbonization time 1-3h.
8. the preparation method according to claim 4, which is characterized in that in the step (3), active component salt solution is nitre
Acid salt solution, chlorination salting liquid；The auxiliary agent salting liquid is cerous nitrate, butyl titanate；
Active component Fe, the Mn quality sum is the 10-30wt.% of complex carrier, and Fe, Mn molar ratio are (1~2): 1；Institute
The 5-10wt.% that adjuvant component Ce, Ti quality sum is complex carrier is stated, Ce, Ti molar ratio are 1:1.
9. the preparation method according to claim 4, which is characterized in that in the step (3), dip time is 12-
24h；Drying temperature is 80-120 DEG C, and maturing temperature is 400-600 DEG C, and calcining time is 3-8h.
10. application of any one of the claim 1-3 complex carrier ozone catalyst in water process, which is characterized in that institute
Complex carrier ozone catalyst catalytic ozonation degradation sanitary sewage, Industry Waste water pollutant are stated, the pollutant is to have
Machine pollutant.
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