CN106732509B - Preparation method, catalytic ozone oxidation catalyst and its application of modified aluminium oxide supports - Google Patents
Preparation method, catalytic ozone oxidation catalyst and its application of modified aluminium oxide supports Download PDFInfo
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- CN106732509B CN106732509B CN201611267017.9A CN201611267017A CN106732509B CN 106732509 B CN106732509 B CN 106732509B CN 201611267017 A CN201611267017 A CN 201611267017A CN 106732509 B CN106732509 B CN 106732509B
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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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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- B01J32/00—
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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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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to water-treatment technology fields, the in particular to preparation method of modified aluminium oxide supports, catalytic ozone oxidation catalyst and its application.A kind of preparation method of modified aluminium oxide supports, comprising the following steps: aluminum oxide base material is provided；A aluminum oxide base material modifying agent of progress is sprayed, primary drying, primary roasting, cooled to room temperature；The aluminum oxide base material second of modifying agent of progress is sprayed, redrying, after baking, cooled to room temperature；Obtain modified aluminium oxide supports.The beneficial effects of the invention are that: using catalytic ozone oxidation catalyst prepared by modified aluminium oxide supports of the present invention, so that COD removal rate increases substantially, to reduce cost of sewage disposal；In addition, digestion of metallic ion rate substantially reduces, to extend the service life of catalyst；Also, the low in cost of catalyst, preparation process are simple, are very suitable to industrialized production.
Description
Technical field
The present invention relates to water-treatment technology fields, the in particular to preparation method of modified aluminium oxide supports, catalysis ozone oxygen
Change catalyst and its application.
Background technique
Catalytic ozonation is as a kind of high-level oxidation technology efficient, practical, without secondary pollution, in the difficult drop of processing
Solution field of sewage is with a wide range of applications, and is the research hotspot of sewage treatment field in recent years.
But the bottleneck problem for restricting catalytic ozonation large-scale application be sewage treatment cost it is too high, and mention
The activity of high catalyst can greatly reduce ozone dosage, to reduce the operating cost of sewage treatment.
Application No. is 200710032553.5 patents of invention to disclose a kind of haydite catalysis for catalytic ozonation
The preparation method of agent, this method include the preparation of haydite materials core, catalyst to the cladding and roasting technique of haydite materials core:
Catalyst is by MnO, MnO to the cladding of haydite materials core2、TiO2、CoO、Co3O4、Fe2O3With it is one or more compound in FeO
Catalyst active component to be ground into partial size be 0.1-1mm, mixed with the raw material of haydite production, and mixture be supported on haydite
On raw material core, the haydite of the coated catalysts of 3-4mm is generated；The ceramsite catalyst for catalytic ozonation is made.
Application No. is 200810128809.7 patents of invention to disclose a kind of hydroxylating zinc ozone catalyst；The hydroxylating
Zinc catalyst is prepared according to the following steps: being stirred continuously concentration and is the soluble Zn salting liquid of 0.2-2.0mol/L, and is slowly added dropwise
Concentration is the alkaline solution of 0.25-2.05mol/L until occurring without precipitating；Regulating step one shortens pH > 12 of suspension into, then
It is placed in 30-60 DEG C of environment and activates 12-20h；Sediment is washed with distilled water to after neutrality and dries to get hydroxyl is arrived by filtering
Base zinc.
Application No. is 201010539704.8 patents of invention to disclose a kind of catalytic ozonation of Treatment of Cyanide-containing Wastewater
The preparation method of catalyst: using unformed aluminium oxide as carrier, in pelletizer, by active ingredient copper, iron, tin with the shape of solution
Formula sprays into, and catalyst is made after maintenance, drying, roasting.
Application No. is 201110046323.0 patents of invention to disclose a kind of ozone oxidation decomposition organic pollutants
Catalyst.The catalyst is ferrospinel or its compound, and wherein ferrospinel is NiFe2O4, MnFe2O4,
CoFe2O4, ZnFe2O4, MgFe2O4, CuFe2O4, CrFe2O4, PbFe2O4, SrFe2O4, BaFe2O4And CaFe2O4One of or
The combination of two of them.
Application No. is 201510394371.7 patent applications to disclose a kind of ozone oxidation for loading poly-metal deoxide
The preparation method of catalyst: carrier is pre-processed first: after carrier is washed, is impregnated, is washed out into acid solution
Property, drying；Pretreated carrier is subjected to impregnation at least once, then dry, roasting.Wherein dipping solution be manganese,
The nitrate of metallic element at least 3 in nickel, iron, cerium, cobalt and copper, sulfate, acetate or chloride mixed solution, and
Concentration of the various metallic elements in dipping solution is 0.01-1.00mol/L.
Application No. is 201510301014.1 patent applications to disclose a kind of preparation method of ozone oxidation catalyst: choosing
It uses industrial hydrotalcite as the persursor material of catalyst carrier, obtains catalyst carrier after Muffle kiln roasting；It will urge again
Agent carrier manganese at a certain temperature, centainly matching, nickel, iron, cerium, cobalt, copper mixing salt solution in one section of concussion dipping
Time, dry after dipping object filtering, then roasting obtains finished catalyst.
Application No. is the patent application of CN201510879919.7 disclose it is a kind of using alumina silicate as the Metal Supported of carrier
The preparation method of type catalyst, preparation method include the following contents: taking kaolin powder, aluminium-hydroxide powder, metal ion living
Property component, pore creating material are sufficiently mixed using blender；Mixed component material is delivered into sugar coating machine, adhesive is sprayed into, will mix
The sizing catalyst Precursors that partial size is 2-4mm are made in powder；Certainly subsequently into drying-heating preheating-constant high temperature roasting-
So cooling.
Application No. is the patent applications of CN201510976885.3 to disclose a kind of catalyst for catalytic ozonation
And preparation method thereof.Active component is supported on carried by active carbon as carrier, with the method mixed in situ using active carbon by the catalyst
On body, preparation method includes crushing, ingredient, molding and drying, charing and activation.
Application No. is 201510617018.0 patent applications to disclose a kind of load type laminated bimetal composite oxide
The preparation method of catalyst, comprising the following steps: pre-process catalyst carrier；By bivalent metal ion and trivalent metal
The mixing salt solution and NaOH and Na of ion2CO3Mixed solution simultaneously be added in full back-mixing rotating liquid-film reactor, react
1-3min obtains the mixed serum containing layered bi-metal complex hydroxide nucleus；Layered double hydroxide will be contained
The mixed solution of nucleus and pretreated catalyst carrier are transferred in reaction kettle, and 60-150 DEG C of reaction 2-24h is dried later
Processing, obtains the precursor of load type laminated bimetal composite oxide catalyst；By above-mentioned precursor in 250-500 DEG C of roasting 2-
8h obtains load type laminated bimetal composite oxide catalyst.
Application No. is the patent applications of CN201610067238.5 to disclose a kind of ozone catalytic oxygen for wastewater treatment
Change catalyst and preparation method thereof, which is made of active component, auxiliary agent and carrier；Wherein, the active component was
Metal oxide is crossed, auxiliary agent is alkali metal oxide, alkaline earth oxide or lanthanide metal oxide；The carrier is oxidation
Aluminium, active carbon or haydite.The present invention still further provides the preparation method of the catalyst, that is, uses infusion process or dry pigmentation will
Active component, auxiliary agent and dispersing agent are supported on carrier, are made after health, drying, roasting.
Application No. is the patent applications of CN201610067240.2 to disclose a kind of ozone catalytic oxygen for wastewater treatment
Change catalyst, is made of active component, auxiliary agent and carrier；Wherein, the active component is transition metal oxide, and auxiliary agent is alkali
Metal oxide, alkaline earth oxide or lanthanide metal oxide；The carrier is the modification through peracid treatment or alkali process
Carrier.The present invention still further provides the preparation method of the catalyst, comprising: carries out through peracid treatment or alkali process to carrier
It is modified, obtain modified support；Active component, auxiliary agent and dispersing agent are supported on the modified support using infusion process；Through supporting
Ozone catalytic oxidation catalyst is made after raw, dry, roasting.
Application No. is the patent application of CN201610149834.8 disclose it is a kind of for ozone in water decompose solid urge
Agent and preparation method thereof and the method for decomposing ozone in water, treated that red mud Supported Manganese is made by dealkalize for the solid catalyst
Beaded catalyst.The preparation method comprises the following steps: preparing catalyst using industrial waste red mud, CO is used2After gas carries out dealkalize to red mud,
Impregnation is carried out with manganese nitrate solution again, after low temperature drying impregnates the red mud of manganese nitrate, then high-temperature roasting is made particle and urges
Agent.
With the raising of sewage drainage standard, to sewage treatment high-level oxidation technology, especially catalytic ozonation
Requirement it is higher and higher, and catalyst be catalytic ozonation can large-scale application one of key factor.Above-mentioned hair
The catalytic ozone oxidation catalyst that bright process is prepared, performance can't fully meet the needs of industrial application.
Therefore, developing catalyst industrialization technology with independent intellectual property rights is just particularly important and urgently.The present invention is exactly needle
The improvement made to the above-mentioned prior art, is first modified alumina support, then uses the modified aluminium oxide as load
Body, has obtained a kind of catalytic performance and digestion of metallic ion is better than the catalytic ozone oxidation catalyst of the prior art.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of preparation method of modified aluminium oxide supports；
A second object of the present invention is to provide a kind of modified aluminium oxide supports preparation catalytic ozone oxidation catalyst and
Its application in sewage treatment；
Cost-effective solution problems of the prior art.
Specific technical solution of the present invention is as follows:
A kind of preparation method of modified aluminium oxide supports, comprising the following steps:
Aluminum oxide base material is provided；A aluminum oxide base material modifying agent of progress is sprayed, primary drying, primary roasting,
Cooled to room temperature；The aluminum oxide base material second of modifying agent of progress is sprayed, redrying, after baking, it is naturally cold
But to room temperature；Obtain modified aluminium oxide supports.
Further, a maturing temperature is 300-800 DEG C, time 2-4h.
Further, the after baking temperature is 300-800 DEG C, time 2-4h.
Further, a modifying agent is one of nitrogen group element, carbon group element, halogen or multiple element
Compound water solution.
Further, a modifying agent mass content is 0-10mmol/g.
Further, described twice-modified dose is one of the first major element, the second major element or multiple element
Compound water solution.
Further, the twice-modified dose of mass content is 0.1-10mmol/g.
Further, a kind of catalytic ozone oxidation catalyst, using the preparation method system of the modified aluminium oxide supports
Carrier of the modified aluminium oxide supports obtained as catalyst, is used for sewage treatment.
Compared with the prior art, the present invention has the following beneficial effects:
(1) in the preparation method of modified aluminium oxide supports of the present invention, since aluminum oxide base material has aquation,
Certain groups are formed in the liquid phase, so that particle surface is no longer neutral；It is twice-modified when twice-modified dose of dosage is less
Agent is modified alumina support, and by roasting, the twice-modified dose of lattice for being able to enter aluminum oxide is positively charged
Cation is fixed on the skeleton of carrier, is not easily runed off；But when twice-modified dose of dosage is larger, twice-modified dose cannot be complete
Portion enters the lattice of aluminium oxide, to be easy to be lost；Before twice-modified dose sprays, using a modifying agent to carrying alumina
Body is modified, and forms it into negatively charged chemical bond, thus make twice-modified dose be easier it is immobilized in carrier surface.Separately
Outside, modification twice is bonded active component and carrier stronger, thus greatly reduces the dissolution of active component.
(2) rate determining step of Organic substance in water and ozone reaction is dynamics Controlling, equally distributed catalyst pair
Rate determining step is that the reaction of dynamics Controlling is most advantageous.Twice-modified dose is modified by introducing band aluminum oxide base material
The mode of positive charge cation changes the cellular structure and polarity of carrier, is conducive to formation and its performance hair of catalytic active site
It waves, is conducive to active component and forms uniform type；And active component is more difficult to assemble, so as to cause active component dispersion degree
It improves, to improve its catalytic activity and service life.
(3) catalytic ozone oxidation catalyst that carrying transition metal compound is prepared into not only increases COD in sewage
Removal rate, and the amount of dissolution of active component is low, and stability is high.In addition, the mechanical performance of the catalyst is high, can iterative cycles make
With, reduction secondary pollution, while reducing the investment operating cost of sewage treatment.
(4) catalyst made of carrier provided in an embodiment of the present invention is not limited to the MBR of advanced treating municipal wastewater
It is reverse osmosis concentrated that (membrane bioreactor, similarly hereinafter) produces water, DF film (microfiltration membranes, similarly hereinafter) concentrated water in municipal wastewater bi-membrane method, refinery
Water, coal chemical industry reverse osmosis concentrated water are also applied for the reverse osmosis concentrated water of other systems such as processing oil recovery reverse osmosis concentrated water, meanwhile,
Suitable for the sewage treatment of other systems, such as processing dyeing and printing sewage, phenol-containing wastewater, ester-contaning compounds, arene chemical combination
The sewage etc. of object and small molecule acid.
Specific embodiment
A specific embodiment of the invention is clearly and completely described below in conjunction with embodiment, it is clear that described
Embodiment be a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without making creative work belongs to what the present invention protected
Range.
Heretofore described, a kind of preparation method of modified aluminium oxide supports, comprising the following steps:
Aluminum oxide base material is provided；A aluminum oxide base material modifying agent of progress is sprayed, primary drying, primary roasting,
Cooled to room temperature.
Heretofore described, a modifying agent is one of nitrogen group element, carbon group element, halogen or a variety of members
The compound water solution of element；
Heretofore described, a modifying agent mass content is 0-10mmol/g；Preferably, a modifying agent matter
Amount content is 0-6mmol/g；Surplus is carrier；
Heretofore described, primary drying temperature is 120-150 DEG C, time 3-4h；
Heretofore described, a maturing temperature is 300-800 DEG C, time 2-4h；
The aluminum oxide base material second of modifying agent of progress is sprayed, redrying, after baking, naturally cools to room
Temperature；Obtain modified aluminium oxide supports.
Heretofore described, twice-modified dose is one of the first major element, the second major element or a variety of members
The compound water solution of element；
Heretofore described, twice-modified dose of mass content is 0.1-10mmol/g；Preferably, described twice-modified dose
Mass content is 0.1-6mmol/g；Surplus is carrier；
Positively charged cation is securely seated between carrier by negatively charged chemical bond in described twice-modified dose
On skeleton.The twice-modified dose of cellular structure and polarity that can change carrier, is conducive to active component and forms uniform type, to prolong
The service life of catalyst is grown.
Heretofore described, redrying temperature is 100-150 DEG C, time 3-5h；
Heretofore described, after baking temperature is 300-800 DEG C, time 2-4h；
A heretofore described modifying agent, which is modified alumina support, can form on the surface of the carrier with negative
The chemical bond of charge is more advantageous to immobilized twice-modified dose.
Heretofore described, a kind of catalytic ozone oxidation catalyst, using the preparation of the modified aluminium oxide supports
Carrier of the modified aluminium oxide supports made from method as catalyst.
Heretofore described, a kind of preparation method of catalytic ozone oxidation catalyst, comprising the following steps:
Preparing metal ion concentration by weight percentage, is 10% manganese acetate, iron nitrate solution, then presses 20:
10 volume ratio measures above two solution respectively and is configured to mixed impregnant liquor, then above-mentioned mixed impregnant liquor is sprayed in aluminium oxide
On carrier, then in 120 DEG C of dry 5h, the catalytic ozone oxidation catalyst finally is made in 500 DEG C of roasting 3h.
Heretofore described, a kind of purposes of the catalytic ozone oxidation catalyst is used for sewage treatment.
The catalyst that embodiment is prepared is used to handle sewage in fixed bed reactors, test condition is as follows:
Sewage is derived from the DF of bi-membrane method in Beijing Bishuiyuan Science and Technology Co., Ltd's municipal wastewater processing engineering project
Film concentrated water, COD content are 105mg/L.
Performance evaluation is carried out to catalytic ozone oxidation catalyst with the fixed bed reactors of internal diameter 40mm.Catalyst bed body
Product is 200ml, and sewage volume space velocity is 1h-1(i.e. the residence time is 60min), ozone dosage O3/ COD=2 (W).In room
Under temperature when continuous operation 10h, 20h and 30h, catalyst performance evaluation test is measured.
Using modified aluminium oxide supports of the present invention, transition metal active component in load is prepared into heterogeneous urge
Change ozone oxidation reaction catalyst, since the rate determining step of O3 catalytic oxidation removal COD reaction is dynamics Controlling, institute
With should be by catalyst preparation at uniform type.In addition, the Active components distribution of catalyst can be reduced catalyst inside particle
The abrasion of active component in the reactor, substantially increases its stability, not easily runs off active component, is conducive to extend catalysis
The service life of agent.
Comparative example 1
Described in the present embodiment, selects the aluminium oxide that partial size is 3-5mm as carrier, carrier is not modified.
Described in the present embodiment, the preparation method of catalytic ozone oxidation catalyst, comprising the following steps:
Preparing metal ion concentration by weight percentage, is 10% manganese acetate, iron nitrate solution, then presses 20:
10 volume ratio measures above two solution respectively and is configured to mixed impregnant liquor, then above-mentioned mixed impregnant liquor is sprayed in aluminium oxide
On carrier, then in 120 DEG C of dry 5h, the catalytic ozone oxidation catalyst finally is made in 500 DEG C of roasting 3h.
Catalytic ozone oxidation catalyst obtained by the present embodiment is tested for the property, test result is as shown in table 1.
Embodiment 1
Described in the present embodiment, a kind of preparation method of modified aluminium oxide supports, comprising the following steps:
Aluminum oxide base material is provided, 0.1mmol/g ammonium fluoride aqueous solution is sprayed on the aluminum oxide base material of 3-5mm, then
In 120 DEG C of dry 4h, in 300 DEG C of roasting 4h, cooled to room temperature；
2mmol/g sodium hydrate aqueous solution is sprayed for the second time on the aluminum oxide base material, then in 100 DEG C of dryings
4h, then in 400 DEG C of roasting 4h, cooled to room temperature is to obtain the modified alumina support in surface.
Described in the present embodiment, the preparation method of catalytic ozone oxidation catalyst, comprising the following steps:
Preparing metal ion concentration by weight percentage, is 10% manganese acetate, iron nitrate solution, then presses 20:
10 volume ratio measures above two solution respectively and is configured to mixed impregnant liquor, then above-mentioned mixed impregnant liquor is sprayed in aluminium oxide
On carrier, then in 120 DEG C of dry 5h, the catalytic ozone oxidation catalyst finally is made in 500 DEG C of roasting 3h.To this implementation
Example gained catalytic ozone oxidation catalyst is tested for the property, and test result is as shown in table 1.
Embodiment 2
The present embodiment be it is improved on the basis of embodiment 1, content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeats herein.
Described in the present embodiment, a kind of preparation method of modified aluminium oxide supports, comprising the following steps:
Aluminum oxide base material is provided, 4mmol/g polyacrylamide solution is sprayed on the aluminum oxide base material of 3-5mm, so
Afterwards in 120 DEG C of dry 3h, in 500 DEG C of roasting 2h, cooled to room temperature；
10mmol/g potassium nitrate aqueous solution is sprayed for the second time on the aluminum oxide base material, then in 100 DEG C of dry 4h,
Then in 300 DEG C of roasting 4h, cooled to room temperature is to obtain the modified alumina support in surface.
Catalytic ozone oxidation catalyst obtained by the present embodiment is tested for the property, test result is as shown in table 1.
Embodiment 3
The present embodiment be it is improved on the basis of embodiment 1, content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeats herein.
Described in the present embodiment, a kind of preparation method of modified aluminium oxide supports, comprising the following steps:
Aluminum oxide base material is provided, 5mmol/g ethylenediamine tetra-acetic acid (EDTA) aqueous solution is sprayed into the alumina base in 3-5mm
On material, then in 120 DEG C of dry 3h, in 800 DEG C of roasting 3h, cooled to room temperature；
3mmol/g prodan aqueous solution is sprayed for the second time on the aluminum oxide base material, then in 120 DEG C of dryings
4h, then in 500 DEG C of roasting 3h, cooled to room temperature is to obtain the modified alumina support in surface.
Catalytic ozone oxidation catalyst obtained by the present embodiment is tested for the property, test result is as shown in table 1.
Embodiment 4
The present embodiment be it is improved on the basis of embodiment 1, content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeats herein.
Described in the present embodiment, a kind of preparation method of modified aluminium oxide supports, comprising the following steps:
Aluminum oxide base material is provided, 10mmol/g dodecyl benzene sulfonic acid aqueous solution is sprayed to the aluminum oxide base material in 3-5mm
On, then in 150 DEG C of dry 3h, in 400 DEG C of roasting 2h, cooled to room temperature；
6mmol/g lithium nitrate aqueous solution is sprayed for the second time on the aluminum oxide base material, then in 150 DEG C of dry 3h,
Then in 800 DEG C of roasting 3h, cooled to room temperature is to obtain the modified alumina support in surface.
Catalytic ozone oxidation catalyst obtained by the present embodiment is tested for the property, test result is as shown in table 1.
Embodiment 5
The present embodiment be it is improved on the basis of embodiment 1, content described in embodiment 1 is also the present embodiment institute
Have, no longer specifically repeats herein.
Described in the present embodiment, a kind of preparation method of modified aluminium oxide supports, comprising the following steps:
Aluminum oxide base material is provided, 0.1mmol/g sodium citrate aqueous solution is sprayed on the aluminum oxide base material of 3-5mm, so
Afterwards in 120 DEG C of dry 4h, in 500 DEG C of roasting 3h, cooled to room temperature is to obtain the modified alumina support in surface.
Catalytic ozone oxidation catalyst obtained by the present embodiment is tested for the property, test result is as shown in table 1.
1 catalytic ozone oxidation catalyst performance evaluation test result of table
As shown in Table 1, embodiment 1 is prepared compared to the unmodified alumina support of comparative example 1, modified aluminium oxide supports
Catalytic ozone oxidation catalyst improves 30% to COD average removal rate；Embodiment 2 averagely removes COD compared to comparative example 1
Rate improves 34%；Embodiment 3 improves 39% to COD average removal rate compared to comparative example 1；Embodiment 4 is compared to comparison
Example 1 improves 34% to COD average removal rate；Embodiment 5 improves 37% to COD average removal rate compared to comparative example 1.
To sum up, used modified aluminium oxide supports prepare catalytic ozone oxidation catalyst so that in sewage COD removal
Rate improves 30%-40% compared to the catalyst of unmodified alumina support preparation, so that the operating cost of sewage treatment
It substantially reduces；Digestion of metallic ion rate is greatly reduced, to substantially prolong the service life of catalyst, reduce investment at
This.When for DF film concentrated water in advanced treating municipal wastewater bi-membrane method, COD content therein can be made to be brought down below 50mg/L,
Reach town sewage level-one emission standard A.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (6)
1. a kind of preparation method of modified aluminium oxide supports, it is characterised in that: the following steps are included:
Aluminum oxide base material is provided；A aluminum oxide base material modifying agent of progress is sprayed, primary drying, primary roasting, it is natural
It is cooled to room temperature, a maturing temperature is 300-800 DEG C；To the aluminum oxide base material carry out twice-modified dose spray, two
Secondary drying, after baking, cooled to room temperature, the after baking temperature are 300-800 DEG C；Obtain modified aluminas load
Body, a modifying agent are one of ammonium fluoride, polyacrylamide, ethylenediamine tetra-acetic acid, dodecyl benzene sulfonic acid or more
The aqueous solution of kind compound, described twice-modified dose is one of lithium, sodium, potassium or the compound water solution of multiple element.
2. the preparation method of modified aluminium oxide supports as described in claim 1, it is characterised in that: a calcining time is
2-4h。
3. the preparation method of modified aluminium oxide supports as described in claim 1, it is characterised in that: the after baking time is
2-4h。
4. the preparation method of modified aluminium oxide supports as described in claim 1, it is characterised in that: a modifying agent quality
Content is 0-10mmol/g, and a modifying agent mass content is not 0.
5. the preparation method of modified aluminium oxide supports as described in claim 1, it is characterised in that: the twice-modified dose of quality
Content is 0.1-10mmol/g.
6. a kind of catalytic ozone oxidation catalyst, it is characterised in that: use modified oxidized as described in claim any one of 1-5
Carrier of the modified aluminium oxide supports made from the preparation method of alumina supporter as catalyst is used for sewage treatment.
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| CN115245832B (en) * | 2021-12-28 | 2023-12-01 | 浙江理工大学 | Preparation method, product and application of fluorine doped metal oxide catalyst |
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