CN108816272A - A kind of novel ferrimanganic two-component catalyst and catalytic degradation acetone method - Google Patents

A kind of novel ferrimanganic two-component catalyst and catalytic degradation acetone method Download PDF

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CN108816272A
CN108816272A CN201810462514.7A CN201810462514A CN108816272A CN 108816272 A CN108816272 A CN 108816272A CN 201810462514 A CN201810462514 A CN 201810462514A CN 108816272 A CN108816272 A CN 108816272A
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molecular sieve
micro porous
porous molecular
ferrimanganic
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林旭锋
席燕燕
陈碧丽
蔡文金
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China University of Petroleum East China
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

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Abstract

The invention belongs to be catalyzed and chemical field, it is related to a kind of micro porous molecular sieve load ferrimanganic two-component catalyst preparation method for containing vapour deposition process, and the method using micro porous molecular sieve load ferrimanganic two-component catalyst catalyzing oxidizing degrading acetone.Wherein, the preparation method of catalyst includes the following steps：One, solidliquid mixture is prepared；Two, ion exchange process；Three, the material before being vapor-deposited loads；Four, it is heat-treated for the first time；Five, it is heat-treated for second；Six, third time is heat-treated.The present invention also provides the methods that above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst is used for acetone catalyzing oxidizing degrading.Good effect of the present invention has：Involved catalyst preparation process safe operation, step are simple, at low cost；The micro porous molecular sieve that provided preparation process obtains through the invention loads ferrimanganic two-component catalyst, can be used for acetone catalytic oxidation；Due to being solid catalyst, catalyst also has the advantages that be easy to separate with liquid reactions system.

Description

A kind of novel ferrimanganic two-component catalyst and catalytic degradation acetone method
Technical field
The invention belongs to be catalyzed and chemical field, be related to it is a kind of based on vapour deposition process prepare ferrimanganic two-component catalyst and A kind of method of catalytic degradation acetone, and in particular, to micro porous molecular sieve load two component of ferrimanganic for containing vapour deposition process Method for preparing catalyst, and the side using micro porous molecular sieve load ferrimanganic two-component catalyst catalyzing oxidizing degrading acetone Method.
Background technique
Problem of environmental pollution is one of significant challenge of human kind sustainable development.Each major country is for environmental protection, green The attention of the industries such as color chemical industry all refers to the height of national strategy.Remove the organic pollutant that the industries such as industry, medical treatment generate It is one of pith and the difficult point of environmental protection；Wherein, carrying out catalyzing oxidizing degrading to organic matter by catalyst is one It is a efficiently, the method that is concerned by people.The key of this method is to prepare to have urging for efficient catalytic performance for the oxidation of organic matter Agent.Surface, transition-metal catalyst, including common carrier-borne transition metal catalysts are studied, are had for acetone, formaldehyde etc. The deep oxidation of machine object has preferable catalytic activity.Iron, manganese have as the biggish transition metal element of reserves in the earth's crust More variable valence, is suitable for a variety of catalysis reaction types, thus loading type iron or manganese or ferrimanganic two-component catalyst compared with Big research and development value.On the other hand, the specific embodiment that the catalytic performance of catalyst is then prepared with it again is closely related.However it is existing Have the system report in technical data for support type ferrimanganic two-component catalyst standby few, method is limited, while people to its It is short in understanding in the catalytic applications of catalytic organism oxidation.By taking acetone catalysis oxidation as an example, in the technical data being closer to, enemy Thick field etc.（Bibliography：Chou Houtian, Xu Haiping, Shi Guoyin, Deng Liang, ZSM-5 load dream oxide catalyst acetone, Shanghai second Polytechnical university's journal, 2015,32（2）：91-95）It is prepared for the Mn catalyst of ZSM-5 load, it, can be under ultraviolet light By acetone removal up to ~ 65% in for 24 hours.Jin Mei（Bibliography：Jin Mei, the oxidation point of acetone on catalyst of transition metal oxide Solution, master thesis, 2007）Use ZrO2Supported Manganese component can get acetone removal rate and be up under ultraviolet light 77%。
It can be seen that for acetone oxidation removal technology from above-mentioned data, there is also exploitation new catalytics for this field The needs of agent preparation method, especially green, catalyst and preparation method at low cost, there is also optimization catalyst to use work Skill, such as needed without ultra-violet apparatus etc..
Summary of the invention
Of the existing technology to overcome the problems, such as, the present invention, which provides, a kind of to be prepared two component of ferrimanganic based on vapour deposition process and urges Agent and catalytic degradation acetone method.Wherein ferrimanganic two-component catalyst is that micro porous molecular sieve loads ferrimanganic two-component catalyst, Comprising ion exchange and a kind of novel gas-phase deposition in preparation method, this method raw material is without (low) poison, environment friend Good, safe operation, step are simple, at low cost.Micro porous molecular sieve obtained by this method loads ferrimanganic two-component catalyst simultaneously, It can show preferably to be catalyzed acetone oxidation degradation property.
To achieve the goals above, the technical scheme is that：
One kind preparing ferrimanganic two-component catalyst and catalytic degradation acetone method based on vapour deposition process, including micro porous molecular sieve is born The preparation method and micro porous molecular sieve load ferrimanganic two-component catalyst for carrying ferrimanganic two-component catalyst are for acetone catalysis oxygen Change the reaction process of degradation.
The preparation method of above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst, includes the following steps：
Step 1: solidliquid mixture is prepared；The specific method is as follows：
A certain amount of micro porous molecular sieve is mixed with manganese salt solution, forms solidliquid mixture, and the mixture is had such as Lower material mass proportion：
The quality of water is between 10 ~ 100 times of micro porous molecular sieve quality in aqueous solution；The quality of contained manganese element in aqueous solution It is between 0.02 ~ 1 times of micro porous molecular sieve quality；
Wherein, micro porous molecular sieve is one of FAU type, MFI type micro porous molecular sieve or above two is carried out with arbitrary proportion Mixing；
Wherein, manganese salt is one of manganese sulfate, manganese chloride, manganese nitrate and their any form of hydrates or several It is mixed with arbitrary proportion；
Step 2: ion exchange process；The specific method is as follows：
Solidliquid mixture described in step 1 is heated and stirred, heating makes solidliquid mixture temperature in room temperature ~ 95oC it Between；Kept for the time of heating and stirring within the scope of 1 ~ 12 h；
Stop heating and stirring and obtains solid by obtained solidliquid mixture by filtering；
Above-mentioned solid is placed in baking oven and is dried by heating；
Step 3: the material before vapor deposition loads；The specific method is as follows：
This step needs two containers：The first container and second container；Wherein, the first container is characterized in：One open appearance Device, the container can place heating in the heating cavity of a temperature-controllable；
Second container is characterized in：The container can be closed by lid；Volume after closed places a certain amount of powder enough And the first container is whole；The container can place heating in the heating cavity of a temperature-controllable；
The step of certain mass two obtained solids are put into the first container, and the first container is put into second container； The ferrocene of required quality is then put into except the first container and in the space within second container；Then use lid will Second container is closed；
Wherein, the quality of ferrocene is 0.2 ~ 5 times of the solid masses being put into the first container；
Step 4: being heat-treated for the first time；The specific method is as follows：
Second container closed described in step 3 is integrally placed in the heating cavity of a temperature-controllable, so that second container It is integrally heated；Heating temperature is controlled 80 ~ 170oWithin the scope of C, heating time is within the scope of 0.2 ~ 3 h；It is then natural It is cooled to 60oC or less；
Step 5: second is heat-treated；The specific method is as follows：
Second container lid closed described in step 4 is removed, and the first container is also removed；It will remain in second container Ferrocene wipe after, the first container is continued to put back to second container, and second container is closed；Second container is integrally put It is placed in the heating cavity of a temperature-controllable, so that second container is integrally heated；Heating temperature is controlled 180 ~ 250oWithin the scope of C, heating time is within the scope of 0.1 ~ 2 h；Then naturally cool to 60oC or less；
Step 6: third time is heat-treated；The specific method is as follows：
The first container described in step 5 is taken out out of second container, and the first container and its micro porous molecular sieve held are placed on In the heating cavity of one temperature-controllable；The first container is heated, controls heating temperature 350 ~ 650oWithin the scope of C, when heating Between within the scope of 1 ~ 7 h；Then naturally cool to 60oC or less；
After the step is finished, the preparation of micro porous molecular sieve load ferrimanganic two-component catalyst is completed；I.e. in the first container It obtains micro porous molecular sieve and loads ferrimanganic two-component catalyst.
In above-mentioned " step 5 ", " it will remain in after the ferrocene in second container wipes, the first container continued to put back to Second container, and second container is closed ", another substitution operating method is：A new second container is looked for, first is held Device is placed in new second container, and new second container is closed；In this substitution operating method, " new second container " also has There is " second container " feature of " step 3 " defined.
Above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst is used for the reaction process of acetone catalyzing oxidizing degrading, uses Above-mentioned micro porous molecular sieve loads ferrimanganic two-component catalyst, and includes following processing step and condition：
The micro porous molecular sieve supported ferric catalyst for filling certain mass in the reaction vessel is mixed with water, acetone, hydrogen peroxide, so that They meet following proportion：
It is reference with the quality of water, hydrogen peroxide quality is 0.0005 ~ 0.33 times of water quality, and acetone quality is water quality 0.001 ~ 0.01 times, micro porous molecular sieve supported ferric catalyst quality is 0.0002 ~ 0.005 times of water quality；
Solution in said vesse is stirred and is heated, stirring rate is controlled in 50 ~ 1200 revs/min of ranges Interior, heating and temperature control is 25 ~ 75oWithin the scope of C.
Since reaching above-mentioned process conditions, within 24 h, acetone can reach up to 95.0% degradation rate in container.
" degradation rate " of above-mentioned acetone, sees in catalysis or chemical technology field, actually is equivalent to reaction conversion ratio, i.e., The amount of the reactant of chemical conversion occurs（Or quality）, divided by the amount of substance in reaction system before reacting（Or quality）.Therefore, on The degradation rate for stating acetone may be defined as：
(mAcetone, 0 – mAcetone, t) / mAcetone, 0,（Formula 1）
Wherein, mAcetone, 0--- the quality of acetone in preceding container is reacted,
mAcetone, t--- react the quality of acetone in container after having carried out certain time.
Material mass analysis method involved in the calculating of above-mentioned formula 1, belongs to the art conventional method, herein not It illustrates again.For acetone, its containing in liquid system can be measured by spectrophotometry, red, orange, green, blue, yellow (ROGBY) etc. Amount, but it is not limited to the above method.
" a certain amount of micro porous molecular sieve is mixed " described in above-mentioned steps one with manganese salt solution, can be and first prepare manganese Saline solution then mixes molecular sieve with the aqueous solution；Directly molecular sieve and manganese salt solid can also be separately added into water； Due to the solubility of manganese salt, manganese salt solution is spontaneously formed in water, therefore above two operation is no matter from principle or skill See it is all equivalence operation in art.
The chemical molecular formula of above-mentioned " ferrocene " is FeC10H10。
It is well known that FAU type, MFI type micro porous molecular sieve refer to the crystal structure types of micro porous molecular sieve, in this field The crystal type of molecular sieve usually sieves association by International Molecular（International association of zeolite）It is fixed Justice, definition mode disclose all technical staff.
It is well known that it is " silica alumina ratio " that micro porous molecular sieve, which also has a technical parameter, silicon in micro porous molecular sieve is referred to The mole of element and the mole ratio of aluminium element, are usually denoted as " Si/Al ratio " or " Si/Al "；For above-mentioned technical side For case, the Si/Al of any ratio be can carry out.In more excellent scheme, " Si/Al " may be selected in 2.0 ~ 15.0 ranges；? Within the scope of this, above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst can obtain mass percent containing manganese element 1.0 ~ 9.0 Between wt%；Containing ferro element also between 1.0 ~ 9.0 wt%.
" heating makes solidliquid mixture temperature in room temperature ~ 95 in above-mentioned steps twooBetween C ", preferred range 70 ~ 90 oC。
By the operation of solid " drying " described in above-mentioned steps two, carry out preparing material being common operation for this field, it should Operation is to remove in solid for the purpose of volatile liquid；Volatile liquid is water in the present case.Common drying operation is that will contain Water solid is heated to 100 ~ 130oC keeps 3 ~ 18 h；But it is not limited to the drying condition.
" the heating chamber of temperature-controllable involved in the preparation method of above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst Body " belongs to common a kind of device in industrial or laboratory, and with certain inner space, which can be put It sets and is heated object, and the temperature of the inner space can be set by temperature controller device and realize target temperature；Usually But it is not limited to the devices such as baking oven, oven, Muffle furnace.
The positive effect of the present invention is as follows：
（1）, ferrimanganic two-component catalyst preparation process involved in the present invention have raw material it is malicious, environmental-friendly without (low), operation pacify Entirely, simple, the at low cost feature of step.
（2）, ferrimanganic two-component catalyst preparation process involved in the present invention have preferable expansion, those skilled in the art Be easy to by expansion be iron and other metal components two-component catalyst.
（3）, through the invention provided by preparation process obtain micro porous molecular sieve load ferrimanganic two-component catalyst, can For acetone catalytic oxidation；Due to being solid catalyst, catalyst also have be easy to separate with liquid reactions system it is excellent Point.
Specific embodiment
Embodiment one,
One kind preparing ferrimanganic two-component catalyst and catalytic degradation acetone method based on vapour deposition process, including micro porous molecular sieve is born The preparation method and micro porous molecular sieve load ferrimanganic two-component catalyst for carrying ferrimanganic two-component catalyst are for acetone catalysis oxygen Change the reaction process of degradation.
The preparation method of above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst, includes the following steps：
Step 1: solidliquid mixture is prepared；The specific method is as follows：
A certain amount of micro porous molecular sieve is mixed with manganese salt solution, forms solidliquid mixture, and the mixture is had such as Lower material mass proportion：
The quality of water is 50 times of micro porous molecular sieve quality in aqueous solution；The quality of contained manganese element is microporous molecular in aqueous solution 0.59 times for sieving quality；
Wherein, micro porous molecular sieve is MFI type micro porous molecular sieve；
Wherein, manganese salt is manganese sulfate monohydrate；
The silica alumina ratio Si/Al of molecular sieve used is 12.1 in this example, and quality is 10.0 g；According to said ratio, the quality of water is 500 g, i.e., ~ 500 mL；Manganese element quality is 5.9 g, i.e., ~ 0.1 mol；Correspondingly, the quality of manganese sulfate monohydrate is 16.9 g；
Step 2: ion exchange process；The specific method is as follows：
Solidliquid mixture described in step 1 is heated and stirred, heating makes solidliquid mixture temperature 92oC；Keep heating And the time of stirring is 6 h；
Stop heating and stirring and obtains solid by obtained solidliquid mixture by filtering；
Above-mentioned solid is placed in baking oven and is dried by heating；
Step 3: the material before vapor deposition loads；The specific method is as follows：
This step needs two containers：The first container and second container；Wherein, the first container is characterized in：One open appearance Device, the container can place heating in the heating cavity of a temperature-controllable；
Second container is characterized in：The container can be closed by lid；Volume after closed places a certain amount of powder enough And the first container is whole；The container can place heating in the heating cavity of a temperature-controllable；
The step of certain mass two obtained solids are put into the first container, and the first container is put into second container； The ferrocene of required quality is then put into except the first container and in the space within second container；Then use lid will Second container is closed；
In this example, the first container is a quartz container, and second container i.e. its lid is simple glass material；It is put into first Solid masses in container is 8.0 g；
Wherein, the quality of ferrocene is 1.5 times of the solid masses being put into the first container, i.e. 12.0 g；
Step 4: being heat-treated for the first time；The specific method is as follows：
Second container closed described in step 3 is integrally placed in the heating cavity of a temperature-controllable, so that second container It is integrally heated；Controlling heating temperature is 105oC, heating time are 2.0 h；Then naturally cool to 60oC or less；
Step 5: second is heat-treated；The specific method is as follows：
Second container lid closed described in step 4 is removed, and the first container is also removed；It will remain in second container Ferrocene wipe after, the first container is continued to put back to second container, and second container is closed；Second container is integrally put It is placed in the heating cavity of a temperature-controllable, so that second container is integrally heated；Controlling heating temperature is 190oC, heating Time is 1.5 h；Then naturally cool to 60oC or less；
Step 6: third time is heat-treated；The specific method is as follows：
The first container described in step 5 is taken out out of second container, and the first container and its micro porous molecular sieve held are placed on In the heating cavity of one temperature-controllable；The first container is heated, control heating temperature is 550oC, heating time are 6 h；Then Naturally cool to 60oC or less；
After the step is finished, the preparation of micro porous molecular sieve load ferrimanganic two-component catalyst is completed；I.e. in the first container It obtains micro porous molecular sieve and loads ferrimanganic two-component catalyst.
Above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst is used for the reaction process of acetone catalyzing oxidizing degrading, and use is above-mentioned Micro porous molecular sieve loads ferrimanganic two-component catalyst, and includes following processing step and condition：
The micro porous molecular sieve supported ferric catalyst for filling certain mass in the reaction vessel is mixed with water, acetone, hydrogen peroxide, so that They meet following proportion：
It is reference with the quality of water, hydrogen peroxide quality is 0.003 times of water quality, and acetone quality is the 0.0025 of water quality Times, 0.001 times of micro porous molecular sieve supported ferric catalyst；In this example, the quality of water is 200 g.
Solution in said vesse is stirred and is heated, stirring rate is 120 revs/min, and heating temperature is 50 oC。
Since reaching above-mentioned process conditions, after 8 h, Acetone decomposition rate is 59% in container.
Embodiment two,
One kind preparing ferrimanganic two-component catalyst and catalytic degradation acetone method based on vapour deposition process, including micro porous molecular sieve is born The preparation method and micro porous molecular sieve load ferrimanganic two-component catalyst for carrying ferrimanganic two-component catalyst are for acetone catalysis oxygen Change the reaction process of degradation.
The preparation method of above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst, implementation method, other same embodiments One, difference is：
Step 1: solidliquid mixture is prepared；The specific method is as follows：
Wherein, micro porous molecular sieve is FAU type micro porous molecular sieve；The silica alumina ratio Si/Al of molecular sieve used is 2.6 in this example；
Step 4: being heat-treated for the first time；The specific method is as follows：
Second container closed described in step 3 is integrally placed in the heating cavity of a temperature-controllable, so that second container It is integrally heated；Controlling heating temperature is 130oC, heating time are 2.0 h；Then naturally cool to 60oC or less；
Step 5: second is heat-treated；The specific method is as follows：
Second container lid closed described in step 4 is removed, and the first container is also removed；It will remain in second container Ferrocene wipe after, the first container is continued to put back to second container, and second container is closed；Second container is integrally put It is placed in the heating cavity of a temperature-controllable, so that second container is integrally heated；Controlling heating temperature is 200oC, heating Time is 1.0 h；Then naturally cool to 60oC or less；
As in the first embodiment, obtaining " micro porous molecular sieve loads ferrimanganic two-component catalyst " after step 6 terminates.
Above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst is used for the reaction process of acetone catalyzing oxidizing degrading, uses The micro porous molecular sieve that the present embodiment obtains loads ferrimanganic two-component catalyst, and includes following processing step and condition：
With embodiment one.
Since reaching required process conditions, after 8 h, Acetone decomposition rate is 78% in container.

Claims (4)

1. one kind prepares ferrimanganic two-component catalyst and catalytic degradation acetone method, including micro porous molecular sieve based on vapour deposition process The preparation method and micro porous molecular sieve load ferrimanganic two-component catalyst for loading ferrimanganic two-component catalyst are catalyzed for acetone The reaction process of oxidative degradation；It is characterized in that：
The preparation method of above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst, includes the following steps：
Step 1: solidliquid mixture is prepared；The specific method is as follows：
A certain amount of micro porous molecular sieve is mixed with manganese salt solution, forms solidliquid mixture, and the mixture is had such as Lower material mass proportion：
The quality of water is between 10 ~ 100 times of micro porous molecular sieve quality in aqueous solution；The quality of contained manganese element in aqueous solution It is between 0.02 ~ 1 times of micro porous molecular sieve quality；
Wherein, micro porous molecular sieve is one of FAU type, MFI type micro porous molecular sieve or above two is carried out with arbitrary proportion Mixing；
Wherein, manganese salt is one of manganese sulfate, manganese chloride, manganese nitrate and their any form of hydrates or several It is mixed with arbitrary proportion；
Step 2: ion exchange process；The specific method is as follows：
Solidliquid mixture described in step 1 is heated and stirred, heating makes solidliquid mixture temperature in room temperature ~ 95oC it Between；Kept for the time of heating and stirring within the scope of 1 ~ 12 h；
Stop heating and stirring and obtains solid by obtained solidliquid mixture by filtering；
Above-mentioned solid is placed in baking oven and is dried by heating；
Step 3: the material before vapor deposition loads；The specific method is as follows：
This step needs two containers：The first container and second container；Wherein, the first container is characterized in：One open appearance Device, the container can place heating in the heating cavity of a temperature-controllable；
Second container is characterized in：The container can be closed by lid；Volume after closed places a certain amount of powder enough And the first container is whole；The container can place heating in the heating cavity of a temperature-controllable；
The step of certain mass two obtained solids are put into the first container, and the first container is put into second container； The ferrocene of required quality is then put into except the first container and in the space within second container；Then use lid will Second container is closed；
Wherein, the quality of ferrocene is 0.2 ~ 5 times of the solid masses being put into the first container；
Step 4: being heat-treated for the first time；The specific method is as follows：
Second container closed described in step 3 is integrally placed in the heating cavity of a temperature-controllable, so that second container It is integrally heated；Heating temperature is controlled 80 ~ 170oWithin the scope of C, heating time is within the scope of 0.2 ~ 3 h；It is then natural It is cooled to 60oC or less；
Step 5: second is heat-treated；The specific method is as follows：
Second container lid closed described in step 4 is removed, and the first container is also removed；It will remain in second container Ferrocene wipe after, the first container is continued to put back to second container, and second container is closed；Second container is integrally put It is placed in the heating cavity of a temperature-controllable, so that second container is integrally heated；Heating temperature is controlled 180 ~ 250oWithin the scope of C, heating time is within the scope of 0.1 ~ 2 h；Then naturally cool to 60oC or less；
Step 6: third time is heat-treated；The specific method is as follows：
The first container described in step 5 is taken out out of second container, and the first container and its micro porous molecular sieve held are placed on In the heating cavity of one temperature-controllable；The first container is heated, controls heating temperature 350 ~ 650oWithin the scope of C, when heating Between within the scope of 1 ~ 7 h；Then naturally cool to 60oC or less；
After the step is finished, the preparation of micro porous molecular sieve load ferrimanganic two-component catalyst is completed；I.e. in the first container It obtains micro porous molecular sieve and loads ferrimanganic two-component catalyst.
2. a kind of vapour deposition process that is based on according to claim 1 prepares ferrimanganic two-component catalyst and catalytic degradation acetone Method, preparation method and micro porous molecular sieve including micro porous molecular sieve load ferrimanganic two-component catalyst load two groups of ferrimanganic Divided catalyst is used for the reaction process of acetone catalyzing oxidizing degrading；It is characterized in that：In above-mentioned " step 5 ", " will be remained in After ferrocene in two containers is wiped, the first container is continued to put back to second container, and second container is closed ", it is another A substitution operating method is：A new second container is looked for, the first container is placed in new second container, and by new second Container closure；In this substitution operating method, " new second container " is also with " second container " feature of " step 3 " defined.
3. a kind of vapour deposition process that is based on according to claim 1 to 2 prepares ferrimanganic two-component catalyst and catalytic degradation third Ketone method, preparation method and micro porous molecular sieve including micro porous molecular sieve load ferrimanganic two-component catalyst load ferrimanganic two Component catalyst is used for the reaction process of acetone catalyzing oxidizing degrading；It is characterized in that：
Above-mentioned micro porous molecular sieve load ferrimanganic two-component catalyst is used for the reaction process of acetone catalyzing oxidizing degrading, and use is above-mentioned Micro porous molecular sieve loads ferrimanganic two-component catalyst, and includes following processing step and condition：
The micro porous molecular sieve supported ferric catalyst for filling certain mass in the reaction vessel is mixed with water, acetone, hydrogen peroxide, so that They meet following proportion：
It is reference with the quality of water, hydrogen peroxide quality is 0.0005 ~ 0.33 times of water quality, and acetone quality is water quality 0.001 ~ 0.01 times, micro porous molecular sieve supported ferric catalyst quality is 0.0002 ~ 0.005 times of water quality；
Solution in said vesse is stirred and is heated, stirring rate is controlled in 50 ~ 1200 revs/min of ranges Interior, heating and temperature control is 25 ~ 75oWithin the scope of C.
4. a kind of vapour deposition process that is based on according to claim 1 to 3 prepares ferrimanganic two-component catalyst and catalytic degradation third Ketone method, preparation method and micro porous molecular sieve including micro porous molecular sieve load ferrimanganic two-component catalyst load ferrimanganic two Component catalyst is used for the reaction process of acetone catalyzing oxidizing degrading；It is characterized in that：From reaching technique item described in claim 3 Part starts, and within 24 h, acetone can reach up to 95.0% degradation rate in container.
CN201810462514.7A 2018-05-15 2018-05-15 A kind of novel ferrimanganic two-component catalyst and catalytic degradation acetone method Pending CN108816272A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070004944A1 (en) * 2005-07-01 2007-01-04 The Regents Of The University Of California Process and catalyst for oxidation of hydrocarbons
CN102824925A (en) * 2012-05-30 2012-12-19 浙江工业大学 Ferrum-molecular sieve catalyst and application thereof
CN103383321A (en) * 2013-07-24 2013-11-06 上海交通大学 Fenton-method sample pretreatment method for metal-heteroatom zeolite molecular sieves
CN103934042A (en) * 2014-04-29 2014-07-23 中国石油大学(华东) Vapor-phase deposition preparation method of load type iron catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070004944A1 (en) * 2005-07-01 2007-01-04 The Regents Of The University Of California Process and catalyst for oxidation of hydrocarbons
CN102824925A (en) * 2012-05-30 2012-12-19 浙江工业大学 Ferrum-molecular sieve catalyst and application thereof
CN103383321A (en) * 2013-07-24 2013-11-06 上海交通大学 Fenton-method sample pretreatment method for metal-heteroatom zeolite molecular sieves
CN103934042A (en) * 2014-04-29 2014-07-23 中国石油大学(华东) Vapor-phase deposition preparation method of load type iron catalyst

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