CN108033458A - Micro- mesoporous yolk-shell composite molecular sieve of a kind of carried metal and preparation method thereof and a kind of cigarette - Google Patents

Micro- mesoporous yolk-shell composite molecular sieve of a kind of carried metal and preparation method thereof and a kind of cigarette Download PDF

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Publication number
CN108033458A
CN108033458A CN201711325417.5A CN201711325417A CN108033458A CN 108033458 A CN108033458 A CN 108033458A CN 201711325417 A CN201711325417 A CN 201711325417A CN 108033458 A CN108033458 A CN 108033458A
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molecular sieve
compound
preparation
mesoporous
micro
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马扩彦
俞海军
戴亚
汪长国
唐杰
刘如灿
杜红毅
曾天
曾天一
邱光明
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Chongqing China Tobacco Industry Co Ltd
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Chongqing China Tobacco Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/14—Type A
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume

Abstract

The present invention provides a kind of preparation method of micro- mesoporous yolk shell composite molecular sieve of carried metal.Micro- mesoporous yolk shell composite molecular sieve of carried metal provided by the present invention, make full use of the cavity of yolk shell structure, acted on by the structure and metal composite in a variety of ducts of mesoporous and micropore, can effectively adsorb different size of pernicious gas molecule, reduce the harmfulness of cigarette.There is notable adsorption effect to the particularly benzo of the harmful substance in cigarette smoke [a] pyrene, crotonaldehyde etc..

Description

A kind of micro- mesoporous yolk-shell composite molecular sieve of carried metal and preparation method thereof with A kind of and cigarette
Technical field
The invention belongs to Harm reduction techniques technical field, and in particular to a kind of micro- mesoporous compound point of yolk-shell of carried metal Son sieve and preparation method thereof and a kind of cigarette.
Background technology
With the development of the society, smoking and environmental problem are of interest for the whole world.《The Framework Convention on Tobacco Control》Will Ask national governments to work up more severe " tobacco control " laws and regulations, promote tobacco productive corporation reducing releasing content of coke tar in cigarette While, more strictly to control the burst sizes of main harmful components in cigarette smoke.2009, by Zhengzhou, tobacco research institute took the lead The cigarette smoke for having carried out Chinese-style cigarette endangers sex index research, has filtered out 7 kinds of representative components and has endangered as cigarette Evil property evaluation index, such as CO, HCN, NNK, B [a] P, phenol.Porous material has abundant pore structure, regular duct point Cloth, has been used to reduce tobacco harmful components.In addition, in order to further improve the adsorption efficiency of the harmful components of porous material, Liu Shaomin etc. has synthesized the Me-MCM-48 of metallic element doping, it is found that the positive effect of Me-MCM-48 reduction benzoins is better than MCM-48 materials, but above-mentioned Metal Supported technology be easy to cause and comes off or block duct, under causing material specific surface area significantly Drop, so as to reduce the adsorption effect of pernicious gas.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of carried metal for reducing cigarette harmful components Micro- mesoporous yolk-shell composite molecular sieve and preparation method thereof, micro- mesoporous yolk-shell of carried metal provided by the invention is compound Molecular sieve makes full use of the cavity of yolk-shell structure, by the compound action of multi-pore channel and metal, effectively reduces the harm of cigarette Property.
The present invention provides a kind of preparation method of micro- mesoporous yolk-shell composite molecular sieve of carried metal, including it is following Step：
A) zeolite molecular sieve, alkaline matter, phenolic compound, aldehyde compound and water are mixed, carry out cross-linked polymeric Reaction, obtains the molecular sieve-phenolic resin compound with nucleocapsid structure；
B) by template, the aqueous solution of alcohol, alkaline matter, step A) obtained compound and organosilicon source compound mix Close, reacted, obtain having nucleocapsid structure does not remove mesoporous template agent silicon-phenolic resin-micropore molecular sieve composite material, The template is tetradecyltrimethylammonium bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide；
C) under the conditions of protective atmosphere, by step B) obtained composite material carries out low-temperature sintering, obtain mesoporous silico-carbo- Micropore molecular sieve composite material；
D) by step C) after obtained composite material impregnates in the aqueous solution containing metal ion, in air atmosphere condition Under, high-temperature calcination is carried out, obtains the composite molecular screen of yolk-shell structure of carried metal.
Preferably, the zeolite molecules are screened from type A zeolite molecular sieve, ZSM-5 molecular sieve, Y-type zeolite molecular sieve It is one or more.
Preferably, the phenolic compound is selected from phenol or resorcinol, and the aldehyde compound is selected from formaldehyde or acetaldehyde, Step A) in, the alkaline matter is selected from ammonium hydroxide, potassium hydroxide or sodium hydroxide, step B) in, the alkaline matter is selected from ammonia Water, potassium hydroxide or sodium hydroxide.
Preferably, the temperature of the cross-linking reaction is 60~80 DEG C, and the time of the cross-linking reaction is 4~12h.
Preferably, the organosilicon source compound is selected from methyl orthosilicate, ethyl orthosilicate or positive silicic acid propyl ester.
Preferably, step B) time for being reacted is 12~24h.
Preferably, the protective atmosphere condition is selected from nitrogen or argon gas, and the low sintering temperature is 300~400 DEG C, The low sintering time is 2~4h, and the temperature of the high-temperature calcination is 600~800 DEG C, and the time of the high-temperature calcination is 4~8h.
Preferably, the metal ion in the aqueous solution containing metal ion is selected from Ce3+、Ce4+、Cu2+And La3+In One or more, the concentration of the metal ion is 0.01mol/L~0.02mol/L.
Present invention also offers micro- mesoporous yolk-shell composite molecular sieve that a kind of above-mentioned preparation method is prepared.
Present invention also offers a kind of cigarette, including smoke and stub, the smoke tail end is connected with the stub head end, The stub includes the acetate fiber section that with the addition of composite molecular screen being alternately arranged successively from head end to tail end and is not added with multiple The acetate fiber section of molecular sieve is closed, the compound molecule is prepared screened from the preparation method described in claim 1~8 any one Obtained micro- mesoporous yolk-shell composite molecular sieve, the additive amount of the composite molecular screen is 10~30mg/ branch cigarette.
Compared with prior art, the present invention provides a kind of carried metal micro- mesoporous yolk-shell composite molecular sieve system Preparation Method, comprises the following steps：A) zeolite molecular sieve, alkaline matter, phenolic compound, aldehyde compound and water are mixed, Cross-linking polymerization is carried out, obtains the molecular sieve-phenolic resin compound with nucleocapsid structure；B) by template, alcohol it is water-soluble Liquid, alkaline matter, step A) obtained compound and the mixing of organosilicon source compound, reacted, obtained with nucleocapsid structure Do not remove mesoporous template agent silicon-phenolic resin-micropore molecular sieve composite material, the template is selected from tetradecyltrimethylammonium bromine Change ammonium, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide；C) under the conditions of protective atmosphere, by step B) The composite material arrived carries out low-temperature sintering, obtains mesoporous silico-carbo-micropore molecular sieve composite material；D) by step C) answering of obtaining After condensation material impregnates in the aqueous solution containing metal ion, under the conditions of air atmosphere, high-temperature calcination is carried out, obtains gold-supported The composite molecular screen of yolk-shell structure of category.Micro- mesoporous yolk-shell composite molecular sieve of carried metal provided by the present invention, The cavity of yolk-shell structure is made full use of, is acted on by the structure and metal composite in a variety of ducts of mesoporous and micropore, can be effective Ground adsorbs different size of pernicious gas molecule, reduces the harmfulness of cigarette.To the particularly benzene of the harmful substance in cigarette smoke And [a] pyrene, crotonaldehyde etc. have notable adsorption effect.
Brief description of the drawings
Fig. 1 is the adsorption desorption curve of ZSM-5 (a) and the micro- mesoporous yolk-shell composite molecular sieve B (b) of Cu-.
Embodiment
The present invention provides a kind of preparation method of micro- mesoporous yolk-shell composite molecular sieve of carried metal, including it is following Step：
A) zeolite molecular sieve, alkaline matter, phenolic compound, aldehyde compound and water are mixed, carry out cross-linked polymeric Reaction, obtains the molecular sieve-phenolic resin compound with nucleocapsid structure；
B) by template, the aqueous solution of alcohol, alkaline matter, step A) obtained compound and organosilicon source compound mix Close, reacted, obtain having nucleocapsid structure does not remove mesoporous template agent silicon-phenolic resin-micropore molecular sieve composite material, The template is selected from tetradecyltrimethylammonium bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide；
C) under the conditions of protective atmosphere, by step B) obtained composite material carries out low-temperature sintering, obtain mesoporous silico-carbo- Micropore molecular sieve composite material；
D) by step C) after obtained composite material impregnates in the aqueous solution containing metal ion, in air atmosphere condition Under, high-temperature calcination is carried out, obtains the composite molecular screen of yolk-shell structure of carried metal.
The present invention first mixes zeolite molecular sieve, alkaline matter, phenolic compound, aldehyde compound and water, carries out Cross-linking reaction, obtains the molecular sieve-phenolic resin compound with nucleocapsid structure.
Specifically, zeolite molecular sieve will be distributed in aqueous solution by the present invention first, then, alkaline matter is added, then add Enter phenolic compound and aldehyde compound, the phenolic compound and aldehyde compound gather in zeolite molecular sieve surfaces cross-link Reaction is closed, obtains reaction product；
The reaction product is washed through alcohol and water respectively, is centrifugally separating to obtain molecular sieve-phenolic aldehyde with nucleocapsid structure Resin complexes.
In the present invention, the zeolite molecules are screened from type A zeolite molecular sieve, ZSM-5 molecular sieve, Y-type zeolite molecular sieve In one or more.The phenolic compound is selected from phenol or resorcinol, and the aldehyde compound is selected from formaldehyde or acetaldehyde, The alkaline matter is selected from ammonium hydroxide, potassium hydroxide or sodium hydroxide.
The temperature of the cross-linking reaction is 60~80 DEG C, is preferably 65~75 DEG C；The time of the cross-linking reaction for 4~ 12h, is preferably 7~9h.
In the molecular sieve-phenolic resin compound, the molecular sieve and phenolic compound, aldehyde with generating phenolic resin Class compound quality ratio is 1：(0.4~0.6)：(0.6~0.8).
Then, template, the aqueous solution of alcohol, alkaline matter, compound obtained above and organosilicon source compound are mixed Close, reacted, obtain having nucleocapsid structure does not remove mesoporous template agent silicon-phenolic resin-micropore molecular sieve composite material.
The present invention first adds alkaline matter in the aqueous solution of alcohol, then adds after template stirs evenly, then Compound obtained above is added, carries out ultrasonic disperse, organosilicon source compound is added dropwise, is mixed, is reacted, is obtained anti- Answer product；
The reaction product is washed through alcohol and water respectively, is centrifugally separating to obtain and does not remove mesoporous mould with nucleocapsid structure Version agent silicon-phenolic resin-micropore molecular sieve composite material.
Wherein, the alkaline matter is selected from ammonium hydroxide, potassium hydroxide or sodium hydroxide；The template is tetradecyl trimethyl Base ammonium bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide；The organosilicon source compound is selected from positive silicon Sour methyl esters, ethyl orthosilicate or positive silicic acid propyl ester.
Wherein, the template, step A) obtained compound and organosilicon source compound mass ratio for (0.4~ 0.6)：1：(0.5~0.8).
The temperature room temperature of the reaction, time are 12~24h, are preferably 16~20h.
After reaction, obtain having nucleocapsid structure not except mesoporous template agent silicon-phenolic resin-micro porous molecular sieve is multiple Condensation material.
Then, under the conditions of protective atmosphere, by composite material obtained above carry out low-temperature sintering, obtain mesoporous silico-carbo- Micropore molecular sieve composite material.
The protective atmosphere condition is selected from nitrogen or argon gas, is preferably nitrogen.
The low sintering temperature is 300~400 DEG C, is preferably 330~370 DEG C；The low sintering time is 2 ~4h, is preferably 3~4h.
The above-mentioned mesoporous template agent of sintering process is removed.
Then, after composite material obtained above is impregnated in the aqueous solution containing metal ion, in air atmosphere bar Under part, high-temperature calcination is carried out, obtains the composite molecular screen of yolk-shell structure of carried metal.
Metal ion in the aqueous solution containing metal ion is selected from Ce3+、Ce4+、Cu2+And La3+In one kind or more Kind, the concentration of the metal ion is 0.01mol/L~0.02mol/L.
The temperature of the high-temperature calcination is 600~800 DEG C, is preferably 650~750 DEG C；The time of the high-temperature calcination is 4 ~8h, is preferably 5~7h.
Present invention also offers a kind of micro- mesoporous yolk-shell composite molecular sieve being prepared using above-mentioned preparation method.
The micro- mesoporous yolk-shell composite molecular sieve being prepared using above-mentioned preparation method can be added in cigarette, used In reduction cigarette harmful components.
Present invention also offers a kind of cigarette, including smoke and stub, the smoke tail end is connected with the stub head end, The stub includes the acetate fiber section that with the addition of composite molecular screen being alternately arranged successively from head end to tail end and is not added with multiple The acetate fiber section of molecular sieve is closed, the compound molecule is multiple screened from micro- mesoporous yolk-shell that above-mentioned preparation method is prepared Molecular sieve is closed, the additive amount of the composite molecular screen is 10~30mg/ branch cigarette.
Wherein, the head end of the stub is that the tail end of the acetate fiber section and the smoke that with the addition of composite molecular screen connects Touch, the tail end of the stub is the acetate fiber section for being not added with composite molecular screen.
Since harmful constituents in cigarette flue gas molecular size is different, single aperture is difficult to realize the comprehensive drop of harmful components It is low, and micro- mesoporous yolk-shell composite molecular sieve of carried metal provided by the present invention, it is excellent micro--meso-hole structure to be played at the same time Gesture, so as to effectively adsorb different size of pernicious gas molecule.
Preparation method of the present invention is all very easy with operation and equipment requirement, cheap, has a good application prospect. Simple metal salt dipping provided by the present invention, makes full use of the cavity of yolk-shell structure, passes through answering for multi-pore channel and metal Cooperation is used, and effectively reduces the harmfulness of cigarette.
The binary combined filter tip (stub) made of composite molecular screen material of the present invention, by additivated acetate fiber Section and common acetate fiber section are combined.Additive acetate fiber section be dispersed in by composite molecular screen material it is loose Formed in acetate silk, additive additive amount is 10-30mg/ branch.To the particularly benzo of the harmful substance in cigarette smoke [a] pyrene, crotonaldehyde etc. have notable adsorption effect.
For a further understanding of the present invention, micro- mesoporous egg with reference to embodiment to carried metal provided by the invention Huang-shell composite molecular sieve and preparation method thereof and cigarette illustrate, and protection scope of the present invention is from following embodiments Limitation.
Embodiment 1
(1) 1g Y molecular sieves are added in 500ml water mixed solutions, add 0.6ml ammonium hydroxide, then added between 0.6g Biphenol and 0.8ml formaldehyde, stir 4h at 80 DEG C, are washed respectively repeatedly with ethanol and water, be centrifugally separating to obtain solid powder A；
(2) 0.6ml ammonium hydroxide is added in 250ml water, in the mixed solution of 250ml ethanol, by 0.4g template cetyls Trimethylammonium bromide is dissolved in mixed solution, and after stirring to clarify, the solid powder A of 1g is divided under 200W ultrasonications Dissipate, after being uniformly dispersed, add tetramethoxysilance 0.6g.After when reaction 12 is small at room temperature, by product centrifuge washing to neutrality, Then 400 DEG C of calcining 4h on the tubular type road of nitrogen protection, obtain the mesoporous silico-carbo of nucleocapsid-micropore molecular sieve composite material A；
(3) the mesoporous silico-carbo of 1g nucleocapsids-micropore molecular sieve composite material A is impregnated into Ce (SOs of the 100ml in 0.01mol/l4)2 In aqueous solution.Again through 800 DEG C of calcining 6h of air high-temperature calcination, load C eO is obtained2Micro- mesoporous yolk-shell composite molecular sieve B, Its physical property SBETFor 730.5m2/ g, SmicroFor 221.6m2/ g, DmesoFor 3.2nm, pore volume VmicroFor 0.13cm3/g, Vex For 0.32cm3/g。
(4) composite A is added in the stub of cigarette, can effectively reduces [a] pyrene of benzo in flue gas and crotonaldehyde Content.By adding the acetate fiber section of composite A and not adding the acetate fiber section of composite A to be combined binary combined filter tip (stub), addition composite A acetate fiber section is that shape in loose acetate silk is dispersed in by composite A Into additive additive amount is 15mg/ branch.
Not plus the acetate fiber section of composite A is with adding composite A acetate fiber section formation binary for composite compound Filter tip, compound tense does not add the acetate fiber section of composite A and adds composite A acetate fiber section to be alternately arranged, wherein not adding The acetate fiber section of composite A adds composite A acetate fiber section to contact cigarette in the front end of stub in the end of stub Silk end.Benzo [a] pyrene in cigarette smoke and crotonaldehyde release amount are detected, testing result is shown in Table 1.
Table 1：Carried metal CeO2Micro- mesoporous yolk-shell composite molecular sieve A harm reduction effect
In table 1, blank is comparative example 1, and not add composite A in stub, i.e. stub is entirely by acetate fiber It is prepared.Me-MCM-48 is comparative example 2, i.e., the composite A in embodiment 1 is replaced with Me-MCM-48.
Embodiment 2
(1) 1g ZSM-5 molecular sieves are added in 500ml water mixed solutions, add 0.5ml ammonium hydroxide, then add 0.6g phenol and 0.8ml formaldehyde, stir 4h at 80 DEG C, are washed respectively repeatedly with ethanol and water, be centrifugally separating to obtain solid powder B；
(2) 0.5ml ammonium hydroxide is added in 120ml water, in the mixed solution of 330ml ethanol, by 0.6g template myristyls Trimethylammonium bromide dissolving stir to clarify solution after, then by the solid powder B of 1g under 200W ultrasonications disperse, wait to disperse After uniformly, tetraethoxysilance 0.8g is added.After when reaction 24 is small at room temperature, by product centrifuge washing to neutrality, nitrogen protection Tube furnace on 400 DEG C calcining 2h, obtain the mesoporous silico-carbo of nucleocapsid-micropore molecular sieve composite material B；
(3) the mesoporous silico-carbo of 1g nucleocapsids-micropore molecular sieve composite material B is impregnated into CuSOs of the 100ml in 0.01mol/l4Gold Belong in solution.600 DEG C of calcining 8h in air, obtain micro- mesoporous yolk-shell composite molecular sieve of carried metal CuO in Muffle furnace B, its physical property SBETFor 526.6m2/ g, SmicroFor 197.6m2/ g, DmesoFor 3.6nm, pore volume VmicroFor 0.11cm3/ g, VexFor 0.28cm3/g。
(4) composite material B is added in stub, can effectively reduces [a] pyrene of benzo in flue gas and crotonaldehyde
Content.By adding the acetate fiber section of composite material B and not adding the acetate fiber section of composite material B to be combined two First composite filter tip (stub), addition composite material B acetate fiber sections are that loose acetate fiber is dispersed in by composite material B Formed in tow, composite material B additive amounts are 10mg/ branch.
Not plus the acetate fiber section of composite material B is with adding composite material B acetate fiber sections formation binary for composite compound Stub, compound tense does not add the acetate fiber section of composite material B and adds composite material B acetate fiber sections to be alternately arranged, wherein not adding The acetate fiber section of composite material B adds composite material B acetate fiber sections to contact cigarette in the front end of stub in the end of stub Silk end.Benzo [a] pyrene in cigarette smoke and crotonaldehyde release amount are detected, testing result is shown in Table 2.
Table 2：The harm reduction effect of micro- mesoporous yolk-shell composite molecular sieve B of carried metal CuO
(5) adsorption/desorption is carried out to micro- mesoporous yolk-shell composite molecular sieve B of the above-mentioned carried metal CuO being prepared Test, the result is shown in Figure 1, Fig. 1 are the adsorption desorption curve of ZSM-5 (a) and the micro- mesoporous yolk-shell composite molecular sieve B (b) of Cu-.
Embodiment 3
(1) 1g 5A molecular sieves are added in 500ml water mixed solutions, add 0.8ml ammonium hydroxide, then add 0.6g Phenol and 0.8ml acetaldehyde, stir 12h at 70 DEG C, are washed respectively repeatedly with ethanol and water, be centrifugally separating to obtain solid powder C；
(2) 0.6ml ammonium hydroxide is added in 200ml water, in the mixed solution of 300ml ethanol, by 0.5g template octadecyls Trimethylammonium bromide is dissolved into mixed solution, after stirring to clarify solution, by the solid powder C of 1g under 200W ultrasonications It is scattered, after being uniformly dispersed, add positive the third fat of silicic acid 0.7g.After when reaction 12 is small at room temperature, by product centrifuge washing into Property, nitrogen protection tube furnace on 350 DEG C calcining 3h, obtain the mesoporous silico-carbo of nucleocapsid-micropore molecular sieve composite material C；
(3) the mesoporous silico-carbo of 1g nucleocapsids-micropore molecular sieve composite material C is impregnated into Las of the 100ml in 0.02mol/l2 (SO4)3In aqueous solution.700 DEG C of calcining 6h in air, obtain carried metal La in Muffle furnace2O3Micro- mesoporous yolk-shell it is multiple Close molecular sieve C, its physical property SBETFor 587.1m2/ g, SmicroFor 180.7m2/ g, DmesoFor 3.8nm, pore volume VmicroFor 0.11cm3/ g, VexFor 0.29cm3/g。
(4) above-mentioned gained composite material C is added in stub, can effectively reduces [a] pyrene of benzo in flue gas and crotonaldehyde Content.Composite material C is added in stub, can effectively reduce the content of phenol in flue gas.By the acetic acid for adding composite material C Segment of fiber and not plus the acetate fiber section of composite material C is combined binary combined filter tip (stub).Add composite material C acetic acid Segment of fiber is to be dispersed in loose acetate silk to be formed by composite material C, and additive additive amount is 30mg/ branch.
Not plus composite material C acetate fiber sections are with adding composite material C acetate fiber sections are for composite to form binary composite smoke The base of a fruit, compound tense do not add composite material C acetate fiber sections and add composite material C acetate fiber sections to be alternately arranged, wherein plus compound Material C acetate fiber section adds composite material C acetate fiber sections to contact pipe tobacco end in the front end of stub in the end of stub.It is right Benzo [a] pyrene and crotonaldehyde release amount in cigarette smoke are detected, and testing result is shown in Table 3.
Table 3：Carried metal La2O3Micro- mesoporous yolk-shell composite molecular sieve C harm reduction effect
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. the preparation method of micro- mesoporous yolk-shell composite molecular sieve of a kind of carried metal, it is characterised in that including following step Suddenly：
A) zeolite molecular sieve, alkaline matter, phenolic compound, aldehyde compound and water are mixed, carry out cross-linking polymerization, Obtain the molecular sieve-phenolic resin compound with nucleocapsid structure；
B) by template, the aqueous solution of alcohol, alkaline matter, step A) obtained compound and the mixing of organosilicon source compound, into Row reaction, obtain having nucleocapsid structure does not remove mesoporous template agent silicon-phenolic resin-micropore molecular sieve composite material, the mould Plate agent is selected from tetradecyltrimethylammonium bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide；
C) under the conditions of protective atmosphere, by step B) obtained composite material carries out low-temperature sintering, obtain mesoporous silico-carbo-micropore Molecular sieves compound material；
D) by step C) after obtained composite material impregnates in the aqueous solution containing metal ion, under the conditions of air atmosphere, High-temperature calcination is carried out, obtains the composite molecular screen of yolk-shell structure of carried metal.
2. preparation method according to claim 1, it is characterised in that the zeolite molecules screened from type A zeolite molecular sieve, One or more in ZSM-5 molecular sieve, Y-type zeolite molecular sieve.
3. preparation method according to claim 1, it is characterised in that the phenolic compound is selected from phenol or isophthalic two Phenol, the aldehyde compound are selected from formaldehyde or acetaldehyde, step A) in, the alkaline matter is selected from ammonium hydroxide, potassium hydroxide or hydrogen-oxygen Change sodium, step B) in, the alkaline matter is selected from ammonium hydroxide, potassium hydroxide or sodium hydroxide.
4. preparation method according to claim 1, it is characterised in that the temperature of the cross-linking reaction is 60~80 DEG C, institute The time for stating cross-linking reaction is 4~12h.
5. preparation method according to claim 1, it is characterised in that the organosilicon source compound is selected from positive silicic acid first Ester, ethyl orthosilicate or positive silicic acid propyl ester.
6. preparation method according to claim 1, it is characterised in that step B) time for being reacted is 12~24h.
7. preparation method according to claim 1, it is characterised in that the protective atmosphere condition is selected from nitrogen or argon gas, The low sintering temperature is 300~400 DEG C, and the low sintering time is 2~4h, and the temperature of the high-temperature calcination is 600~800 DEG C, the time of the high-temperature calcination is 4~8h.
8. preparation method according to claim 1, it is characterised in that the metal in the aqueous solution containing metal ion Ion is selected from Ce3+、Ce4+、Cu2+And La3+In one or more, the concentration of the metal ion for 0.01mol/L~ 0.02mol/L。
A kind of 9. micro- mesoporous yolk-shell composite molecular that preparation method as described in claim 1~8 any one is prepared Sieve.
10. a kind of cigarette, including smoke and stub, the smoke tail end is connected with the stub head end, it is characterised in that described Stub includes the acetate fiber section that with the addition of composite molecular screen being alternately arranged successively from head end to tail end and is not added with compound point The acetate fiber section of son sieve, the compound molecule are prepared screened from the preparation method described in claim 1~8 any one Micro- mesoporous yolk-shell composite molecular sieve, the additive amount of the composite molecular screen is 10~30mg/ branch cigarette.
CN201711325417.5A 2017-12-13 2017-12-13 Micro- mesoporous yolk-shell composite molecular sieve of a kind of carried metal and preparation method thereof and a kind of cigarette Pending CN108033458A (en)

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Application publication date: 20180515