CN103638897B - Metal pillared montmorillonite coated mesoporous silica composite material and preparation method thereof - Google Patents
Metal pillared montmorillonite coated mesoporous silica composite material and preparation method thereof Download PDFInfo
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- CN103638897B CN103638897B CN201310653100.XA CN201310653100A CN103638897B CN 103638897 B CN103638897 B CN 103638897B CN 201310653100 A CN201310653100 A CN 201310653100A CN 103638897 B CN103638897 B CN 103638897B
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Abstract
The present invention discloses a metal pillared montmorillonite coated mesoporous silica composite material and a preparation method thereof. The preparation method comprises the following steps: preparation of a metal pillared agent, namely slowly dropwise adding soluble metal salt into an aqueous solution of Na2CO3 or water with stirring, fully hydrolyzing at 60 to 80 DEG C and aging for 24 to 48 hours; preparation of a metal pillared montmorillonite suspension, namely adding the water into montmorillonite, stirring at room temperature to disperse the montmorillonite sufficiently, slowly dropwise adding the metal pillared agent into the montmorillonite suspension, reacting for 2 to 4 hours at the temperature of 60 to 80 DEG C, stopping stirring, standing for one night, washing, centrifuging, drying, and adding water to prepare the metal pillared montmorillonite suspension with the mass percentage of 20 to 30 percent; uniformly mixing the metal pillared montmorillonite suspension and a porous silicon material to obtain a mixture, and drying the mixture. The composite material prepared by adopting the method combines the properties of montmorillonite minerals and mesoporous materials, and can effectively reduce the emission amount of harmful components in cigarette smoke.
Description
Technical field
The present invention relates to a kind of coating mesoporous silicon composite of metal column montmorillonite that effectively can reduce harmful substances in flue gas content and preparation method thereof.
Background technology
Along with the progress of society, smoking and environmental problem are by the whole world is paid close attention to." Framework Convention on Tobacco Control " requires that national governments work up more severe " Tobacco Control " laws and regulations, impels tobacco productive corporation while reduction releasing content of coke tar in cigarette, more strictly will control the burst size of main harmful components in cigarette smoke.2009, studied by the Zhengzhou tobacco research institute cigarette smoke harmfulness index having carried out Chinese-style cigarette of taking the lead, filter out 7 kinds of representative compositions as cigarette Evaluation of Harmfulness index, as CO, HCN, NNK, B [a] P, phenol etc.In last century Mo, mineral material due to its cost low, abundance, as mouth rod additive, be subject to a lot of tobacco science and technology person and pay close attention to.Wherein montmorillonite is a kind of monoclinic moisture layer silicate mineral, and intermediate layer has polarity, can absorb hydrone or other polar molecules.Montmorillonite is made cigarette filter tip by Hui Boran, for optionally adsorbing the polarity harmful substance in cigarette mainstream flue gas.Yan Jinghui etc. reduce the free radical in coke tar in cigarette with the composite filter tip that montmorillonite is made.But above-mentioned adopted imvite, the impact that the specific area by itself is low, interlamellar spacing is too little, causes its adsorption effect undesirable, has no application at present in production of cigarettes.
Summary of the invention
In order to solve above-mentioned technical problem, the present invention with purification imvite for raw material, make full use of expansiveness and the ion exchangeable of imvite mineral lamellar structure, metal column-supporting agent is adopted to insert the interlayer of imvite, layer structure equally struts by statuary column, obtain the metal pillared montmorillonite (original layers spacing 0.99nm) with 1.5nm-2.0nm interlamellar spacing, form the poromerics of two dimension, be coated on 40-80 object mesoporous silicon material again, this micro--Jie's composite fully combines the lamellar character of imvite and the performance with more macropore and specific area of mesoporous material.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
A preparation method for the coating mesoporous silicon composite of metal column montmorillonite, comprises the following steps:
Step one: the preparation of metal column-supporting agent: under the condition stirred, by the slaine of solubility, be slowly added drop-wise to Na
2cO
3in the aqueous solution or water, be fully hydrolyzed at 60-80 DEG C, aging 24-48h, stand-by;
Step 2: the preparation of metal pillared montmorillonite suspension: imvite is added water and is mixed with montmorillonite suspension liquid, stirring at room temperature makes imvite fully disperse, obtained metal column-supporting agent is slowly added drop-wise in montmorillonite suspension liquid, 2 ~ 4h is reacted at 60 ~ 80 DEG C, stop stirring, left undisturbed overnight, then through washing, centrifugal, oven dry, add water and be mixed with the metal column montmorillonite suspension that mass fraction is 20 ~ 30%;
Step 3: after metal column montmorillonite suspension is mixed with porous silica material, dry, obtain micro--mesoporous composite material.
Further technical scheme is: described metal column-supporting agent is iron column-supporting agent, aluminium column-supporting agent, zirconium column-supporting agent or above-mentioned multi-element metal compound.
Further technical scheme is: described micro--mesoporous composite material in the content of metal column montmorillonite be 10 ~ 30%.
Further technical scheme is: the particle diameter of described porous silica material is 40 ~ 80 orders.
Further technical scheme is: the mass fraction of described montmorillonite suspension liquid is 1 ~ 6%.
The coating mesoporous silicon composite of a kind of metal column montmorillonite, the preparation method described in employing is prepared from.
A kind of binary combined filter tip, be composited by additivated acetate fiber section and acetate fiber section, described additivated acetate fiber section is that the coating mesoporous silicon composite of metal column montmorillonite is dispersed in loose acetate fibres, additivated acetate fiber section and acetate fiber section are alternately arranged, the front end of filter tip connects additivated acetate fiber section, and the end of filter tip connects acetate fiber section.
Further technical scheme is: the addition of the described coating mesoporous silicon composite of metal column montmorillonite is 2 ~ 30mg.
The present invention compared with prior art, has following beneficial effect:
(1) this method technique simple, with low cost, can industrial applications, reaction condition is gentle, and reaction condition is easy to control.
(2) composite prepared combines the performance of imvite mineral and mesoporous material, and this composite adds filter tip to in cigarette, effectively can reduce the burst size of harmful constituents in cigarette flue gas, reduce phenol and NNK effects obvious.
(3) composite of the present invention on cigarette sensory quality substantially without impact, nontoxic, the processing technology of binary compound bar can be met, in low harm cigarette processing, have application prospect.
Detailed description of the invention
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Embodiment 1:
Take 242.4 grams of Fe (NO
3)
3.9H
2o, is dissolved in water, and at room temperature stirs, and slowly adds 63.6 grams of natrium carbonicum calcinatum powder, is diluted with water 2000mL, continues stirring 2 hours, and at 60 DEG C, ageing 24 hours in water bath with thermostatic control, obtains the iron column-supporting agent that brown is transparent.
Take 100 grams of commercially available purification imvites, add water 2000mL, is made into suspension, under 60 DEG C of constant temperature stir, drip iron column-supporting agent 350ml, then react 2 hours, then ageing 24 hours at 60 DEG C, then through washing, centrifugal, dry, prepare iron prop montmorillonite.
Take 200g iron prop montmorillonite, add water and be configured to the suspension of 30wt%, after the 40-80 object mesoporous silicon adding 1800g stirs, the dry composite 1 obtaining the coating mesoporous silicon of iron prop montmorillonite at 100 DEG C.Joined in filter tip by gained composite 1 and be prepared into binary combined filter tip, effectively can reduce the content of phenol and NNK in flue gas, testing result is in table 1.
Above-mentioned binary combined filter tip is composited by additivated acetate fiber section and acetate fiber section, additivated acetate fiber section is be scattered in by composite in loose acetate fibres uniformly, additivated acetate fiber section and acetate fiber section are alternately arranged, the front end of filter tip connects additivated acetate fiber section, and the end of filter tip connects acetate fiber section.
Table 1:
Embodiment 2:
Take the iron prop montmorillonite in 400g embodiment 1, add water and be configured to the suspension of 30wt%, after the 40-80 object mesoporous silicon adding 1600g stirs, the dry composite 2 obtaining the coating mesoporous silicon of iron prop montmorillonite at 100 DEG C.Added in filter tip according to the method for embodiment 1 by composite 2 and be prepared into binary combined filter tip, testing result is in table 2.
Table 2:
Embodiment 3:
Take the iron prop montmorillonite of 600g embodiment 1, add water and be configured to the suspension of 30wt%, after the 40-80 object mesoporous silicon adding 1400g stirs, the dry composite 3 obtaining the coating mesoporous silicon of iron prop montmorillonite at 100 DEG C.Testing result is in table 3.
Table 3:
Embodiment 4:
First the AlCl of 0.5mol/L is configured
3the Na of solution and 1.0mol/L
2cO
3solution, then under stirring and temperature 80 DEG C of conditions, by 300ml Na
2cO
3solution slowly instills the AlCl of 500mL
3in solution, be diluted with water to 1000ml, continue stirring 2 hours, then solution is put into 60 DEG C of water bath with thermostatic control ageings 2 days, obtain aluminium column-supporting agent.
Take 150 grams of purification imvites, add water 2500ml, is made into suspension, under 60 DEG C of constant temperature stir, drip aluminium column-supporting agent 500ml, react 2 hours, then ageing 24 hours at 60 DEG C, then through washing, centrifugal, dry, prepare a certain amount of aluminium pillared montmorillonite.
Then take 600g aluminium pillared montmorillonite, add water and be configured to the suspension of 30wt%, after the 40-80 object mesoporous silicon adding 1400g stirs, the dry composite 4 obtaining the coating mesoporous silicon of aluminium pillared montmorillonite at 100 DEG C.Testing result is in table 4
Table 4:
Embodiment 5:
First the ZrOCl of 0.1mol/L is configured
2.8H
2o solution, then stirs 2-4h under temperature 80 DEG C of conditions, then ageing 24h at this temperature, obtains zirconium column-supporting agent.
Take 150 grams of purification imvites, add water 2500ml, is made into suspension, under 60 DEG C of constant temperature stir, drips zirconium column-supporting agent 500ml, react 2 hours, then ageing 24 hours at 60 DEG C, then through washing, centrifugal, oven dry, prepare zirconium pillared montmorillonite.
Then take 500g zirconium pillared montmorillonite, add water and be configured to the suspension of 30wt%, after the 40-80 object mesoporous silicon adding 1500g stirs, the dry composite 5 obtaining the coating mesoporous silicon of zirconium pillared montmorillonite at 100 DEG C.Testing result is in table 5
Table 5:
Embodiment 6:
Adopt method described in embodiment 1 and embodiment 4 to prepare iron column-supporting agent and aluminium column-supporting agent respectively, by volume 1:1 is mixed to get composite pillared dose of iron aluminium.
Take 150 grams of purification imvites, add water 2500ml, is made into suspension, under 60 DEG C of constant temperature stir, drip iron aluminium composite pillared dose of 500ml, react 2 hours, then ageing 24 hours at 60 DEG C, then through washing, centrifugal, dry, prepare a certain amount of aluminium-iron composite column montmorillonite.
Then take 600g iron aluminium pillared montmorillonite, add water and be configured to the suspension of 30wt%, after the 40-80 object mesoporous silicon adding 1400g stirs, the dry composite 5 obtaining the coating mesoporous silicon of iron aluminium composite column montmorillonite at 100 DEG C.Testing result is in table 6
Table 6:
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only the present invention's preferably embodiment, embodiments of the present invention are not restricted to the described embodiments, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.
Claims (2)
1. a preparation method for the coating mesoporous silicon composite of metal column montmorillonite, is characterized in that comprising the following steps:
Step one: the preparation of metal column-supporting agent: under the condition stirred, by the slaine of solubility, be slowly added drop-wise to Na
2cO
3in the aqueous solution or water, be fully hydrolyzed at 60-80 DEG C, aging 24-48h, stand-by; Described metal column-supporting agent is iron column-supporting agent, aluminium column-supporting agent, zirconium column-supporting agent or above-mentioned multi-element metal compound;
Step 2: the preparation of metal column montmorillonite suspension: imvite is added water and is mixed with montmorillonite suspension liquid, stirring at room temperature makes imvite fully disperse, obtained metal column-supporting agent is slowly added drop-wise in montmorillonite suspension liquid, 2 ~ 4h is reacted at 60 ~ 80 DEG C, stop stirring, left undisturbed overnight, then through washing, centrifugal, oven dry, add water and be mixed with the metal column montmorillonite suspension that mass fraction is 20 ~ 30%;
Step 3: after metal column montmorillonite suspension is mixed with porous silica material, dry, obtain micro--mesoporous composite material, described micro--mesoporous composite material in the content of metal column montmorillonite be 10 ~ 30%.
2. the preparation method of the coating mesoporous silicon composite of metal column montmorillonite according to claim 1, is characterized in that the particle diameter of described porous silica material is 40 ~ 80 orders.
3. the preparation method of the coating mesoporous silicon composite of metal column montmorillonite according to claim 1, is characterized in that the mass fraction of described montmorillonite suspension liquid is 1 ~ 6%.
4. the coating mesoporous silicon composite of metal column montmorillonite, is characterized in that adopting the preparation method described in any one of claim 1 ~ 3 to be prepared from.
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| CN106723343B (en) * | 2017-04-06 | 2020-04-14 | 上海烟草集团有限责任公司 | Composite cigarette filter stick capable of reducing tar release amount of cigarettes and preparation method thereof |
| CN110797495B (en) * | 2019-09-28 | 2021-08-10 | 合肥国轩高科动力能源有限公司 | High-strength composite PE diaphragm and preparation method thereof |
| CN114804134B (en) * | 2022-04-12 | 2023-07-25 | 中国科学院广州地球化学研究所 | Mesoporous material preparation method based on clay mineral |
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| CN103212371A (en) * | 2013-04-19 | 2013-07-24 | 云南烟草科学研究院 | Modified montmorillonite filter additive containing iron oxide or/and hydroxy iron and application |
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Effective date of registration: 20161229 Address after: Nanping Nan'an District of Chongqing City Road 400060 No. 2 Patentee after: CHONGQING CHINA TOBACCO INDUSTRIAL CO., LTD. Patentee after: CHINA TOBACCO SICHUAN INDUSTRIAL CO., LTD. Address before: 610000 Jackie Chan Road, Chengdu economic and Technological Development Zone, Longquanyi District, Sichuan, China, No. 2, No. Patentee before: China Tobacco Chuanyu Industry Co., Ltd. |
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Granted publication date: 20150520 Termination date: 20171205 |