CN102499479A - Complex adsorbent capable of reducing release amount of heavy metals in mainstream smoke of cigarettes, preparation method for complex adsorbent and application of complex adsorbent - Google Patents
Complex adsorbent capable of reducing release amount of heavy metals in mainstream smoke of cigarettes, preparation method for complex adsorbent and application of complex adsorbent Download PDFInfo
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- CN102499479A CN102499479A CN2011103436292A CN201110343629A CN102499479A CN 102499479 A CN102499479 A CN 102499479A CN 2011103436292 A CN2011103436292 A CN 2011103436292A CN 201110343629 A CN201110343629 A CN 201110343629A CN 102499479 A CN102499479 A CN 102499479A
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Abstract
The invention discloses a complex adsorbent capable of reducing the release amount of heavy metals in smoke of cigarettes, a preparation method for the complex adsorbent and application of the complex adsorbent. The complex adsorbent contains a load of natural amino acid consisting of amino and carboxyl functional groups, and carriers such as silica gel, alumina, a molecular sieve or acetate fiber and the like. The amino acid can be immobilized onto the surfaces of the carriers in a chemical binding mode, and a complex is obtained through drying treatment. A binary composite filter stick prepared by adding the complex adsorbent into a cigarette filter tip stick is used for rolling and connecting the cigarettes; and smoke analysis shows that the cigarettes containing the complex adsorbent can effectively reduce the content of heavy metal cadmium (Cd) in mainstream smoke of the cigarettes by 15-40 percent and the content of As by 5-20 percent. The invention is characterized in that: the complex adsorbent capable of reducing the release amount of the heavy metals in the smoke of the cigarettes is safe and stable, can be industrially produced conveniently and basically does not affect the taste of the cigarettes, the preparation method is simple and the like.
Description
Technical field
The invention belongs to cigarette processing and manufacturing and cigarette lowering harm and decreasing coking field, be specifically related to have Application of Additives that reduces cigarette mainstream flue gas heavy metal burst size and preparation method thereof.
Background technology
Tobacco is as a kind of special consumer goods; Prop up through cigarette and to get into human body after burning forms flue gas; Wherein the heavy metal in the flue gas (plumbous (Pb), arsenic (As), cadmium (Cd), chromium (Cr), mercury (Hg) etc.) is prone to enrichment in human body and produces harm with the form of aerosol or metal oxide; In 107 kinds of cigarette smoke harmful components were listed 7 heavy metal elements such as As, Cd, Cr, Pb, Ni, Cu, Hg by the U.S. in 1989, and nineteen ninety Hoffman inventory is also listed 7 heavy metal elements such as As, Cd, Cr, Pb, Ni, Se, Hg in the tobacco 44 kinds of harmful components.These heavy metals in the flue gas are mainly derived from the tobacco leaf enrichment in the tobacco planting process; After tobacco leaf is processed into cigarette; Because the low major part of heavy metal element volatility can continue to remain in the pipe tobacco, these heavy metals burn and suck can partly transfer in the main flume in the process at cigarette the smoker are constituted health risk.It is reported [Zhang Lingdi etc., Chinese sanitary inspection magazine, 2001,11 (5): 520] that in smoking process, plumbous volatility is less in the cigarette, and, work the mischief less active smoker and involuntary smoker through cigarette end and filter-tip absorption; And the volatility of cadmium is bigger, and the filter tip adsorbance is less, so all possibly work the mischief to active smoker and involuntary smoker.Have research report to show, smoking male sex blood cadmium concentration is obviously than non-smoker high [Xin Nan etc., Chinese Medicine biotechnology, 2009,4 (5): 390].Therefore, how reducing smoking is imperative key subjects to the harm of human body, carries out to reduce the content of beary metal that cigarette burns and sucks in the process and will have important scientific meaning and using value.
In waste water and waste gas treatment process, having a lot of new materials and new technology to can be used for heavy metal administers; But these materials and the technological heavy metal processing that is difficult to be applicable to cigarette smoke; This be because be used for the heavy metal material of treatment of cigarette flue gas must safety non-toxic with flue gas heavy metal is had the adsorption capacity mutually of gas-solid fast; And this additive will be easy to add and do not influence cigarette odor-absorbing in the cigarette process; Because it is also very limited that these special requirements, research and development can reduce the new material and the new technology of content of beary metal in the flue gas.
There are some researches show that active carbon filter is respectively 4.25,3.58 and 1.61 times of acetate fiber filter tip to the adsorption capacity of Cd, Ni and As, adsorption effect obviously strengthens [Liu Ruoman etc.; Environment and health magazine, 1999,16 (4): 204]; But active carbon does not have selectivity to the absorption of smoke components; When reducing harmful ingredients in flue gas, also can adsorb other flavor components in the flue gas, have a strong impact on cigarette odor-absorbing and be difficult to accepted by the consumer.Also have and report that the active carbon composite filter tip of chitosan-containing has stronger adsorption capacity [Guo Limin etc., Chemical Engineer, 2002,1:17] to the heavy metal in the flue gas and other harmful substances, but still have absorption non-selectivity and the problem that influences cigarette odor-absorbing.The composite filter tip of acetate fiber and the preparation of yellow Siberian cocklebur; Can effectively reduce cadmium and plumbous paramorphogen in the cigarette main flume; Suck heavy metal lead, cadmium and in lung, deposit and have positive effect [Tang Pingtao etc., Chinese public health journal, 1995 for reducing the smoker; 14 (4): 231], but its mechanization manufacture and be still waiting research.J.W. lesser calorie draws dimension to wait to have invented a kind of cigarette filter that [the J.W. lesser calorie draws dimension etc.; Chinese patent CN 101043826A]; Contain in its filter with the mutually crosslinked shitosan of glutaraldehyde with the mutually crosslinked shitosan of glyoxal and process the porous resin material of high surface area/mass ratio; Alternative aldehyde, hydrogen cyanide, carbonyls and the heavy metal of removing in the cigarette smoke etc., but this type material influences cigarette odor-absorbing owing to reducing the carbonyls with fragrance effect.Chen Yuru etc. adopt phthalocyanine-like compound as cigarette harm-reducing agent [Chen Yuru etc.; Chinese patent CN 1709171A]; Phthalocyanine-like compound has tangible reduction effect to harmful substances such as the CO in the flue gas, nitrogen oxide, aldehydes, amines; Can also remove heavy metal ion, cancellation free radical, but such phthalocyanine-like compound cost is high and exist safety issue to be difficult to industrial applications.Zhou Guojun etc. join triacetin three esters with a kind of in copper chlorophyll and the chlorophyllin sodium or two kinds, spray in the tow, perhaps are prepared into 40-80 order particle and add in the mouth rod; Can effectively catching heavy metal [Zhou Guojun etc.; Chinese patent CN 101238913A], but green plain copper and chlorophyllin sodium are insoluble to triacetin three esters basically, exist to add difficulty and influence problem such as wire-beam forming; And green plain copper itself is exactly a kind of complex compound, and complexing power is limited again to heavy metal.
Summary of the invention
The present invention is intended to the deficiency to prior art, and a kind of complexing adsorbent that reduces the cigarette flue gas heavy metal burst size is provided.In the complexing adsorbent of the present invention's preparation; Can form complex compound with the heavy metal ion selective reaction, improve counterweight Metal Ion Selective Electrode property absorption property and be retained down, the preparation process of this additive is simple simultaneously; Be easy to industrial applications; Possess application prospect, in addition, this complexing adsorbent can also partly improve cigarette odor-absorbing.
The complexing adsorbent that provides of the present invention is amino acid to be carried on inorganic carrier particle or the acetate fiber carrier form.
Complexing adsorbent of the present invention has the removal effect to the heavy metal measurer that discharges in the flue gas.
The present invention is carried on amino acid on the carriers such as silica gel, aluminium oxide, molecular sieve or acetate fiber, the support type amino-acid complex adsorbent of a kind of solid granular that the chemical reaction through amino acid and carrier obtains.
Described inorganic carrier particle is silica gel, aluminium oxide or sieve particle.Granular size is the 10-100 order, is preferably the 40-60 order.
Described amino acid refers to glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, tyrosine, serine, cysteine, methionine, asparagine, glutamine, threonine, one or more in aspartic acid, glutamic acid, lysine, arginine, the histidine.
The mass loading amount of described amino acid on inorganic carrier particle or acetate fiber carrier is 1-20%.Be preferably 5-10%.
A kind of preparation method with the complexing adsorbent that reduces the cigarette flue gas heavy metal burst size of the present invention is that inorganic carrier impregnated in the Freamine, gets final product after having amino acid whose carrier to take out oven dry load again; Or amino acid made an addition on the acetate fiber carrier.
Described preparation method with inorganic carrier particle complexing adsorbent is for to process solution with amino acid ligand, and inorganic carrier is immersed in wherein reaction, oven dry get final product described complexing adsorbent.Described soak time is 5 minutes～5 hours; Be preferably 1 hour-3 hours.Described bake out temperature is 80 ℃-180 ℃, is preferably 100 ℃-150 ℃; Drying time is 3-24 hour, is preferably 5-2 hour.
The concrete preparation process of additive of cigarette filter stick of the present invention is following:
Amino acid ligand is processed solution, it is added respectively in silica gel, aluminium oxide or the molecular sieve, equal-volume infuse certain hour moves into wet stock in the baking oven, and baking is cooled off the removal fine powder that sieves and promptly got required complexing adsorbent until drying.
The Freamine concentration that complexing adsorbent of the present invention is prepared in the preparation process can be decided according to demand and amino acid character, and described Freamine concentration is preferably 0.1%-20%.
Complexing adsorbent of the present invention contains natural amino acid amino and that carboxyl functional group is formed, and carriers such as silica gel, aluminium oxide, molecular sieve or acetate fiber; Amino acid can be immobilized in carrier surface through the mode of chamical binding, through dried, obtains compound.Complexing adsorbent of the present invention adds the binary compound filter candle that makes in the cigarette filter tip to; Cigarette cigarette, flue gas analysis show, contain the cigarette of complexing adsorbent; Can effectively reduce heavy metal cadmium (Cd) the content 15-40% in the cigarette mainstream flue gas, As content 5-20%.The complexing adsorbent of reduction cigarette flue gas heavy metal burst size provided by the invention have safety and stability, preparation method simple, be convenient to industrialized production and do not influence characteristics such as cigarette odor-absorbing basically.
Application of the present invention is, with the adsorbent of complexing adsorbent of the present invention as the cigarette filter rod of heavy metal burst size in the reduction cigarette mainstream flue gas.
The complexing adsorbent of preparation is made an addition to and processes binary compound filter candle in the cigarette filter tip, can effectively reduce the content of heavy metal in the flue gas.
The addition of complexing adsorbent in cigarette filter rod with inorganic carrier particle is that 1-40mg/ props up.Preferred addition is that 2-30mg/ props up.
The present invention compared with prior art, its maximum characteristics are that additive preparation technology is simple, are fit to industrialized production; Complexing agent is the natural amino acid of safety non-toxic, can not bring new harm to cigarette, and this complexing adsorbent has the effect that reduces heavy metal in the flue gas preferably simultaneously, and improves cigarette odor-absorbing to a certain extent.
The specific embodiment
Following examples are intended to explain the present invention rather than the present invention are further limited.
Embodiment 1
Prepare 5% arginine solution 100g with distilled water, the silochrom 50g that weighs slowly adds arginine solution in the silica gel, stirs simultaneously, and the equal-volume infuse made it abundant infiltration in 1 hour; In wet particle thing immigration baking oven, under 80 ℃ of conditions, cause thermal response and toast 24h with this understanding, material is fully reacted and drying, naturally cool to room temperature, it is for use that the removal fine powder that sieves is got 40-60 order particle.
The complexing adsorbent that makes propped up with 40mg/ add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample is after temperature humidity balance, resistance to suction and weight screening; Carry out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004; Heavy metal adopts the static trap tube to capture in the main flume grain phase constituent, and heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition, and the heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed.The flue gas analysis result shows that this material can effectively reduce cadmium in the flue gas (Cd) 31%, reduces arsenic (As) 15%.
Embodiment 2
Prepare 5% phenylalanine solution 100g with distilled water, the aluminium oxide of weighing 50g slowly adds arginine solution in the aluminium oxide, stirs simultaneously, and the equal-volume infuse made it abundant infiltration in 2 hours; The wet particle thing is moved in the baking oven, and baking made material fully dry in 10 hours under 150 ℃ of conditions, naturally cooled to room temperature, and it is for use that the removal fine powder that sieves is got 40-60 order particle.
The complexing adsorbent that makes propped up with 30mg/ add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample is after temperature humidity balance, resistance to suction and weight screening; Carry out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004; Heavy metal adopts the static trap tube to capture in the main flume grain phase constituent, and heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition, and the heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed.The flue gas analysis result shows that this material can effectively reduce cadmium in the flue gas (Cd) 21%, reduces arsenic (As) 10%.
Embodiment 3
Prepare 5% arginine solution 100g with distilled water, claim A molecular sieve 50g, arginine solution is slowly added in the A molecular sieve, stir simultaneously, the equal-volume infuse made it abundant infiltration in 2 hours; The wet particle thing is moved in the baking oven, and baking made material fully dry in 10 hours under 150 ℃ of conditions, naturally cooled to room temperature, and it is for use that the removal fine powder that sieves is got 40-60 order particle.
The complexing adsorbent that makes propped up with 30mg/ add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample is after temperature humidity balance, resistance to suction and weight screening; Carry out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004; Heavy metal adopts the static trap tube to capture in the main flume grain phase constituent, and heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition, and the heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed.The flue gas analysis result shows that this material can effectively reduce cadmium in the flue gas (Cd) 15%, reduces arsenic (As) 6%.
Embodiment 4
Prepare 5% histidine solution 100g with distilled water, the aluminium oxide of weighing 50g slowly adds arginine solution in the aluminium oxide, stirs simultaneously, and the equal-volume infuse made it abundant infiltration in 2 hours; The wet particle thing moved in the baking oven baking made material fully dry in 24 hours under 100 ℃ of conditions, naturally cool to room temperature, sieve and remove fine powder to get 40-60 order particle for use.
The complexing adsorbent that makes propped up with 40mg/ add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample is after temperature humidity balance, resistance to suction and weight screening; Carry out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004; Heavy metal adopts the static trap tube to capture in the main flume grain phase constituent, and heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition, and the heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed.The flue gas analysis result shows that this material can effectively reduce cadmium in the flue gas (Cd) 25%, reduces arsenic (As) 13%.
Embodiment 5
Prepare proline (5%) and arginine (2%) mixed solution 100g with distilled water, the silica gel 50g that weighs slowly adds mixed solution in the molecular sieve, stirs simultaneously, and the equal-volume infuse made it abundant infiltration in 2 hours; The wet particle thing is moved in the baking oven, and baking made material fully dry in 24 hours under 100 ℃ of conditions, naturally cooled to room temperature, and it is for use that the removal fine powder that sieves is got 40-60 order particle.
The complexing adsorbent that makes propped up with 30mg/ add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample is after temperature humidity balance, resistance to suction and weight screening; Carry out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004; Heavy metal adopts the static trap tube to capture in the main flume grain phase constituent, and heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition, and the heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed.The flue gas analysis result shows that this material can effectively reduce cadmium in the flue gas (Cd) 28%, reduces arsenic (As) 15%.
Embodiment 6
Prepare arginine (5%) and glycine (5%) mixed solution 100g with distilled water, the silica gel 50g that weighs slowly adds mixed solution in the silica gel, stirs simultaneously, and the equal-volume infuse made it abundant infiltration in 2 hours; In wet particle thing immigration baking oven, 100 ℃ of conditions cause thermal responses and toast 24h with this understanding fully reacts material and drying, naturally cools to room temperature, and it is for use that the removal fine powder that sieves is got 40-60 order particle.
The complexing adsorbent that makes propped up with 40mg/ add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample is after temperature humidity balance, resistance to suction and weight screening; Carry out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004; Heavy metal adopts the static trap tube to capture in the main flume grain phase constituent, and heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition, and the heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed.The flue gas analysis result shows that this material can effectively reduce cadmium in the flue gas (Cd) 40%, reduces arsenic (As) 20%.
Embodiment 7
Prepare alanine (3%), serine (2%) and arginine (2%) mixed solution 100g with distilled water, the silica gel 50g that weighs slowly adds mixed solution in the silica gel, stirs simultaneously, and the equal-volume infuse made it abundant infiltration in 4 hours; The wet particle thing is moved in the baking oven, and baking made material fully react in 24 hours and drying under 100 ℃ of conditions, naturally cooled to room temperature, and it is for use that the removal fine powder that sieves is got 40-60 order particle.
The complexing adsorbent that makes propped up with 30mg/ add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample is after temperature humidity balance, resistance to suction and weight screening; Carry out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004; Heavy metal adopts the static trap tube to capture in the main flume grain phase constituent, and heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition, and the heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed.The flue gas testing result shows that this material can effectively reduce cadmium in the flue gas (Cd) 32%, reduces arsenic (As) 18%.
Embodiment 8
Tryptophan propped up with 4mg/ add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample carries out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004 after temperature humidity balance, resistance to suction and weight screening, heavy metal adopts the static trap tube to capture in the main flume grain phase constituent; Heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition; The heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed, and the flue gas analysis testing result shows that tryptophan can effectively reduce cadmium in the flue gas (Cd) 15%, reduces arsenic (As) 5%.
Embodiment 9
Tryptophan and arginine (mass ratio is 1: 1) are propped up with 5mg/ and add in the cigarette composite filter tip; Roll into cigarette; Cigarette sample is after temperature humidity balance, resistance to suction and weight screening; Carry out cigarette smoking with R200H type disk type smoking machine according to GB/T 16450-2004; Heavy metal adopts the static trap tube to capture in the main flume grain phase constituent, and heavy metal adopts the absorption bottle of the salpeter solution that is added with 20mL10% to collect in the gas phase composition, and the heavy metal that the heavy metal analysis adopts the ICP-MS method that two parts are collected in the sample is analyzed; The flue gas analysis testing result shows that tryptophan and arginic mixture can effectively reduce cadmium in the flue gas (Cd) 18%, reduces arsenic (As) 10%.
Claims (18)
1. the complexing adsorbent that can reduce cigarette mainstream flue gas heavy metal burst size is that amino acid is carried on inorganic carrier particle or the acetate fiber carrier.
2. complexing adsorbent according to claim 1, described inorganic carrier particle is silica gel, aluminium oxide or molecular sieve.
3. complexing adsorbent according to claim 1 and 2, said inorganic carrier granular size is the 10-100 order.
4. complexing adsorbent according to claim 3, said inorganic carrier granular size is the 40-60 order.
5. complexing adsorbent according to claim 1; Described amino acid refers to glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, tyrosine, serine, cysteine, methionine, asparagine, glutamine, threonine, one or more in aspartic acid, glutamic acid, lysine, arginine, the histidine.
6. according to claim 1 or 2 or 5 described complexing adsorbents, it is characterized in that the mass loading amount of described amino acid on inorganic carrier particle or acetate fiber carrier is 1-20%.
7. complexing adsorbent according to claim 6 is characterized in that, the mass loading amount of described amino acid on inorganic carrier particle or acetate fiber carrier is 5-10%.
8. the preparation method of claim 1 or 2 or 5 complexing adsorbent is characterized in that, inorganic carrier impregnated in the Freamine, gets final product after having amino acid whose carrier to take out oven dry load again; Or amino acid made an addition on the acetate fiber carrier.
9. method according to claim 8 is characterized in that, the mass percent concentration of said Freamine is 0.1%-20%.
10. method according to claim 8 is characterized in that, described dip time is 5 minutes～5 hours.
11. method according to claim 10 is characterized in that, described dip time is 1 hour～3 hours.
12. method according to claim 8 is characterized in that, described bake out temperature is 80 ℃～180 ℃.
13. method according to claim 12 is characterized in that, described bake out temperature is 100 ℃～150 ℃.
14., it is characterized in that described drying time is 3～24 hours according to claim 12 or 13 described methods.
15. method according to claim 14 is characterized in that, described drying time is 5～12 hours.
16. the application of claim 1 or 2 or 5 described complexing adsorbents is characterized in that, with the adsorbent of described complexing adsorbent as the cigarette filter rod of heavy metal burst size in the reduction cigarette mainstream flue gas.
17. the application of complexing adsorbent according to claim 16, the addition of complexing adsorbent in cigarette filter rod with inorganic carrier particle is that 1-40mg/ props up.
18. the application of complexing adsorbent according to claim 16, the addition of complexing adsorbent in cigarette filter rod with inorganic carrier particle is that 2-30mg/ props up.
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Application publication date: 20120620 |