CN108142987B - Additive for reducing nitride in flue gas and application thereof - Google Patents

Additive for reducing nitride in flue gas and application thereof Download PDF

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Publication number
CN108142987B
CN108142987B CN201711452332.3A CN201711452332A CN108142987B CN 108142987 B CN108142987 B CN 108142987B CN 201711452332 A CN201711452332 A CN 201711452332A CN 108142987 B CN108142987 B CN 108142987B
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additive
solution
hydroxyapatite
smoke
cigarette
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CN108142987A (en
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郭磊
罗娟敏
李赓
胡巍耀
苏加坤
田耀伟
罗海涛
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China Tobacco Jiangxi Industrial Co Ltd
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China Tobacco Jiangxi Industrial Co Ltd
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    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/24Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
    • A24B15/26Use of organic solvents for extraction
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B3/00Preparing tobacco in the factory
    • A24B3/12Steaming, curing, or flavouring tobacco

Abstract

The invention discloses an additive for reducing nitride in smoke, which is prepared from the following raw materials in parts by weight: 15-75% of hydroxyapatite, 5-50% of cyclodextrin, 1-25% of polyester nanofiber or polyethyleneimine and polyvinyl alcohol, and optionally blending iron or ferrous compounds or copper and cuprous compounds. The invention obviously reduces the content of nitride in the cigarette smoke by utilizing natural renewable resources, transition metals and other low-cost materials, does not generate negative influence on the sensory quality of the cigarette, and has important academic significance and practical significance for the development of tobacco science and tobacco industry. The preparation method is simple in preparation process, easy to realize coating application mode addition, low in application cost and good in actual production application prospect.

Description

Additive for reducing nitride in flue gas and application thereof
Technical Field
The invention relates to the technical field of cigarette flavors, in particular to an additive for reducing nitrides in smoke.
Background
Smoking not only causes chronic diseases such as pulmonary diseases and heart diseases, but also causes death of many people every year. Cigarettes contain over 4 thousands of chemicals, 43 of which are known carcinogens, and at least 250 of which are substances harmful to health. Smokers have an average life span 14 years less than non-smokers, and thus smoking habits are considered as the leading preventable cause of disease and death.
Smoking is harmful to health, nitrides (NO, NO)XHCN, carcinogenic nitroso compound and the like) are one of harmful components in cigarette smoke, and the reduction of the content of nitride has important value for improving the safety of cigarettes.
In the Hoffman list, the harmful nitrogen oxides are mainly NO, NOXResearch shows that NO is the main nitrogen oxide in cigarette smoke. The cigarette mainstream smoke and the side stream smoke both contain a certain amount of NO, but the content of the NO is greatly different from that of the side stream smoke, the content of the NO in the cigarette mainstream smoke is about 100-600 mu g/cigarette, and the cigarette is generated by smolderingThe amount of NO is much larger than that generated by suction, and the content of NO in the side stream smoke is 3-13 times of that in the main stream smoke. Exogenous nitrogen oxide (NOx) is toxic and NOx is one of the most important components in air pollution. NO has been considered as a cause of underground storage compartment disease. Early studies thought that a portion of NO itself was toxic to lung tissue, but in fact this was because early researchers could not control the oxidation of NO to form nitrogen dioxide (NO) in aerobic conditions2) Thus NO is added2The partial toxic effect of (a) is mistaken for NO, leading to erroneous conclusions. Inhalation of high concentrations of NO and NO2The mixed gas can cause fatal pulmonary edema and methemoglobinopathy of human beings and experimental animals, and dogs are placed in 5000-. The adverse effects and toxicity of NO and its metabolites on the body may have several aspects: (1) forms MetHb upon binding to Hb; (2) oxidation to form NO2(ii) a Formation of peroxynitrite (OONO-), with superoxide anion; (4) forming nitroso-mercaptol compounds with mercapto groups; (5) teratogenic and carcinogenic potential. However, medical scientists believe that trace amounts of NO are signal molecules of the nervous system, act as anti-infective weapons, as a regulator of blood pressure, and as a caretaker of blood entering different organs. Clinical application of NO proves that NO has the effects of treating and relieving various diseases (such as cardiovascular diseases, nervous system diseases, lung diseases, tumors and the like). Therefore, if the NO in the cigarette smoke can be reduced to a trace amount required by treatment, the harm can be changed into the benefit.
The existing technology for reducing the nitrides in the smoke of the cigarettes has the technical bottlenecks of fragrance weakening, dry throat and cigarette comfort reduction, and the main problem is to reduce the harm of the cigarettes and simultaneously reduce the negative influence on the sensory quality of the cigarettes as much as possible.
Cyclodextrin is a natural renewable resource, is widely applied to the chemical industry, sewage treatment and daily cosmetics industry, is increasingly concerned in the cigarette industry, and can be synthesized to have long service life, good mechanical property or high dispersion property by constructing the cyclodextrin on other carriersThe adsorbent material of (1). The carriers are mainly classified into inorganic molecules, organic synthetic polymers and natural product polymers. Inorganic carrier including graphene oxide, carbon nanotube and SiO2Nanoparticles, magnetic Fe3O4Nanoparticles, zeolites, and the like; the organic synthetic polymer carrier comprises high polymer such as polyethyleneimine, polyvinyl alcohol, polypropylene, polystyrene, polyester nanofiber and the like; the natural polymer carrier comprises cellulose and its derivatives, wood powder, hydroxyapatite, gelatin, sodium alginate, etc.
The cyclodextrin has wide source and low cost. Transition metals are also much less expensive than precious metals. Therefore, the research on the smoke forming mechanism can actively promote the smooth progress of the smoke harm reduction problem by reducing the harmful components in the smoke by using the low-cost natural renewable resources cyclodextrin and the carrier thereof as well as the transition metal.
Disclosure of Invention
The invention aims to provide an additive for reducing nitrides in smoke, which utilizes natural renewable resources, transition metals and other low-cost materials to reduce the nitrides in the mainstream smoke of cigarettes and has important academic significance and practical significance for the development of tobacco science and tobacco industry.
The invention discloses an additive for reducing nitride in smoke, which is prepared from the following raw materials in parts by weight: 15-75% of hydroxyapatite, 5-50% of cyclodextrin, 1-25% of polyester nanofiber or polyethyleneimine, and optionally blending iron or ferrous compounds or copper and cuprous compounds.
Further, the iron or ferrous compound may be an organic acid salt of iron or ferrous, an inorganic acid salt of iron or ferrous, iron oxide or ferrous oxide powder, iron hydroxide or ferrous oxide powder, freshly prepared iron oxide or ferrous oxide, freshly prepared iron hydroxide or ferrous hydroxide.
Further, the copper or cuprous compound may be an organic acid salt of copper or cuprous, an inorganic acid salt of copper or cuprous, cupric oxide or cuprous oxide powder, cupric hydroxide or cuprous hydroxide powder, or freshly prepared cupric oxide or cuprous oxide, cupric hydroxide or cuprous hydroxide.
The preparation method of the additive for reducing the nitride in the flue gas comprises the following steps: dissolving hydroxyapatite by using 1% HCl to prepare 2% hydroxyapatite solution, adjusting the pH value of the solution to 4-5 by using 25wt% NaOH solution, respectively adding ferric nitrate solution and copper sulfate solution, adding 25wt% NaOH solution under strong stirring to adjust the pH value of the solution to 8-9, after the reaction is finished, adding 95% ethanol to precipitate hydroxyapatite metal compound, filtering and precipitating, filtering and washing the precipitate by using hot distilled water, adding ethanol solution of cyclodextrin and polyethyleneimine under strong stirring, standing, precipitating and crystallizing, and drying at 75-90 ℃ to obtain the additive.
The application mode of the additive for reducing the nitride in the smoke in the cigarette is as follows: diluting the additive by 0.01-0.1 ‰, spraying onto tobacco shred, air drying, balancing at 22 deg.C and 60% humidity for more than 10 hr, and making into cigarette.
Compared with the prior art, the invention has the advantages and positive effects that:
the invention obviously reduces the content of nitride in the cigarette smoke by utilizing natural renewable resources, transition metals and other low-cost materials, does not generate negative influence on the sensory quality of the cigarette, and has important academic significance and practical significance for the development of tobacco science and tobacco industry.
The preparation method is simple in preparation process, easy to realize coating application mode addition, low in application cost and good in actual production application prospect.
Detailed Description
The technical scheme of the invention is explained in detail by combining the following embodiments:
example 1
An additive for reducing nitride in smoke is prepared from the following raw materials by weight: 57 percent of hydroxyapatite, 25 percent of cyclodextrin, 15 percent of polyethyleneimine, ferric nitrate and copper sulfate are randomly prepared.
The preparation method of the additive for reducing the nitride in the flue gas comprises the following steps: dissolving hydroxyapatite by using 1% HCl to prepare 2% hydroxyapatite solution, adjusting the pH value of the solution to 4-5 by using 25wt% NaOH solution, respectively adding ferric nitrate solution and copper sulfate solution, adding 25wt% NaOH solution under strong stirring to adjust the pH value of the solution to 8-9, after the reaction is finished, adding 95% ethanol to precipitate hydroxyapatite metal compound, filtering and precipitating, filtering and washing the precipitate by using hot distilled water, adding ethanol solution of cyclodextrin and polyethyleneimine under strong stirring, standing, precipitating and crystallizing, and drying at 75-90 ℃ to obtain the additive.
Example 2
An additive for reducing nitride in smoke is prepared from the following raw materials by weight: 29 percent of hydroxyapatite, 43 percent of cyclodextrin, 17 percent of polyester nanofiber, ferric oxide and copper nitrate are randomly prepared.
The preparation method of the additive for reducing the nitride in the flue gas comprises the following steps: dissolving hydroxyapatite by using 1% HCl to prepare 2% hydroxyapatite solution, adjusting the pH value of the solution to 4-5 by using 25wt% NaOH solution, respectively adding ferric oxide solution and copper nitrate solution, adding 25wt% NaOH solution under strong stirring to adjust the pH value of the solution to 8-9, after the reaction is finished, adding 95% ethanol to precipitate hydroxyapatite metal compound, filtering and precipitating, filtering and washing the precipitate by using hot distilled water, adding ethanol solution of cyclodextrin and polyester nanofiber under strong stirring, standing, precipitating and crystallizing, and drying at 75-90 ℃ to obtain the additive.
Example 3
An additive for reducing nitride in smoke is prepared from the following raw materials by weight: 65% of hydroxyapatite, 21% of cyclodextrin, 13% of polyethyleneimine, ferric nitrate and copper nitrate are optionally blended.
The preparation method of the additive for reducing the nitride in the flue gas comprises the following steps: dissolving hydroxyapatite by using 1% HCl to prepare 2% hydroxyapatite solution, adjusting the pH value of the solution to 4-5 by using 25wt% NaOH solution, respectively adding ferric nitrate solution and copper nitrate solution, adding 25wt% NaOH solution under strong stirring to adjust the pH value of the solution to 8-9, after the reaction is finished, adding 95% ethanol to precipitate hydroxyapatite metal compound, filtering and precipitating, filtering and washing the precipitate by using hot distilled water, adding ethanol solution of cyclodextrin and polyethyleneimine under strong stirring, standing, precipitating and crystallizing, and drying at 75-90 ℃ to obtain the additive.
Test examples
(I) the nitride NO and NO in the smoke after the sample is placed for three monthsXHCN and NH3Is released from
Testing the nitrides NO, HCN and NH in the smoke of the blank cigarettes and the samples added with the additives for reducing the nitrides in the smoke of the examples 1-3 after being placed for three months according to the methods of the corresponding national standards and the tobacco industry standards3The results are shown in table 1 below:
TABLE 1 cigarette samples after three months of storage nitrided NO, HCN and NH3Is released from
Sample (I) NO/(mg. branched)-1) HCN/(μ g, count)-1) NH3/(. mu.g.ramus)-1)
Control 10.8 84 8.1
Example 1 9.7 72 7.4
Example 2 9.6 69 7.1
Example 3 9.8 70 7.3
The results of the nitride emissions in Table 1 all show that the cigarettes containing the smoke nitride reducing additives of examples 1-3 of the present invention, the nitrides NO, HCN and NH3The amount of release of (a) is reduced.
(II) sensory evaluation
Reference is made to GB5606.4-2005 cigarette part 4: sensory technical requirements and YC/T497-:
TABLE 2 cigarette sensory evaluation
The sensory evaluation results in table 2 all show that the cigarettes added with the additives for reducing the nitrides in the smoke of the invention in the examples 1-3 have pleasant fresh scent and obvious sweet feeling of the smoke, can play the roles of reducing the dryness of the mouth and throat and relieving the smoke irritation in the smoking process of the cigarettes, and are suitable for high-quality cigarettes.
The above embodiments are merely preferred embodiments of the present invention, and any simple modification, modification and substitution changes made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.

Claims (2)

1. The additive for reducing the nitride in the smoke is characterized by being prepared from 5 raw materials of hydroxyapatite, cyclodextrin, polyethyleneimine, ferric nitrate and copper sulfate, wherein the total weight of the 5 raw materials is 100%, the hydroxyapatite accounts for 15-75% of the total weight, the cyclodextrin accounts for 5-50% of the total weight, the polyethyleneimine accounts for 1-25% of the total weight, and the balance of the ferric nitrate and the copper sulfate are prepared in any proportion;
and the preparation method of the additive for reducing the nitride in the flue gas comprises the steps of dissolving hydroxyapatite by using 1% HCl to prepare a 2% hydroxyapatite solution, adjusting the pH value to 4-5 by using a 25wt% NaOH solution, adding a ferric nitrate solution and a copper sulfate solution respectively, adding a 25wt% NaOH solution under strong stirring to adjust the pH value of the solution to 8-9, adding 95% ethanol to precipitate a hydroxyapatite metal compound after the reaction is finished, filtering and precipitating, filtering and washing the precipitate by using hot distilled water, adding an ethanol solution of cyclodextrin and polyethyleneimine under strong stirring, standing, precipitating crystals, and drying at 75-90 ℃ to obtain the additive.
2. The application of the additive for reducing the nitrides in the smoke in the cigarette as claimed in claim 1, wherein the additive is diluted according to 0.01-0.1 per thousand, and then uniformly sprayed on the cut tobacco, and then the cut tobacco is naturally dried, and is balanced for more than 10 hours at the temperature of 22 ℃ and the humidity of 60%, and then the cut tobacco is made into the cigarette by a cigarette making device.
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CN110754685A (en) * 2019-11-12 2020-02-07 广东中烟工业有限责任公司 Cigarette with low harmful components in smoke and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1288018A (en) * 2000-10-25 2001-03-21 南京比特福贸易有限公司 Cyclodextrin liquid additive used for lowering content of nitrosamine in smoke of cigarette
CN1513386A (en) * 2003-07-07 2004-07-21 长沙卷烟厂 Matter for lowering contents of tar and like harmful matter in smoke of cigarette
CN1720828A (en) * 2004-07-13 2006-01-18 青木秀希 Tobacco and cigarette with reduced harmful components
CA2500750A1 (en) * 2005-03-21 2006-09-21 Roger Ouellette Liquid compound added to the preparation of cigarette, cigar and pipe tobacco and chewing tobacco. designed to reduce the risk of disease caused by tobacco smoke.
CN101669678A (en) * 2009-09-24 2010-03-17 中国烟草总公司郑州烟草研究院 Filter additive material for selectively reducing hydrocyanic acid emission amount in mainstream smoke of cigarette and preparation method thereof
CN102987564A (en) * 2012-12-12 2013-03-27 湖南中烟工业有限责任公司 Cigarette filtering rod additive for reducing content of ammonia in mainstream smoke as well preparation method and application thereof
CN103190704A (en) * 2013-04-17 2013-07-10 江苏中烟工业有限责任公司 Method for selectively reducing specific nitrosamines in cigarette smoke
CN105342006A (en) * 2015-12-09 2016-02-24 中国烟草总公司郑州烟草研究院 Liquid function material for selectively reducing HCN in cigarette main stream smoke and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1288018A (en) * 2000-10-25 2001-03-21 南京比特福贸易有限公司 Cyclodextrin liquid additive used for lowering content of nitrosamine in smoke of cigarette
CN1513386A (en) * 2003-07-07 2004-07-21 长沙卷烟厂 Matter for lowering contents of tar and like harmful matter in smoke of cigarette
CN1720828A (en) * 2004-07-13 2006-01-18 青木秀希 Tobacco and cigarette with reduced harmful components
CA2500750A1 (en) * 2005-03-21 2006-09-21 Roger Ouellette Liquid compound added to the preparation of cigarette, cigar and pipe tobacco and chewing tobacco. designed to reduce the risk of disease caused by tobacco smoke.
CN101669678A (en) * 2009-09-24 2010-03-17 中国烟草总公司郑州烟草研究院 Filter additive material for selectively reducing hydrocyanic acid emission amount in mainstream smoke of cigarette and preparation method thereof
CN102987564A (en) * 2012-12-12 2013-03-27 湖南中烟工业有限责任公司 Cigarette filtering rod additive for reducing content of ammonia in mainstream smoke as well preparation method and application thereof
CN103190704A (en) * 2013-04-17 2013-07-10 江苏中烟工业有限责任公司 Method for selectively reducing specific nitrosamines in cigarette smoke
CN105342006A (en) * 2015-12-09 2016-02-24 中国烟草总公司郑州烟草研究院 Liquid function material for selectively reducing HCN in cigarette main stream smoke and application thereof

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