CN115364819A - Preparation method of porous functional millet particles for cigarette filter - Google Patents
Preparation method of porous functional millet particles for cigarette filter Download PDFInfo
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- CN115364819A CN115364819A CN202210987230.6A CN202210987230A CN115364819A CN 115364819 A CN115364819 A CN 115364819A CN 202210987230 A CN202210987230 A CN 202210987230A CN 115364819 A CN115364819 A CN 115364819A
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- millet
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- porous functional
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- 244000062793 Sorghum vulgare Species 0.000 title claims abstract description 120
- 235000019713 millet Nutrition 0.000 title claims abstract description 120
- 235000019504 cigarettes Nutrition 0.000 title claims abstract description 70
- 239000002245 particle Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 102000004190 Enzymes Human genes 0.000 claims abstract description 29
- 108090000790 Enzymes Proteins 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229940088598 enzyme Drugs 0.000 claims abstract description 29
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 22
- 238000011282 treatment Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 102000004139 alpha-Amylases Human genes 0.000 claims abstract description 11
- 108090000637 alpha-Amylases Proteins 0.000 claims abstract description 11
- 229940024171 alpha-amylase Drugs 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 230000000694 effects Effects 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- -1 iron ions Chemical class 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000003906 humectant Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000796 flavoring agent Substances 0.000 claims description 3
- 235000019634 flavors Nutrition 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 238000004042 decolorization Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 28
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 abstract description 14
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 abstract description 12
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 239000013538 functional additive Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000007864 aqueous solution Substances 0.000 description 24
- 238000001035 drying Methods 0.000 description 22
- 238000001914 filtration Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 239000000779 smoke Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 230000003472 neutralizing effect Effects 0.000 description 8
- 230000000391 smoking effect Effects 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 235000009508 confectionery Nutrition 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000002255 enzymatic effect Effects 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 239000007974 sodium acetate buffer Substances 0.000 description 5
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 235000014633 carbohydrates Nutrition 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 239000000686 essence Substances 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 230000001953 sensory effect Effects 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012735 amaranth Nutrition 0.000 description 1
- 239000004178 amaranth Substances 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- A24D3/02—Manufacture of tobacco smoke filters
-
- 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
- A24D3/04—Tobacco smoke filters characterised by their shape or structure
- A24D3/048—Tobacco smoke filters characterised by their shape or structure containing additives
-
- 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
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- 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
-
- 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
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
Abstract
The invention belongs to the field of adsorption additives for filter tips, and particularly relates to a preparation method of porous functional millet particles for cigarette filter tips. The preparation method of the porous functional millet particles comprises the following steps: (1) Decolorizing millet in alcohol solvent to obtain decolorized millet; (2) Performing pore-forming treatment on the decolored millet by using saccharifying enzyme and alpha-amylase to obtain porous millet; (3) Carrying out oxidation treatment on the porous millet under the action of a catalyst and an oxidant to obtain porous oxidized millet; (4) And loading metal ions on the porous oxidized millet to prepare the porous functional millet. The functional additive for the cigarette filter is prepared by taking millet as a main raw material, and has the advantages that the reduction rate of hydrogen cyanide reaches 40-60%, the reduction rate of crotonaldehyde reaches 25-35%, and the reduction rate of ammonia reaches 30-45%; after the functional components are carried, the functions of richer material color change, cigarette aroma enhancement and moisture retention and the like can be realized, so that the quality of the cigarettes is improved, and the characteristics of the cigarettes are improved.
Description
Technical Field
The invention belongs to the field of adsorption additives for filter tips, and particularly relates to a preparation method of porous functional millet particles for cigarette filter tips.
Background
The cigarette filter is an important component of cigarette products, can effectively intercept tar and partial harmful components in smoke, and is generally regarded and widely applied. As a very important carrier on cigarettes, the cigarette filter plays more and more important roles in reducing harmful ingredients in cigarette smoke, improving the sensory quality of cigarette products and the like by carrying functional additives.
Chinese patent application publication No. CN112890277A discloses a method for preparing color-changing sweet harm-reducing granules for cigarette filter sticks, which comprises the following steps: preparing sweet syrup, broken sugar blocks, a harm reducing liquid obtained by the reaction of a solution of amino acid and choline, a harm reducing powder obtained by the harm reducing liquid and fructose powder, granulating to obtain sweet harm reducing granules, and loading a color-changing agent to obtain the color-changing sweet harm reducing granules. The color-changing sweet harm-reducing particles can react with and adsorb harmful components to reduce harm, and the color-changing agent can generate color change after contacting with smoke, thereby bringing multiple sensory experiences to consumers.
Although the color-changing sweet harm-reducing particles realize multifunction, the effect of reducing CO, ammonia, phenol and crotonaldehyde in smoke is basically not reduced, and the overall harm-reducing effect needs to be further improved.
Disclosure of Invention
The invention aims to provide a preparation method of porous functional millet particles for cigarette filters, which has better effect of reducing harmful ingredients such as hydrogen cyanide, crotonaldehyde, ammonia and the like in mainstream smoke of cigarettes, can exert a color change function, and can realize richer color change of materials and aroma enhancement and moisture retention of the cigarettes after carrying functional ingredients further.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of porous functional millet particles for cigarette filters comprises the following steps:
(1) Decolorizing millet in alcohol solvent to obtain decolorized millet;
(2) Carrying out pore-forming treatment on the decolored millet by using saccharifying enzyme and alpha-amylase to obtain porous millet;
(3) Carrying out oxidation treatment on the porous millet under the action of a catalyst and an oxidant to obtain porous oxidized millet; the catalyst is copper sulfate;
(4) Loading metal ions on the porous oxidized millet to prepare porous functional millet; the metal ions are selected from one or the combination of more than two of divalent copper ions, divalent zinc ions, trivalent iron ions and trivalent aluminum ions.
The preparation method of the porous functional millet particles for the cigarette filter comprises the steps of preparing a cigarette filter functional additive by taking millet as a main raw material, and after compound modification, keeping a higher level in the aspect of reducing the release amount of harmful components such as hydrogen cyanide, crotonaldehyde and ammonia in cigarette smoke, wherein the reduction rate of the hydrogen cyanide reaches 40-60%, the reduction rate of the crotonaldehyde reaches 25-35% and the reduction rate of the ammonia reaches 30-45%. Some of them metal ion self-colored, still can appear the colour change when the flue gas passes through, increase visual experience. After functional components are further carried, the functions of richer material color change, cigarette aroma enhancement and moisture retention and the like can be realized, so that the quality of the cigarettes is improved, and the characteristics of the cigarettes are improved.
Preferably, in the step (1), the alcohol solvent is absolute ethyl alcohol or an ethanol solution; the decolorization is carried out by keeping the temperature at 25-70 ℃ for 1-10 h.
Preferably, in the step (2), the pore-forming treatment is performed under the condition of pH = 4.5-6; every 50g of decolorized millet corresponds to 0.3-0.7 g of enzyme and 150-200 g of solvent; the enzyme activity ratio of the saccharifying enzyme to the alpha-amylase is (1.5-6): 1. further preferably, the temperature of the pore-forming treatment is 35-65 ℃, and the heat preservation time is 2.5-20 h.
Preferably, in step (3), the oxidizing agent is hydrogen peroxide; the hydrogen peroxide is added in the form of an aqueous hydrogen peroxide solution. Further preferably, the oxidation treatment is performed at a pH =8 to 10; every 30g of porous millet corresponds to 0.05-0.26 g of copper sulfate, 85-115 g of water and 0.9-2.8 g of hydrogen peroxide solution, and the mass fraction of the hydrogen peroxide solution is 30%.
More preferably, the temperature of the oxidation treatment is 40-65 ℃, the hydrogen peroxide solution adopts a dropwise adding system, the dropwise adding time is 1-2 h, and the heat preservation reaction is continued for 1-4 h after the dropwise adding. Most preferably, the oxidation treatment is followed by the use of a reducing agent to remove unreacted hydrogen peroxide.
Preferably, in the step (4), the load is in the form of dipping the metal ion salt solution, and the molar concentration of the metal ion salt solution is 0.1-0.8 mol/L.
Further preferably, after the metal ions are loaded, the paint also comprises carried pigment, essence and flavor and/or humectant.
Detailed Description
The raw material used by the invention is millet, which has the advantages of wide source, environmental protection and the like, and the millet is spherical-like, and the shape and the size of the millet meet the basic requirements of the cigarette filter additive.
The mechanism of millet composite modification of the invention is illustrated as follows:
(1) The millet mainly comprises carbohydrates, proteins, amino acids, fats, fatty acids and the like. The carbohydrate provides a chemical basis for the porous modification of the cigarette, amino groups in the protein and the amino acid have a certain chemisorption effect on hydrogen cyanide and crotonaldehyde, and the fatty acid and carboxyl groups in the protein and the amino acid have a certain neutralization effect on ammonia, so that the carbohydrate provides a certain physical and chemical basis for removing harmful components such as hydrogen cyanide, crotonaldehyde and ammonia in cigarette smoke.
(2) The surface of millet is distributed with a layer of pigment, so that the subsequent modification reaction can be effectively carried out, the invention firstly adopts ethanol to carry out decoloration treatment on the millet.
(3) Because the millet is rich in carbohydrates such as starch and the like, the porous millet is prepared by adopting an enzyme method under the condition of keeping the integrity of the millet particles, and the porous characteristic of the porous millet is favorable for adsorbing harmful ingredients in cigarette smoke.
(4) In order to effectively adsorb harmful ingredients such as hydrogen cyanide and ammonia in cigarette smoke, the porous modified porous millet is further modified by two steps of oxidation and metal ion impregnation, the porous millet contains more carboxyl groups after being modified by oxidation and is easy to load metal ions, and the metal ions can be complexed with the hydrogen cyanide and the ammonia, so that the adsorption effect is improved. Meanwhile, some metal ions have colors, and the color of the smoke can be changed after the smoke passes through the metal ions, so that the visual experience is improved.
(5) The porous characteristic of the porous functional millet also provides a foundation for further carrying other functional components, so that pigments, flavors, fragrances, humectants and the like can be further carried, the effects of richer material color change, cigarette aroma enhancement, moisturizing and the like are realized, and the characteristics and quality of cigarette products are improved.
The addition amount of the porous functional millet particles prepared by the method is generally 10-60mg per cigarette, and preferably 20-50mg per cigarette.
The invention will be further described with reference to the following examples, but the scope of the invention is not limited to these examples. In the following examples, reagents used were all commercially available conventional species unless otherwise specified. The enzyme activity of the saccharifying enzyme is 120U/mg, and the enzyme activity of the alpha-amylase is 30U/mg.
1. Specific embodiment of the method for preparing porous functional millet particles for cigarette filters
Example 1
The preparation method of the porous functional millet particles for the cigarette filter comprises the following steps:
(1) And (3) decoloring: adding 100g of millet into 800g of 65% ethanol, preserving heat at 30 ℃ for 7.5h, filtering, washing with water, and drying (drying at 60 ℃ for 12h, recorded as 60 ℃/12 h) to obtain decolorized millet.
(2) Performing enzymatic pore-forming: adding 50g of decolorized millet into 150g of acetic acid-sodium acetate buffer solution with pH =4.5, heating to 30 ℃, preheating for 15min, adding 0.3g of complex enzyme, wherein the complex enzyme adopts saccharifying enzyme and alpha-amylase with the enzyme activity ratio of 6, keeping the temperature at 35 ℃ for 20h, then neutralizing to neutrality (pH = 7) with 3% sodium hydroxide aqueous solution, filtering, washing with water, and drying (60 ℃/12 h) to obtain the porous millet.
(3) And (3) oxidation: adding 30g of porous millet into 85g of water, adjusting the pH value of a system to 8-10 by using a 3% sodium hydroxide aqueous solution, adding 0.05g of copper sulfate, heating to 65 ℃, slowly dropwise adding 0.9g of a hydrogen peroxide solution (30 wt.%) within 1h, continuously carrying out heat preservation reaction for 1h after dropwise adding is finished, continuously dropwise adding a 3% sodium hydroxide aqueous solution during the reaction process to stabilize the pH value of the system to 8-10, reducing unreacted hydrogen peroxide by using ferrous sulfate after the reaction is finished, neutralizing the solution to be neutral (pH = 7) by using a 2% hydrochloric acid aqueous solution, filtering, washing with water, and drying (60 ℃/12 h) to obtain the porous oxidized millet.
(4) Impregnating metal ions: and adding 10g of porous oxidized millet into 40g of 0.6mol/L copper nitrate aqueous solution, stirring for 3h at 30 ℃, filtering, washing with water, and drying (60 ℃/12 h) to obtain the porous millet.
Example 2
The difference between the preparation method of porous functional millet particles for cigarette filters of the embodiment and the embodiment 1 is described as follows:
(1) And (3) decoloring: adding 100g of millet into 400g of 95% ethanol, preserving heat at 65 ℃ for 1.5h, filtering, washing with water, and drying at 60 ℃/12h to obtain the decolored millet.
(2) Performing enzymatic pore-forming: adding 50g of decolorized millet into 170g of acetic acid-sodium acetate buffer solution with pH =5.8, heating to 30 ℃, preheating for 25min, adding 0.59g of complex enzyme, preserving the temperature for 5h at 65 ℃ by adopting saccharifying enzyme and alpha-amylase with the enzyme activity ratio of 1.5, neutralizing by using 3% sodium hydroxide aqueous solution to be neutral, filtering, washing with water, and drying at 60 ℃/12h to obtain the porous millet.
(3) Adding 30g of porous millet into 90g of water, adjusting the pH value of a system to 8-10 by using a 3% sodium hydroxide aqueous solution, adding 0.18g of copper sulfate, heating to 55 ℃, slowly dropwise adding 2.8g of a hydrogen peroxide solution (30 wt.%) within 2h, continuously carrying out heat preservation reaction for 3h after dropwise adding is finished, continuously dropwise adding a 3% sodium hydroxide aqueous solution in the reaction process to stabilize the pH value of the system to 8-10, reducing unreacted hydrogen peroxide by using ferrous sulfate after the reaction is finished, neutralizing by using a 2% hydrochloric acid aqueous solution to be neutral, filtering, washing with water, and drying at 60 ℃/12h to obtain the porous oxidized millet.
(4) Impregnating metal ions: adding 10g of porous oxidized millet into 33g of 0.5mol/L aluminum sulfate aqueous solution, stirring for 5h at 25 ℃, filtering, washing with water, and drying at 60 ℃/12h to obtain the porous functional millet.
Example 3
The difference between the preparation method of porous functional millet particles for cigarette filters of the embodiment and the embodiment 1 is described as follows:
(1) And (3) decoloring: adding 100g of millet into 700g of absolute ethyl alcohol, preserving heat for 1h at 70 ℃, filtering, washing with water, and drying at 60 ℃/12h to obtain the decolored millet.
(2) Performing enzymatic pore-forming: adding 50g of decolorized millet into 155g of acetic acid-sodium acetate buffer solution with pH =4.9, heating to 30 ℃, preheating for 20min, adding 0.70g of complex enzyme, preserving the heat for 7h at 58 ℃ by adopting saccharifying enzyme and alpha-amylase with the enzyme activity ratio of 3.
(3) And (3) oxidation: adding 30g of porous millet into 115g of water, adjusting the pH value of a system to 8-10 by using a 3% sodium hydroxide aqueous solution, adding 0.22g of copper sulfate, heating to 40 ℃, slowly dropwise adding 2.0g of a hydrogen peroxide solution (30 wt.%) within 1.5h, continuously carrying out heat preservation reaction for 4h after dropwise adding is finished, continuously dropwise adding a 3% sodium hydroxide aqueous solution in the reaction process to stabilize the pH value of the system to 8-10, reducing unreacted hydrogen peroxide by using ferrous sulfate after the reaction is finished, neutralizing by using a 2% hydrochloric acid aqueous solution to be neutral, filtering, washing by using water, and drying at 60 ℃/12h to obtain the porous oxidized millet.
(4) Impregnation of metal ions: adding 10g of porous oxidized millet into 35g of 0.2mol/L ferric nitrate aqueous solution, stirring for 1.5h at 50 ℃, filtering, washing with water, and drying at 60 ℃/12h to obtain the porous millet.
Example 4
The difference between the preparation method of porous functional millet particles for cigarette filters of the embodiment and the embodiment 1 is described as follows:
(1) And (3) decoloring: adding 100g of millet into 600g of 90% ethanol, preserving heat for 4h at 55 ℃, filtering, washing with water, and drying at 60 ℃/12h to obtain the decolorized millet.
(2) Performing enzymatic pore-forming: adding 50g of decolorized millet into 195g of acetic acid-sodium acetate buffer solution with the pH value of 5.2, heating to 30 ℃, preheating for 18min, adding 0.48g of complex enzyme, preserving the temperature for 3.5h at 60 ℃ by adopting saccharifying enzyme and alpha-amylase with the enzyme activity ratio of 4, neutralizing by using 3% sodium hydroxide aqueous solution to be neutral, filtering, washing with water, and drying at 60 ℃/12h to obtain the porous millet.
(3) And (3) oxidation: adding 30g of porous millet into 95g of water, adjusting the pH value of a system to 8-10 by using a 3% sodium hydroxide aqueous solution, adding 0.15g of copper sulfate, heating to 60 ℃, slowly dropwise adding 2.2g of a hydrogen peroxide solution (30 wt.%) within 1.5h, continuously carrying out heat preservation reaction for 2h after dropwise adding is finished, continuously dropwise adding a 3% sodium hydroxide aqueous solution during the reaction process to stabilize the pH value of the system to 8-10, reducing unreacted hydrogen peroxide by using ferrous sulfate after the reaction is finished, neutralizing by using a 2% hydrochloric acid aqueous solution to be neutral, filtering, washing by using water, and drying at 60 ℃/12h to obtain the porous oxidized millet.
(4) Impregnating metal ions: and adding 10g of porous oxidized millet into 35g of 0.8mol/L zinc chloride aqueous solution, stirring for 4h at 35 ℃, filtering, washing with water, and drying at 60 ℃/12h to obtain the porous millet.
Example 5
The difference between the preparation method of porous functional millet particles for cigarette filters of the embodiment and the embodiment 1 is described as follows:
(1) And (3) decoloring: adding 100g of millet into 550g of 55% ethanol, preserving the heat for 10h at 25 ℃, filtering, washing with water, and drying at 60 ℃/12h to obtain the decolorized millet.
(2) Performing enzymatic pore-forming: adding 50g of decolorized millet into 165g of acetic acid-sodium acetate buffer solution with pH =5.5, heating to 30 ℃, preheating for 28min, adding 0.65g of complex enzyme, preserving the temperature for 4h at 62 ℃ by adopting saccharifying enzyme and alpha-amylase with the enzyme activity ratio of 2.
(3) And (3) oxidation: adding 30g of porous millet into 100g of water, adjusting the pH value of a system to 8-10 by using a 3% sodium hydroxide aqueous solution, adding 0.26g of copper sulfate, heating to 50 ℃, slowly dropwise adding 1.8g of a hydrogen peroxide solution (30 wt.%) within 1.5h, continuously carrying out heat preservation reaction for 2.5h after the dropwise adding is finished, continuously dropwise adding a 3% sodium hydroxide aqueous solution in the reaction process to stabilize the pH value of the system to 8-10, reducing unreacted hydrogen peroxide by using ferrous sulfate after the reaction is finished, neutralizing to be neutral by using a 2% hydrochloric acid aqueous solution, filtering, washing by using water, and drying at 60 ℃/12h to obtain the porous oxidized millet.
(4) Impregnating metal ions: adding 10g of porous oxidized millet into 32g of 0.15mol/L aluminum sulfate aqueous solution, stirring for 2h at 45 ℃, filtering, washing with water, and drying at 60 ℃/12h to obtain the porous functional millet.
Example 6
The difference between the preparation method of the porous functional millet granules for cigarette filters and the embodiment 2 is as follows:
5g of the porous functional millet granules obtained in example 2 was added to 20g of 0.01% amaranth aqueous solution, and the mixture was immersed and stirred for 2 hours, filtered, washed with water, and dried to obtain color-changing porous functional millet granules.
Example 7
According to the preparation method of the porous functional millet, 0.06g of tobacco essence (special for golden leaves) is added to 10g of the porous functional millet in the embodiment 2 in a spraying manner, and the porous functional millet with the aroma enhancement function is obtained after drying.
Example 8
In the preparation method of the porous millet of the embodiment, 0.12g of the tobacco humectant (propylene glycol) is added to 10g of the porous millet of the embodiment 2 in a mist spray manner, and the porous millet with the moisture preserving function is obtained after drying.
Example 9
According to the preparation method of the porous millet, 0.06g of tobacco essence (same as example 7) is added to 10g of the porous millet in example 6 in a spraying manner, and the porous millet with the color changing and aroma enhancing functions is obtained after drying.
2. Examples of the experiments
Experimental example 1
The 9 materials prepared in examples 1-9 were applied to a ternary hollow transparent composite filter rod, the addition amount was 50mg per cigarette, and the cigarettes were respectively labeled as test cigarettes 1-9, and the cigarette without any adsorbing material added to the ternary hollow transparent composite filter rod was used as a control cigarette.
Before testing, the cigarettes are balanced for 48 hours under the conditions of temperature (22 +/-1) DEG C and relative humidity (60 +/-2)% and then sorted by weight (average weight +/-0.02 g) and draw resistance (average draw resistance +/-49 Pa) to pick out the test cigarettes meeting the standard. Cigarette smoking tests were performed on a smoking machine according to standard smoking conditions and the amounts of hydrogen cyanide, crotonaldehyde, and ammonia released were measured according to standards YCT253-2008, YCT254-2008, and YCT377-2017, respectively, with the results shown in table 1.
TABLE 1 results of the amount of Hydrogen cyanide, crotonaldehyde, and Ammonia released in cigarette mainstream smoke
As can be seen from Table 1, the 9 materials in the examples can effectively reduce the release amount of hydrogen cyanide, crotonaldehyde and ammonia in the mainstream smoke of cigarettes, wherein the reduction rate of hydrogen cyanide is 40-60%, the reduction rate of crotonaldehyde is 25-35% and the reduction rate of ammonia is 30-45%. In addition, the material in examples 6 to 9 was reduced in the harm reduction effect to a different extent than the material in example 2, but the reduction range was limited. The porous millet still has good harm reduction performance after being subjected to treatments of color change, aroma enhancement, moisture retention and the like. In example 9, the effect of reducing the release amount of hydrogen cyanide, crotonaldehyde, ammonia and phenol in the mainstream smoke of cigarettes is still basically maintained by loading the pigment and the essence at the same time.
Experimental example 2
The materials prepared in example 1, example 6 and example 9 were applied to a ternary hollow transparent composite filter rod, respectively, with an addition of 50mg per cigarette. Before testing, the cigarettes are balanced for 48 hours under the conditions of temperature (22 +/-1) DEG C and relative humidity (60 +/-2)% and then sorted by weight (average weight +/-0.02 g) and draw resistance (average draw resistance +/-49 Pa) to pick out the test cigarettes meeting the standard.
The cigarette smoking test was performed on a smoking machine according to standard smoking conditions, and after smoking, the material prepared in example 1 changed from blue to pale green, the material prepared in example 6 changed from red to pale pink, and the material prepared in example 9 changed from red to pale pink.
Experimental example 3
The materials prepared in the embodiment 2 and the embodiments 7 to 9 are respectively applied to the ternary hollow transparent composite filter stick, the addition amount of the material is 50mg per cigarette, and the sensory evaluation of the cigarette is carried out on the filter stick. The results of the comparison with the material of example 2 show that the materials of example 7 and example 9 have the effects of increasing the fragrance of cigarettes and improving the comfort of cigarettes, and the material of example 8 has the effects of reducing irritation and improving the smoking quality.
Claims (10)
1. A preparation method of porous functional millet particles for cigarette filters is characterized by comprising the following steps:
(1) Decolorizing millet in alcohol solvent to obtain decolorized millet;
(2) Carrying out pore-forming treatment on the decolored millet by using saccharifying enzyme and alpha-amylase to obtain porous millet;
(3) Carrying out oxidation treatment on the porous millet under the action of a catalyst and an oxidant to obtain porous oxidized millet; the catalyst is copper sulfate;
(4) Loading metal ions on the porous oxidized millet to prepare porous functional millet; the metal ions are selected from one or the combination of more than two of divalent copper ions, divalent zinc ions, trivalent iron ions and trivalent aluminum ions.
2. The method for preparing porous functional millet particles for cigarette filters according to claim 1, wherein in the step (1), the alcohol solvent is absolute ethyl alcohol or an ethanol solution; the decolorization is carried out by keeping the temperature at 25-70 ℃ for 1-10 h.
3. The method for preparing porous functional millet particles for cigarette filters according to claim 1, wherein in the step (2), the pore-forming treatment is performed under the condition of pH = 4.5-6; every 50g of decolorized millet corresponds to 0.3-0.7 g of enzyme and 150-200 g of solvent; the enzyme activity ratio of the saccharifying enzyme to the alpha-amylase is (1.5-6): 1.
4. the method for preparing porous functional millet particles for cigarette filters according to claim 3, wherein the temperature for pore-forming treatment is 35-65 ℃ and the holding time is 2.5-20 h.
5. The method for preparing porous functional millet particles for cigarette filters according to claim 1, wherein in the step (3), the oxidizing agent is hydrogen peroxide; the hydrogen peroxide is added in the form of an aqueous hydrogen peroxide solution.
6. The method for preparing porous functional millet particles for cigarette filters according to claim 5, wherein the oxidation treatment is performed under the condition of pH = 8-10; every 30g of porous millet corresponds to 0.05-0.26 g of copper sulfate, 85-115 g of water and 0.9-2.8 g of hydrogen peroxide solution, and the mass fraction of the hydrogen peroxide solution is 30%.
7. The method for preparing porous functional millet particles for cigarette filters according to claim 5 or 6, wherein the temperature of the oxidation treatment is 40-65 ℃, the hydrogen peroxide solution adopts a dropwise adding system, the dropwise adding time is 1-2 h, and the reaction is continued for 1-4 h after dropwise adding.
8. The method for preparing porous functional millet particles for cigarette filters according to claim 7, wherein a reducing agent is used to remove unreacted hydrogen peroxide after the oxidation treatment.
9. The method of preparing porous functional millet particles for cigarette filters according to claim 1, wherein in the step (4), the loading is in the form of dipping the metal ion salt solution, and the molar concentration of the metal ion salt solution is 0.1-0.8 mol/L.
10. The method for preparing porous functional millet particles for cigarette filters according to claim 1 or 9, wherein the method further comprises loading pigments, flavors and fragrances and/or humectants after loading metal ions.
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