WO2001095748A1 - Smokable filler material containing a fruit material - Google Patents
Smokable filler material containing a fruit material Download PDFInfo
- Publication number
- WO2001095748A1 WO2001095748A1 PCT/GB2001/002563 GB0102563W WO0195748A1 WO 2001095748 A1 WO2001095748 A1 WO 2001095748A1 GB 0102563 W GB0102563 W GB 0102563W WO 0195748 A1 WO0195748 A1 WO 0195748A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- filler material
- smokable filler
- material according
- fruit
- smokable
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 212
- 239000000945 filler Substances 0.000 title claims abstract description 104
- 235000013399 edible fruits Nutrition 0.000 title claims abstract description 70
- 239000011230 binding agent Substances 0.000 claims abstract description 38
- 239000011256 inorganic filler Substances 0.000 claims abstract description 27
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 27
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 15
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 239000000443 aerosol Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 235000010443 alginic acid Nutrition 0.000 claims description 13
- 229920000615 alginic acid Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 235000000346 sugar Nutrition 0.000 claims description 11
- 230000000391 smoking effect Effects 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000012766 organic filler Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 7
- 229940072056 alginate Drugs 0.000 claims description 7
- 235000010980 cellulose Nutrition 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 240000006365 Vitis vinifera Species 0.000 claims description 5
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 235000011869 dried fruits Nutrition 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Chemical class 0.000 claims description 5
- 244000099147 Ananas comosus Species 0.000 claims description 3
- 235000007119 Ananas comosus Nutrition 0.000 claims description 3
- 235000004936 Bromus mango Nutrition 0.000 claims description 3
- 235000014826 Mangifera indica Nutrition 0.000 claims description 3
- 240000007228 Mangifera indica Species 0.000 claims description 3
- 235000009184 Spondias indica Nutrition 0.000 claims description 3
- 239000001814 pectin Substances 0.000 claims description 3
- 235000010987 pectin Nutrition 0.000 claims description 3
- 229920001277 pectin Polymers 0.000 claims description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N 2,3,4,5-tetrahydroxypentanal Chemical compound OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 2
- 235000009434 Actinidia chinensis Nutrition 0.000 claims description 2
- 244000298697 Actinidia deliciosa Species 0.000 claims description 2
- 235000009436 Actinidia deliciosa Nutrition 0.000 claims description 2
- 244000144730 Amygdalus persica Species 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 244000131522 Citrus pyriformis Species 0.000 claims description 2
- 235000011430 Malus pumila Nutrition 0.000 claims description 2
- 235000015103 Malus silvestris Nutrition 0.000 claims description 2
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 2
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 2
- 244000018633 Prunus armeniaca Species 0.000 claims description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- 229910000323 aluminium silicate Chemical class 0.000 claims description 2
- 235000021028 berry Nutrition 0.000 claims description 2
- 235000020971 citrus fruits Nutrition 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 244000061176 Nicotiana tabacum Species 0.000 claims 4
- 241000220225 Malus Species 0.000 claims 1
- 240000008790 Musa x paradisiaca Species 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 241000208125 Nicotiana Species 0.000 abstract description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 30
- 235000019504 cigarettes Nutrition 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000779 smoke Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- 239000000796 flavoring agent Substances 0.000 description 6
- 235000019634 flavors Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 235000010413 sodium alginate Nutrition 0.000 description 6
- 239000000661 sodium alginate Substances 0.000 description 6
- 229940005550 sodium alginate Drugs 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000012384 transportation and delivery Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 235000008504 concentrate Nutrition 0.000 description 4
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 235000010407 ammonium alginate Nutrition 0.000 description 3
- 239000000728 ammonium alginate Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 3
- 229960002715 nicotine Drugs 0.000 description 3
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 230000008570 general process Effects 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010451 perlite Substances 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
- 239000012254 powdered material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- 235000011514 Anogeissus latifolia Nutrition 0.000 description 1
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- 241000416162 Astragalus gummifer Species 0.000 description 1
- 235000013912 Ceratonia siliqua Nutrition 0.000 description 1
- 240000008886 Ceratonia siliqua Species 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 235000017788 Cydonia oblonga Nutrition 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 229920000855 Fucoidan Polymers 0.000 description 1
- SNVFDPHQAOXWJZ-UHFFFAOYSA-N Furcelleran Chemical compound CCOC(=O)C1=C(C)NC(C=2C=CC=CC=2)=C(C(=O)OCC=2C=CC=CC=2)C1C#CC1=CC=CC=C1 SNVFDPHQAOXWJZ-UHFFFAOYSA-N 0.000 description 1
- 240000004670 Glycyrrhiza echinata Species 0.000 description 1
- 235000001453 Glycyrrhiza echinata Nutrition 0.000 description 1
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 description 1
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- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000001922 Gum ghatti Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 229920000881 Modified starch Polymers 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 241001364096 Pachycephalidae Species 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 235000015125 Sterculia urens Nutrition 0.000 description 1
- 240000001058 Sterculia urens Species 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- DIOLOCSXUMYFJN-UHFFFAOYSA-N calcium;azane Chemical compound N.[Ca+2] DIOLOCSXUMYFJN-UHFFFAOYSA-N 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
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- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- -1 for example Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000013572 fruit purees Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
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- 239000001087 glyceryl triacetate Substances 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940010454 licorice Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
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- 235000010408 potassium alginate Nutrition 0.000 description 1
- 239000000737 potassium alginate Substances 0.000 description 1
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
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- 239000010875 treated wood Substances 0.000 description 1
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- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical class OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
- A24B15/165—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes comprising as heat source a carbon fuel or an oxidized or thermally degraded carbonaceous fuel, e.g. carbohydrates, cellulosic material
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
Definitions
- This invention relates to a smokable filler material, in particular but not exclusively, a smokable filler material to be used in cigarettes.
- the main organic combustible material i.e. the main fuel material, in the latter is selected from chaff, straw, bran or shell material, i.e. the waste products of cereals or nuts.
- This invention is able to provide a smokable filler material in which fruit material is the or one of the main combustible fuel materials of the smokable filler material.
- the invention is also able to be used with or without additional tobacco material, whether cut tobacco leaf or cut reconstituted tobacco sheet material.
- the smokable filler material has a smoking quality that enables the product developer to select appropriate flavours and casings in order to provide an acceptable smoking taste and flavour.
- the smoke derived from smokable filler material according to the invention also provides significant reduction to the smoker of some smoke components.
- the present invention provides a smokable filler material comprising a non-combustible inorganic filler, a binder, and as a major organic combustible fuel material, a fruit material .
- the inorganic filler material is in the range of 30-90% by weight of the dry materials.
- Smokable filler material produced by means of casting advantageously comprises inorganic filler material in the range of 50-80%, and more preferably >60% and even more preferably >70% by weight of the dry materials.
- smokable filler material produced by means of an extrusion process preferably comprises inorganic filler material in the range of 30-70% by weight of the dry materials. More preferably the inorganic filler material is in the range of 35-60%, and is even more preferably in the range 45-55% and more preferably about 50% by weight of the dry materials.
- the binder is preferably in the range of 3-25% by weight of the dry materials. More preferably the binder is in the range of 5-15%, and is more preferably less then 12% or even more preferably less than 10% by weight of dry materials.. The binder may advantageously be about 7.5% by weight of dry materials .
- the fruit material is preferably in the range of 2-50% by weight of the dry materials.
- the fruit material is . more preferably in the range of 5-15% and is even more preferably 10% or more, and may advantageously be about 12.5%.
- the fruit material is preferably in the range of 2-50% by weight of dry materials. More preferably the fruit material is in the range of 10-30% and is even more preferably about 20% by weight of the dry materials.
- the smokable filler material made by a casting process may advantageously comprise 10-20% fruit, 10,% sodium alginate, 70% chalk and 10% glycerol .
- An acceptable filler material can be produced using 7.5% sodium alginate with a consequent increase in the fruit content .
- the smokable filler material made by an extrusion process may advantageously comprise 10-20% fruit, 20% starch, 50% chalk, 10% hydroxypropylcellulose and 0-10% glycerol.
- the non-combustible inorganic filler material is preferably • an inorganic filler selected . from the group comprising silicates or alumino-silicates, such as perlite, vermiculite, diatomaceous earth,- talc or colloidal silica; or metal oxides, metal salts or hydroxides such as magnesium oxide, magnesium sulphate, calcium or magnesium carbonate or alumina.
- the inorganic filler is a low density material, suitably of ⁇ 5g/cm 3 , preferably less than 4gcm 3 and more preferably ⁇ 3g/cm 3 . Mixtures of these fillers are also acceptable.
- the smokable filler material may also comprise an organic filler.
- the organic filler material is inert or relatively inert when alone, i.e. will not readily maintain burning, but in a mixture may become more combustible, i.e. will maintain burning.
- Suitable organic fillers include insoluble alginates, such as calcium or magnesium alginate, calcium pectinate or alginic acid, as well as non-modified cellulose, such as treated or non-treated wood pulp or alpha cellulose, for example. Mixtures of inert organic fillers and inorganic fillers may also be used.
- the organic filler is advantageously present in the range of 0-40%.
- the organic filler helps to, improve the ash characteristics of the smokable filler material. It may be advantageous to include a combustible organic material with naturally low nitrogen content, i.e. less than 0.25%, more advantageously less than 0.20% and even more advantageously less than 0.1% dwb of total nitrogen.
- the binder is an organic binder, such as an alginate, a gum, a cellulose (modified or natural) , a pectin or pectinaceous binder, or the Group I or II metal salts of these binders, such as sodium carboxymethylcellulose or sodium alginate.
- organic binder such as an alginate, a gum, a cellulose (modified or natural) , a pectin or pectinaceous binder, or the Group I or II metal salts of these binders, such as sodium carboxymethylcellulose or sodium alginate.
- binders are alginic binders which include soluble alginates such as ammonium alginate, sodium alginate, sodium calcium alginate, calcium ammonium alginate, potassium alginate, triethanol-amine alginate and propylene glycol alginate .
- Alginic binders provide the preferred smoking mechanics and taste and flavour properties for the smokable filler according to the invention.
- Cellulosic binders include, for example, cellulose derivatives, such as sodium carboxymethylcellulose, methyl cellulose, hydroxypropylcellulose, hydroxyethyl cellulose or cellulose ethers. These binders are preferred for extrusion purposes .
- organic binders include gums such as gum arabic, gum ghatti, gum tragacanth, Karaya, locust bean, acacia, guar, quince seed or xanthan gum, or gels such as agar, agarose, carrageenans , fucoidan and furcelleran. Pectins and pectinaceous materials can also be used as binders. Starches can also be used as organic binders. Other suitable gums can be selected by reference to handbooks, such as Industrial Gums, Ed. Whistler (Academic Press) . Inorganic non-combustible binders, such as some cements, for example, Portland cement, may also be used. Combinations of the above may also be used.
- the binder is an alginate, and in particular the monovalent alginates
- the fruit material is suitably one or more of most derivatives from fruit, such as either whole fruit, dried fruit, fruit pulp, fruit concentrate, i.e. the fruit residue arising from the manufacture of fruit juices, fruit paste, fruit puree, a powdered extract of the fruit or a liquid extract of the fruit. If a liquid extract is used, the extract is preferably not purely sugars from the fruit. Mixtures of each class are also acceptable. Granulation of the fruit material by, for example, mixing a fruit liquid or syrup with the inorganic filler, drying and granulating is also advantageous for some fruit derivatives, in terms of ease of processing.
- the fruit selected has a low sugar content, i.e. of the order of 70% or less. It has been found to be advantageous for high sugar containing fruits to have sugar removed, therefrom, so that upon addition of the fruit material the sugar content is preferably less than 20%.
- the fruit material is selected from the class comprising soft fruits, citrus fruit, berries or processed fruit material, such as dried powders or dietary fibre.
- the fruit material is selected to have a low nitrogen content, advantageously of ⁇ 1.8% dwb and more advantageously of ⁇ 1.0% dwb, and even more advantageously of ⁇ 0.6% dwb.
- the fruit is suitably selected from one or more of the following: pineapple, mango, . raisin, apple, banana, apricot, lemon, peach, kiwi or grape. The first three of this list are particularly preferred. Seeds from these materials are not, at this stage, considered to be of value in the present invention.
- Fruit powder or concentrate may each be mixed wi.th water until fully dissolved. Pulp from fruit is suitably pulverised thereby becoming finely divided, yet allowing the fibres to remain relatively intact . Fibres may be separated from the liquid in order to change the ratio of fibres to liquid, if desired. If dried fruit is utilised, the fruit is preferably boiled in water. If high sugar fruits are utilised they are preferably boiled and percolated, for example, to remove a proportion of the organic acids and sugars, and then blended to produce a homogeneous mixture or paste .
- the , aerosol generating source preferably comprises aerosol forming means, such as glycerol and/or other aerosol forming compounds illustrated in our co-pending PCT Application No. WO96/07336. These include polyhydric alcohols, propylene glycol and triethylene glycol, esters such as triethyl citrate, triacetin or triethylene glycol diacetate (TEGDA) , or high boiling point hydrocarbons. Other suitable aerosol forming means will be known to those skilled in the art .
- aerosol generating means is incorporated into the filler material at a level of 0-30%.
- the aerosol generating means is more preferably in the range of 5-15%, and even more preferably about 10% by weight of the dry materials.
- the aerosol generating means is more preferably in the range 0-10% and even more preferably in the range 3-5% or less by weight of dry materials.
- the aerosol generating means is pumped into the barrel of the extruder. Plasticisers are also desirable.
- the plasticiser is the same as one of the list of suitable aerosol forming materials, the plasticiser may suitably be present at a level such that it is not the main aerosol producer.
- the additional components i.e. those other than filler, fruit and binder, are selected according to the final material properties desired.
- flavour materials such as coffee, cocoa, caramel, flavours from roots, such as ginger or licorice, for example, tobacco dust or tobacco extracts may also be added to the smokable filler material at levels ⁇ 10%, and preferably at levels of ⁇ 5%, by weight of the dry materials.
- the smokable filler material is advantageously prepared by mixing all the powdered material (excluding the binder) , adding water, then gradually introducing the binder whilst subjecting the mixture to high shear. Further, water is then added to achieve the desired viscosity.
- the final slurry has a viscosity between 60,000 - 400,000 centipoise and is more preferably in the range of 150,000 - 250,000 centipoise.
- the final viscosity will depend on the method of casting (drum or band) , extrusion or paper making process to be used.
- the final slurry is then suitable for casting whereupon it may then be stored, ' conditioned, and then shredded to produce cut smokable filler material .
- the smokable filler material may alternatively be produced by means of extrusion, which extruded material may be a foamed or non-foamed material.
- Suitable expansion medium or foaming means are described in our co-pending PCT Application No. WO 96/07336, the subject matter thereof in relation to expansion mediums being incorporated herein by reference thereto.
- Suitable expansion mediums include starch, pullulan or other polysaccharides, including cellulose derivatives, solid foaming agents, inorganic salts and organic acids providing in si tu gaseous agents, organic gaseous agents, inorganic gaseous agents and volatile liquid foaming agents.
- the expansion medium may partly replace the inorganic filler.
- the expansion medium may be present in the range of 0-40% by weight of the dry materials and preferably less than 30% and more preferably is about 20%. Water is most commonly the preferred volatile expansion agent for such expansion systems. Alternative expansion agents are well known.
- the smokable filler material is advantageously prepared by mixing all the powdered material including the binder, then pumping water and glycerol into the barrel of the extruder.
- the extruded material may be rods, strands, filaments or sheet material which is then cut to provide filler material. ' Entwining or twisting of the strands or filaments may be desirable to provide air passages, if the extruded material does not allow the drawing of air or smoke therealong. Other downstream processing techniques may also be used to improve pressure drop, if required, if extruded as a rod.
- Various extruded forms are described in our co-pending PCT application and should be taken to be incorporated herein by reference thereto.
- the smokable filler material may also comprise a burn additive to enhance the smoking properties of the filler material .
- the burn additive is either a burn promoter or a burn retardant .
- Suitable burn additives may be selected from one or more of salts of Group I or II metals such as acetates, citrates and other burn promoters known to the skilled man.
- Suitable burn retardants include magnesium hydroxide, mono-ammonium phosphate or magnesium chloride, for example.
- the smokable filler material may also comprise an ash improver, which is advantageously present in the filler in the range of 0-5%.
- ash improvers include one or more of mica, perlite, clays, such as, for example, vermiculite, kaolinites, talcs, saponites, bentonites, as well as ash improvers such as disodium hydrogen orthophosphate, sodium carbonate or diammonium phosphate, for example.
- the present invention also provides a smoking article comprising a rod of smokable filler material, according to an aspect of the present invention, wrapped in a wrapper.
- the smokable filler material may comprise 100% of the rod of material wrapped in a wrapper.
- the smokable filler material of the invention may be blended with cut tobacco or tobacco containing sheet, such as a reconstituted sheet, for example.
- the amount of .tobacco material in such a blend is not more than 40% and is more preferably ⁇ 30% by weight of the final blend.
- the wrapper may suitably be a paper wrapper or a substantially non-combustible wrapper, such as that described in International Patent Application, .Publication No. WO 96/07336.
- the subject matter of that application as it relates to the substantially no -combustible wrapper is incorporated herein by reference .
- the wrapper thereof advantageously contains at least 65% inorganic particulate filler material, such as those inorganic materials described above .
- a conventional cellulose pulp paper wrapper may have a permeability in the range 2-300 CU and preferably less than 100 CU. Such a wrapper may also be a low total filler paper such as disclosed in our European Patent Application No. 0 404 580 and comprising less than 14% magnesium oxide or hydroxide, for example .
- the binder is added gradually to the mix, with more water if required.
- the final viscosity of the slurry should ideally lie between 150,000 and 250,000 centipoise.
- the slurries in the following Examples were cast on a drum caster to produce a uniform sheet .
- the resulting sheet is stored at approximately 60%RH for 24 hours prior to shredding using a Hauni tobacco shredder or a paper-type shredder. After the strands have been conditioned for 48 hours the material is ready to be made into cigarettes on a cigarette maker.
- Cut material of each was then fabricated into cigarettes of 24.70mm diameter, 64mm length with a 20mm cellulose acetate filter and a paper wrapper of 5CU with 0.55% potassium citrate burn additive added thereto.
- This cigarette construction enabled direct comparison to a control commercial cigarette, in this case, a King Size, full flavour, Virginia style cigarette.
- the cigarettes were smoked under standard machine smoking conditions of 35ml puff of 2 second duration per minute. A statistically relevant number of cigarettes were smoked (see Proctor, C. et al . The Analyst, October 1988, v. 113 pl509- 1513) . In this instance, 5 cigarettes per pad on a port and a mean of 4 ports was taken.
- NHFDPM Nicotine and humectant free dry particulate matter NFDPM Nicotine and humectant free dry particulate matter
- the material also performs well in a conventional cigarette manufacturing situation, thereby not requiring modification of existing apparatus.
- a smoke low in nitrogen-derived compounds is obtained. Surprisingly, a low dry particulate matter content of smoke is also obtained. Despite high levels of non-combustible inorganic filler a substantial smoke aerosol is generated which comprises mainly glycerol and water.
- the final product also provides a product low in nitrogen and mean ammonia nitrogen (see Table 4) .
- a dry mix is made up from chalk (50%) , dried fruit or powdered fruit (20%) , pregelatinised starch (20%) and hydroxypropyl cellulose (10%) .
- the mix is then fed into an extruder and water and glycerol (3-5%) pumped into the extruder.
- the extruder barrel is heated at points along the barrel so as to produce temperatures at the heated extruder zones which are typically 70, 100, 110, 120 and 130 degrees Celsius.
- the pressure at the die is typically about 30 bar, and should in any case be less than 100 bar.
- the screw profile of the extruder should be such that enough energy is put into the mix to produce a blown extrudate when the material exits the extruder die.
- the extrudate formed is in the shape of a tube or a foamed sheet. Ideally the tube is produced with a very small diameter hole running longitudinally through the centre.
- the extrudate is carried away from the extruder die by a suitable haul-off system.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Manufacture Of Tobacco Products (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
- Reinforced Plastic Materials (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA02012332A MXPA02012332A (es) | 2000-06-14 | 2001-06-11 | Material de relleno fumable que contiene un material de fruta. |
EP01938397A EP1294242B1 (en) | 2000-06-14 | 2001-06-11 | Smokable filler material containing a fruit product |
HU0302483A HUP0302483A3 (en) | 2000-06-14 | 2001-06-11 | Filling material containing a tobacco substitute material mainly for cigarettes |
IL15342901A IL153429A0 (en) | 2000-06-14 | 2001-06-11 | Improvements relating to smokable filler material |
NZ522795A NZ522795A (en) | 2000-06-14 | 2001-06-11 | A smokable filler material containing an inorganic filler material, such as 10-30% fruit material, and a binder for use as a tobacco substitute |
US10/297,822 US20040074508A1 (en) | 2000-06-14 | 2001-06-11 | Smokable filler material containing a fruit material |
BR0112175-8A BR0112175A (pt) | 2000-06-14 | 2001-06-11 | Material de carga fumável contendo um material de fruta e artigo para fumar |
AU6407601A AU6407601A (en) | 2000-06-14 | 2001-06-11 | Smokable filler material containing a fruit material |
CA002410656A CA2410656A1 (en) | 2000-06-14 | 2001-06-11 | Smokable filler material containing a fruit material |
JP2002509942A JP3742793B2 (ja) | 2000-06-14 | 2001-06-11 | 果実材料を含む喫煙可能な充填材材料 |
DE60122883T DE60122883T2 (de) | 2000-06-14 | 2001-06-11 | Rauchbares füllmaterial enthaltend ein fruchtprodukt |
AU2001264076A AU2001264076B2 (en) | 2000-06-14 | 2001-06-11 | Smokable filler material containing a fruit material |
UA2003010241A UA74378C2 (uk) | 2000-06-14 | 2001-06-11 | Курильний начиняльний матеріал та курильний виріб |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0014465.9 | 2000-06-14 | ||
GBGB0014465.9A GB0014465D0 (en) | 2000-06-14 | 2000-06-14 | Improvements relating to smokable filler material |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001095748A1 true WO2001095748A1 (en) | 2001-12-20 |
WO2001095748B1 WO2001095748B1 (en) | 2002-01-17 |
Family
ID=9893584
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2001/002563 WO2001095748A1 (en) | 2000-06-14 | 2001-06-11 | Smokable filler material containing a fruit material |
Country Status (20)
Country | Link |
---|---|
US (1) | US20040074508A1 (hu) |
EP (1) | EP1294242B1 (hu) |
JP (1) | JP3742793B2 (hu) |
KR (1) | KR20030010709A (hu) |
CN (1) | CN1436050A (hu) |
AT (1) | ATE338474T1 (hu) |
AU (2) | AU2001264076B2 (hu) |
BR (1) | BR0112175A (hu) |
CA (1) | CA2410656A1 (hu) |
CZ (1) | CZ20024031A3 (hu) |
DE (1) | DE60122883T2 (hu) |
GB (1) | GB0014465D0 (hu) |
HU (1) | HUP0302483A3 (hu) |
IL (1) | IL153429A0 (hu) |
MX (1) | MXPA02012332A (hu) |
NZ (1) | NZ522795A (hu) |
RU (1) | RU2256386C2 (hu) |
UA (1) | UA74378C2 (hu) |
WO (1) | WO2001095748A1 (hu) |
ZA (1) | ZA200209416B (hu) |
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- 2001-06-11 RU RU2002135629/12A patent/RU2256386C2/ru not_active IP Right Cessation
- 2001-06-11 CN CN01811193A patent/CN1436050A/zh active Pending
- 2001-06-11 IL IL15342901A patent/IL153429A0/xx unknown
- 2001-06-11 BR BR0112175-8A patent/BR0112175A/pt not_active IP Right Cessation
- 2001-06-11 CA CA002410656A patent/CA2410656A1/en not_active Abandoned
- 2001-06-11 AU AU2001264076A patent/AU2001264076B2/en not_active Ceased
- 2001-06-11 NZ NZ522795A patent/NZ522795A/en unknown
- 2001-06-11 HU HU0302483A patent/HUP0302483A3/hu unknown
- 2001-06-11 UA UA2003010241A patent/UA74378C2/uk unknown
- 2001-06-11 JP JP2002509942A patent/JP3742793B2/ja not_active Expired - Fee Related
- 2001-06-11 CZ CZ20024031A patent/CZ20024031A3/cs unknown
- 2001-06-11 AT AT01938397T patent/ATE338474T1/de not_active IP Right Cessation
- 2001-06-11 WO PCT/GB2001/002563 patent/WO2001095748A1/en active IP Right Grant
- 2001-06-11 US US10/297,822 patent/US20040074508A1/en not_active Abandoned
- 2001-06-11 MX MXPA02012332A patent/MXPA02012332A/es unknown
- 2001-06-11 EP EP01938397A patent/EP1294242B1/en not_active Expired - Lifetime
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CN102423124A (zh) * | 2011-11-01 | 2012-04-25 | 吉林烟草工业有限责任公司 | 一种烟草薄片及其制备方法 |
CN102488316A (zh) * | 2011-12-08 | 2012-06-13 | 上海烟草集团有限责任公司 | 一种改善烟草薄片感官质量的烟用添加剂及其制备方法与应用 |
CN102488316B (zh) * | 2011-12-08 | 2014-06-11 | 上海烟草集团有限责任公司 | 一种改善烟草薄片感官质量的烟用添加剂及其制备方法与应用 |
CN105212260A (zh) * | 2014-05-26 | 2016-01-06 | 何氪 | 一种烟草薄片及卷烟制品 |
CN106701325A (zh) * | 2017-03-08 | 2017-05-24 | 湖北中烟工业有限责任公司 | 一种烟用杏子提取物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE60122883D1 (de) | 2006-10-19 |
CZ20024031A3 (cs) | 2004-01-14 |
KR20030010709A (ko) | 2003-02-05 |
WO2001095748B1 (en) | 2002-01-17 |
ATE338474T1 (de) | 2006-09-15 |
AU6407601A (en) | 2001-12-24 |
RU2256386C2 (ru) | 2005-07-20 |
MXPA02012332A (es) | 2003-06-06 |
JP3742793B2 (ja) | 2006-02-08 |
ZA200209416B (en) | 2004-02-19 |
HUP0302483A2 (hu) | 2003-11-28 |
AU2001264076B2 (en) | 2004-06-03 |
CA2410656A1 (en) | 2001-12-20 |
NZ522795A (en) | 2004-07-30 |
BR0112175A (pt) | 2003-05-20 |
US20040074508A1 (en) | 2004-04-22 |
CN1436050A (zh) | 2003-08-13 |
JP2004503230A (ja) | 2004-02-05 |
EP1294242B1 (en) | 2006-09-06 |
IL153429A0 (en) | 2003-07-06 |
HUP0302483A3 (en) | 2006-03-28 |
DE60122883T2 (de) | 2007-01-04 |
UA74378C2 (uk) | 2005-12-15 |
GB0014465D0 (en) | 2000-08-09 |
EP1294242A1 (en) | 2003-03-26 |
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