CN102733221B - Method for recycling lignin and cellulose in tobacco waste - Google Patents
Method for recycling lignin and cellulose in tobacco waste Download PDFInfo
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- CN102733221B CN102733221B CN201210042673.4A CN201210042673A CN102733221B CN 102733221 B CN102733221 B CN 102733221B CN 201210042673 A CN201210042673 A CN 201210042673A CN 102733221 B CN102733221 B CN 102733221B
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- tobacco waste
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- 229920005610 lignin Polymers 0.000 title claims abstract description 39
- 241000208125 Nicotiana Species 0.000 title claims abstract description 38
- 235000002637 Nicotiana tabacum Nutrition 0.000 title claims abstract description 38
- 229920002678 cellulose Polymers 0.000 title claims abstract description 35
- 239000001913 cellulose Substances 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title abstract 2
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002608 ionic liquid Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 21
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000003381 solubilizing effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 abstract description 25
- 238000001914 filtration Methods 0.000 abstract description 13
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 abstract description 12
- 229960002715 nicotine Drugs 0.000 abstract description 12
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 abstract 1
- 239000002154 agricultural waste Substances 0.000 abstract 1
- 230000001953 sensory effect Effects 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000000284 extract Substances 0.000 description 7
- IECQULMJVNSKDB-RCWTXCDDSA-N 3-[(2s)-1-methylpyrrolidin-2-yl]pyridine;sulfuric acid Chemical compound OS(O)(=O)=O.CN1CCC[C@H]1C1=CC=CN=C1.CN1CCC[C@H]1C1=CC=CN=C1 IECQULMJVNSKDB-RCWTXCDDSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000008030 elimination Effects 0.000 description 6
- 238000003379 elimination reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 235000019504 cigarettes Nutrition 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000021190 leftovers Nutrition 0.000 description 2
- -1 and wherein Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQFCOGRKGVGYBB-UHFFFAOYSA-N ethanol;nitric acid Chemical group CCO.O[N+]([O-])=O HQFCOGRKGVGYBB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
The invention relates a chemical extraction method of agricultural waste, particularly a method for recycling lignin and cellulose in tobacco waste, comprising the following steps: crushing the tobacco waste, adding 10-30 times volume of water, regulating the pH value to 11-13, processing for no less than 1 min under microwave at 100 W to obtain a pretreatment material; filtering the pretreatment material, regulating the pH value of the filter residues to 4.0-5.0, reacting for no less than 40 min, and using an ionic liquid of 1-butyl-3-methyl imidazolium chloride to fully dissolve, carrying out solid-liquid separation to obtain the solid and liquid, wherein the solid is lignin, and the liquid contains cellulose. The method provides a continuous extraction process of nicotine, hemicellulose and cellulose. After nicotine products are obtained with high yield, the residues are used for extracting hemicellulose and cellulose, wherein cellulose has good sensory property and can be used as a high end material. The whole method is green, and the production cost is low.
Description
Technical field
The present invention relates to chemical extraction field, particularly the chemical extraction methods of agricultural residue.
Background technology
China is tobacco leaf production big country, in the accumulating of tobacco leaf and the process of production of cigarettes, not only produces a large amount of scraps, scarp, offal, pollute or go mouldy the tobacco wastes such as tobacco leaf, and the quantity that tobacco grower abandons the discarded tobacco leaf in field every year is also considerable.Containing the multiple chemical composition having value in tobacco leaf, if fully utilize it, then not only improve the pollution of discarded object to environment, simultaneously again for country creates wealth.But because state-of-the-art falls behind, product cost is higher and cause the situation that the market competitiveness is not high, comprehensive utilization ratio is low.
Summary of the invention
The invention provides one from tobacco after continuous extraction nicotine, hemicellulose, remaining waste residue extracts the new method of lignin, cellulose products again, the method environmental protection, is applicable to extensive utilization.
For reaching above object, its technical scheme comprises:
This extraction process can process the filtrate in pretreatment fluid and filter residue respectively, can extraction nicotine and hemicellulose in filtrate, can extract lignin and cellulose in filter residue.This programme design is ingenious, and environmental protection is practical, can realize suitability for industrialized production on a large scale.
Lignin and cellulosic reuse method in tobacco waste, specifically comprise the following steps:
A pretreatment of raw material
Pulverized by tobacco waste, add and be equivalent to tobacco waste volume 10-30 times of water, adjusted to ph is 11-13, is that under the microwave of 100W, process is no less than 1 minute, obtains preliminary treatment material at power;
The extraction of B lignin
Filtered by steps A gained preliminary treatment material, filter residue acid for adjusting pH value is 4.0-5.0, and reaction is not less than 40 minutes, and with the abundant solubilizing reaction of ionic liquid 1-butyl-3-methyl imidazolium villaumite, Separation of Solid and Liquid, obtains liquid and solid, and described solid is lignin.
Further, add deionized water by step B gained liquid, obtain precipitation, described in be precipitated as cellulose, the mass ratio of described cellulose and described ionic liquid 1-butyl-3-methyl imidazolium villaumite is 1: 6 ~ 1: 20.
Further, by gained cellulose cold water flush, suction filtration also carries out vacuumize, and baking temperature is 70 ~ 100 DEG C, and drying time is 10 ~ 12 hours.
Further, described solubilizing reaction carries out under stirring, and the reaction time is 30 ~ 240 minutes.
Further, in step B, the mode of described Separation of Solid and Liquid is specially centrifugation, and the centrifugal time is 5 ~ 8 minutes, and centrifugal speed is 1500 ~ 4000 revs/min.
Further, in stepb, filtered by steps A gained preliminary treatment material, filter residue acid for adjusting pH value is 4.0-5.0, reacts 60 minutes under 70-95 DEG C of condition, cooling.
Further, in stepb, the temperature of solubilizing reaction is 70-95 DEG C, and the time of reaction is 4 hours.
Beneficial effect of the present invention is: this technique provides a kind of nicotine, hemicellulose, lignin and cellulosic continuous extraction process; After the acquisition nicotine products that productive rate is higher, residue is for extracting hemicellulose, lignin and cellulose, and wherein, cellulose sense organ is good, can be used as high end materials; Whole method environmental protection, production cost is low, is suitable for large-scale production.
Detailed description of the invention
In the present invention, the tobacco waste of indication, has another name called tobacco leftovers, is specially: tobacco leaf, the offal of useless time.Low, hypo-tobacco leaf and cigarette leftover bits and pieces in a large number, tobacco waste is a large amount of byproducts produced in production of cigarettes, is rich in various organic principle and secondary metabolite.Tobacco waste also can make material substitution with tobacco.
Tobacco waste in following embodiment comes from Chongqing Yin Fu biological organic fertilizer Co., Ltd, and its moisture accounts for 7% of tobacco waste gross mass.
In following embodiment, cellulosic purity refers to cellulosic yield.
Cellulosic method for detecting purity is nitric acid Ethanol Method.Lignin, the detection method of hemicellulose purity is normal form fibre method.In addition, adopt ionic liquid 1-butyl-3-methyl imidazolium villaumite to extract cellulosic detailed protocol, refer to the Chinese patent application that application number is 201110248519.8.
Embodiment 1
By 20 order 100g tobacco waste powder, add after drying impurity elimination and be equivalent to tobacco waste volume 10 times of normal-temperature water, adjusted to ph is 11, under microwave power 200W, after microwave 20min, filter, filtrate mass fraction be 10% sulfuric acid as solvent carry out distillation extract, vapo(u)rizing temperature is 100 DEG C, obtains product nicotine sulphate, then obtains natural nicotine 3.2g with n-hexane extraction; Residual filtrate HCL regulates filtrate pH value to be 3.0, and centrifugal (under 1500r/min condition centrifugal 10min), obtains hemicellulose A8.6g; The ethanol precipitating of the suspension volume fraction 95% after centrifugal, centrifugal (under 2000r/min condition centrifugal 10min), obtain hemicellulose B 4.2g.
Filter residue after being filtered by steps A gained preliminary treatment material synchronously carries out the extraction of lignin, is specially: filter residue 0.3mol/l HCL adjust ph is 4.0, is heated to 75 DEG C of reactions 1 hour, and cooling, filtration, containing lignin and cellulose in the filter residue of filtration.After being adopted by filter residue ionic liquid 1-butyl-3-methyl imidazolium villaumite to be heated to 80 DEG C of reaction 4h, separating solids and liquid, solid is lignin, adds deionized water immediately and obtain cellulose in liquid, and under 80 DEG C of conditions, be put in dry 12h in vacuum drying chamber.
Can obtain by analysis, hemicellulose is 12.8g, and purity is 85.3%; Cellulose is 28.5g, and purity (yield) is 86.4%; Lignin is 5.4g, and purity is 77.1%.
Embodiment 2
By 20 order 100g tobacco waste powder, add after drying impurity elimination and be equivalent to tobacco waste volume 10 times of normal-temperature water, adjusted to ph is 11, under microwave power 400W, after microwave 30min, filter, filtrate mass fraction be 10% sulfuric acid as solvent carry out distillation extract, vapo(u)rizing temperature is 100 DEG C, obtains product nicotine sulphate, then obtains natural nicotine 3.6g with n-hexane extraction; Residual filtrate HCL regulates filtrate pH value to be 4.0, centrifugal (under 1500r/min condition centrifugal 10min), and obtaining hemicellulose A is 8.8g; Centrifugal 10min under suspension after the centrifugal ethanol precipitating of 95%, centrifugal 2000r/min condition, obtains hemicellulose B 4.7g.
Filter residue after being filtered by steps A gained preliminary treatment material synchronously carries out the extraction of lignin, is specially: filter residue 0.3mol/lHCL adjust ph is 5.0, is heated to 75 DEG C of reactions 1 hour, and cooling, filtration, containing lignin and cellulose in the filter residue of filtration.After being adopted by filter residue ionic liquid 1-butyl-3-methyl imidazolium villaumite to be heated to 80 DEG C of reaction 4h, separating solids and liquid, solid is lignin, adds deionized water immediately and obtain cellulose in liquid, and under 80 DEG C of conditions, be put in dry 12h in vacuum drying chamber.
Can obtain by analysis, hemicellulose is 13.5g, and purity is 96.4%; Cellulose is for being 30.2g, and purity is 91.5%; Lignin is 6.1g, and purity is 87.1%.
Embodiment 3
By 20 order 100g tobacco waste powder, add after drying impurity elimination and be equivalent to tobacco waste volume 10 times of normal-temperature water, adjusted to ph is 11, after effect 30min, filter, filtrate mass fraction be 10% sulfuric acid as solvent carry out distillation extraction, vapo(u)rizing temperature is 100 DEG C, obtain product nicotine sulphate, then obtaining natural nicotine with n-hexane extraction is 1.6g; Residual filtrate HCL regulates filtrate pH value to be 3.0, centrifugal (under 1500r/min condition centrifugal 10min), and obtaining hemicellulose A is 4.8g; Suspension after centrifugal with 95% ethanol precipitating, centrifugal, centrifugal condition is centrifugal 10min under 2000r/min condition), obtaining hemicellulose B is 1.5g.
Filter residue after being filtered by steps A gained preliminary treatment material synchronously carries out the extraction of lignin, is specially: filter residue 0.3mol/lHCL adjust ph is 4.0, is heated to 75 DEG C of reactions 1 hour, and cooling, filtration, containing lignin and cellulose in the filter residue of filtration.After being adopted by filter residue ionic liquid 1-butyl-3-methyl imidazolium villaumite to be heated to 80 DEG C of reaction 4h, separating solids and liquid, solid is lignin, adds deionized water immediately and obtain cellulose in liquid, and under 80 DEG C of conditions, be put in dry 12h in vacuum drying chamber.
Can obtain by analysis, hemicellulose is 6.3g, and purity is 45.0%; Cellulose is 12.3g, and purity is 37.3%; Lignin is 2.1g, and purity is 30.0%.
Embodiment 4
By 20 order 100g tobacco waste powder, tobacco waste volume 10 times of normal-temperature water are added after drying impurity elimination, adjusted to ph is 7, under microwave power 400W, after microwave 30min, filter, filtrate mass fraction be 10% sulfuric acid as solvent carry out distillation extract, vapo(u)rizing temperature is 100 DEG C, obtains product nicotine sulphate, then obtains natural nicotine 2.6g with n-hexane extraction; Residual filtrate HCL regulates filtrate pH value to be 4.0, and centrifugal (under 1500r/min condition centrifugal 10min), obtains hemicellulose A5.8g; Suspension after centrifugal with 95% ethanol precipitating, centrifugal, centrifugal condition is centrifugal 10min under 2000r/min condition, obtains hemicellulose B 3.7g.
Filter residue after being filtered by steps A gained preliminary treatment material synchronously carries out the extraction of lignin, is specially: filter residue 0.3mol/l HCL adjust ph is 5.0, is heated to 75 DEG C of reactions 1 hour, and cooling, filtration, containing lignin and cellulose in the filter residue of filtration.After being adopted by filter residue ionic liquid 1-butyl-3-methyl imidazolium villaumite to be heated to 80 DEG C of reaction 4h, separating solids and liquid, solid is lignin, adds deionized water immediately and obtain cellulose in liquid, and under 80 DEG C of conditions, be put in dry 12h in vacuum drying chamber.
Can obtain by analysis, hemicellulose is 9.5g, and purity is 67.9%; Cellulose is 21.2g, and purity is 64.2%; Lignin is 4.8g, and purity is 68.6%.
Embodiment 5
By 20 order 100g tobacco waste powder, add after drying impurity elimination and be equivalent to tobacco waste volume 30 times of normal-temperature water, adjusted to ph is 11, under microwave power 400W, after microwave 30min, filter, filtrate mass fraction be 10% sulfuric acid as solvent carry out distillation extract, vapo(u)rizing temperature is 100 DEG C, obtains product nicotine sulphate, and then obtaining natural nicotine with n-hexane extraction is 3.6g; Residual filtrate HCL regulates filtrate pH value to be 2.0, and centrifugal (under 1500r/min condition centrifugal 10min), obtains hemicellulose A5.8g; Suspension after centrifugal with 95% ethanol precipitating, centrifugal, centrifugal condition is centrifugal 10min under 2000r/min condition, obtains hemicellulose B 2.3g.
Filter residue after being filtered by steps A gained preliminary treatment material synchronously carries out the extraction of lignin, is specially: filter residue 0.3mol/l HCL adjust ph is 5.0, is heated to 75 DEG C of reactions 1 hour, and cooling, filtration, containing lignin and cellulose in the filter residue of filtration.After being adopted by filter residue ionic liquid 1-butyl-3-methyl imidazolium villaumite to be heated to 80 DEG C of reaction 4h, separating solids and liquid, solid is lignin, adds deionized water immediately and obtain cellulose in liquid, and under 80 DEG C of conditions, be put in dry 12h in vacuum drying chamber.
Can obtain by analysis, hemicellulose is 8.1g, and purity is 57.9%; Cellulose is 22.4g, and purity is 67.9%; Lignin is 5.4g, and purity is 77.1%.
Embodiment 6
By 20 order 100g tobacco waste powder, tobacco waste volume 10 times of normal-temperature water are added after drying impurity elimination, adjusted to ph is 11, under microwave power 100W, after microwave 30min, filter, filtrate mass fraction be 10% sulfuric acid as solvent carry out distillation extract, vapo(u)rizing temperature is 100 DEG C, obtains product nicotine sulphate, then obtains natural nicotine 1.9g with n-hexane extraction; Residual filtrate HCL regulates filtrate pH value to be 4.0, and centrifugal (under 1500r/min condition centrifugal 10min), obtains hemicellulose A2.8g; Suspension after centrifugal with 95% ethanol precipitating, centrifugal, centrifugal condition is centrifugal 10min under 2000r/min condition, obtains hemicellulose B 2.1g.
Filter residue after being filtered by steps A gained preliminary treatment material synchronously carries out the extraction of lignin, is specially: filter residue 0.3mol/l HCL adjust ph is 5.0, is heated to 75 DEG C of reactions 1 hour, and cooling, filtration, containing lignin and cellulose in the filter residue of filtration.After being adopted by filter residue ionic liquid 1-butyl-3-methyl imidazolium villaumite to be heated to 80 DEG C of reaction 4h, separating solids and liquid, solid is lignin, adds deionized water immediately and obtain cellulose in liquid, and under 80 DEG C of conditions, be put in dry 12h in vacuum drying chamber.
Can obtain by analysis, hemicellulose is 4.9g, and purity is 35.0%; Cellulose is 15.3g, and purity is 91.5%; Lignin is 6.1g, and purity is 87.1%.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (4)
1. lignin and cellulosic reuse method in tobacco waste, is characterized in that, specifically comprise the following steps:
A pretreatment of raw material
Pulverized by tobacco waste, add and be equivalent to tobacco waste volume 10-30 times of water, adjusted to ph is 11-13, is to process 20-30min under the microwave of 100W at power, obtains preliminary treatment material;
The extraction of B lignin
Filtered by steps A gained preliminary treatment material, filter residue acid for adjusting pH value is 4.0-5.0, reacts 60 minutes under 70-95 DEG C of condition, cooling, and with the abundant solubilizing reaction of ionic liquid 1-butyl-3-methyl imidazolium villaumite, the temperature of solubilizing reaction is 70-95 DEG C, and the time of reaction is 4 hours; Separation of Solid and Liquid, obtains liquid and solid, and described solid is lignin, containing cellulose in described liquid; Add deionized water by gained liquid, obtain precipitation, described in be precipitated as cellulose, the mass ratio of described cellulose and described ionic liquid 1-butyl-3-methyl imidazolium villaumite is 1:6 ~ 1:20.
2. reuse method according to claim 1, is characterized in that, by gained cellulose cold water flush, suction filtration also carries out vacuumize, and baking temperature is 70 ~ 100 DEG C, and drying time is 10 ~ 12 hours.
3. reuse method according to claim 1, is characterized in that, described solubilizing reaction carries out under stirring, and the reaction time is 30 ~ 240 minutes.
4. reuse method according to claim 1, is characterized in that, in step B, the mode of described Separation of Solid and Liquid is specially centrifugation, and the centrifugal time is 5 ~ 8 minutes, and centrifugal speed is 1500 ~ 4000 revs/min.
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| CN201210042673.4A CN102733221B (en) | 2012-02-23 | 2012-02-23 | Method for recycling lignin and cellulose in tobacco waste |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201221209D0 (en) * | 2012-11-26 | 2013-01-09 | British American Tobacco Co | Treatment of tobacco material |
| CN105484083B (en) * | 2015-11-22 | 2017-05-03 | 北京化工大学 | Green separating process for components of lignocellulose |
| CN106235385B (en) * | 2016-09-12 | 2017-09-29 | 甘肃烟草工业有限责任公司 | Tobacco stalk fibre microwave degradation prepares cigarette feed liquid method and application |
| CN107549869A (en) * | 2017-07-27 | 2018-01-09 | 磐安县派普特生物科技有限公司 | The preparation method of tobacco extract |
| CN107467710A (en) * | 2017-07-27 | 2017-12-15 | 浦江县美泽生物科技有限公司 | Tobacco extract |
| CN111116937A (en) * | 2019-12-26 | 2020-05-08 | 新疆大学 | Ultrasonic-assisted ionic liquid extraction method of cotton stalk lignin-based antioxidant |
| CN111455705B (en) * | 2020-05-25 | 2022-07-12 | 贺先佑 | Method for manufacturing corrugated paper pulp by using tobacco waste |
| CN113933432B (en) * | 2021-10-22 | 2023-08-25 | 中国烟草总公司郑州烟草研究院 | High-sensitivity and high-precision analysis method suitable for detecting alkaloid in tobacco leaves |
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