CN101407550A - Cellulose acetate made from raw material hemp dissolving pulp, preparation and use thereof - Google Patents
Cellulose acetate made from raw material hemp dissolving pulp, preparation and use thereof Download PDFInfo
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- CN101407550A CN101407550A CNA2008102363273A CN200810236327A CN101407550A CN 101407550 A CN101407550 A CN 101407550A CN A2008102363273 A CNA2008102363273 A CN A2008102363273A CN 200810236327 A CN200810236327 A CN 200810236327A CN 101407550 A CN101407550 A CN 101407550A
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Abstract
The invention discloses acetyl cellulose prepared by using hemp pulp as a raw material, a producing method and an application thereof, and products use the hemp pulp as the raw material and are obtained by steps of smashing, activating, acetylating, hydrolyzing, setting out, water washing and drying the hemp pulp and the like. The products are applied in materials of acetate fiber filaments, membranes, semi-permeable membranes, photosensitive films and the like for producing textile. The acetyl cellulose uses the hemp pulp as the raw material, and the invention is easily-obtained in raw material, simple in producing method, easy in operation and good in product quality.
Description
Technical field:
The present invention relates to adopt hemp dissolving pulp is cellulose acetate and the manufacture method and the purposes of feedstock production.
Background technology:
At present, acetic acid synthesized cellulosic pulp raw material is generally from wood pulps.Since the restriction of forest resourceies, the tooling cost height of wood pulps, and problem of environmental pollution is serious, has had how tame production firm to close acetify level wood pulps factory in the world.Because the shortage of wood pulps supply, China's acetic acid synthesized cellulosic raw material at present mainly also relies on import, has limited domestic cellulose acetate industrial expansion to a great extent.
China's hemp resource is very abundant, and great variety of goods has the almost all main crudefiber crops in the world.The main phloem fiber crop of cultivation has ramie, flax, hemp, bluish dogbane (former title mestha), jute, piemarker.Produce the bast-fibre crop that goes up main plantation at present ramie, jute, flax, hemp, bluish dogbane and sisal hemp etc. are arranged, cultivated area is 1,500 ten thousand mu to 2,500 ten thousand mu throughout the year, wherein ramie, hemp, world rankings first, be respectively 200～5,000,000 mu and 100～3,000,000 mu, ten thousand mu of bluish dogbane, jute 400-500, ten thousand mu of flax (comprising oil seed flax) 800-1000, world rankings the 3rd.
Bast-fibre is the important and fine raw materials of light and textile industries, and ramie belongs to perennial root crop for many years, and annual results 3-5 time have higher biological yield and fiber production.Ramie has stronger soil conservation effect again simultaneously; Ramie, flax are very important height, the raw material of middle-grade garment material, in recent years fiber are used hemp, flax, develop clothes, summer sleeping mat and other civil goods, and at home and abroad all there is very important market in market.The exploitation of south flax is the another important behave that China's textile industry is moved towards sustainable development path.Yellow bluish dogbane has that moisture absorption is strong, aproll fast, rub resistance, good characteristic such as pollution-free, is the important wrapping material of protection environment.China is one of jute area of origin, is again one of world's Huang, bluish dogbane three big main product states, weaves a gunnysack every year several hundred million; That the material of construction that ramie, jute, bluish dogbane boon are developed not only has is in light weight, raw material sources advantage widely, and has noise reduction and soundproof effect, becomes a kind of first-class material of construction.In recent years; be the protection China's Forest Resources; reduce the import of papermaking wood pulp, develop the kenaf whole stalk paper-making technique, part substitutes the wood pulp in the proportionaling collecting newsprint; become the mainstay industry of paper pulp of new generation and 21 century Sustainable development; begun to take shape from raw material production, results, the integrated supporting technology of storage, the bluish dogbane papermaking specific breed of seed selection, the slurrying rate is up to 48%; its quality will be opened up brand-new pulping process for China's bluish dogbane field of papermaking, preserve the ecological environment effectively.
Summary of the invention:
The object of the present invention is to provide a kind of raw material to be easy to get, good product quality be cellulose acetate and manufacture method and the purposes that raw material is made with the hemp dissolving pulp.
Technical solution of the present invention is:
A kind of hemp dissolving pulp that adopts is the cellulose acetate that raw material is made, and it is characterized in that: be to be raw material with the hemp dissolving pulp, and the product that makes through pulverizing, activation, acetylize, hydrolysis, precipitating, washing, drying.
Described employing hemp dissolving pulp is the cellulose acetate that raw material is made, and the R-10 value of raw material hemp dissolving pulp is 60%～99.5%, and viscosity is 4dl/g～10dl/g.
A kind of hemp dissolving pulp that adopts is the manufacture method of the cellulose acetate made of raw material, it is characterized in that: comprise the following steps: successively
(1) hemp dissolving pulp is pulverized: with the R-10 value is 60%～99.5%, and viscosity is that the tabular or cotton-shaped hemp dissolving pulp finished product of 4dl/g～10dl/g is ground into velvet-like by shredder;
(2) activation: acetic acid or aqueous acetic acid are sprayed on the hemp dissolving pulp after the pulverizing, perhaps hemp dissolving pulp are immersed in acetic acid or the aqueous acetic acid, carry out activation treatment; The consumption of acetic acid is 20%～300% of a hemp dissolving pulp weight during activation treatment, and the activatory temperature is 20～50 ℃, soak time 30～300 minutes;
(3) acetylize: acetylation is that solvent, aceticanhydride are that acetylizing agent, sulfuric acid are catalyzer with acetic acid, with hemp dissolving pulp weight is benchmark, the aceticanhydride of the sulfuric acid of the acetic acid of 40～800% weight, 1～20% weight, 20～400% weight and hemp dissolving pulp is added in the reactor carry out acetylization reaction;
(4) hydrolysis: to adopt mass concentration be 10～40% the magnesium acetate aqueous solution as the hydrolytic reagent reaction that is hydrolyzed;
(5) precipitating: the slurry dilution after the dilute acetic acid solution of employing 3～10% concentration is finished acetylize, and make it precipitating;
(6) washing: adopt softening water that the cellulose acetate that separates out is washed processing;
(7) drying: under 90 ℃～120 ℃ conditions cellulose acetate after the washing is being carried out drying treatment, with the moisture controlled of cellulose acetate product 1～5%, product.
The initial temperature of acetylization reaction is from-10 ℃～35 ℃, and temperature rise rate is controlled at 0.5 ℃/min～3.0 ℃/min, and the time of acetylization reaction was controlled at 20～90 minutes.
During hydrolysis, hydrolytic reagent divides 2～4 addings, and the temperature of hydrolytic process is controlled at 50～200 ℃.
When washing was handled, washing temperature was controlled at 40～90 ℃, and the washing time is 20～120 minutes.
A kind of hemp dissolving pulp that adopts is the application of the cellulose acetate made of raw material at preparation weaving acetate fibre filament, polarizer protective membrane, colour filter, the film that is used for photochromics, semipermeable partition or sensitive film.
By being carried out acetylize, hemp dissolving pulp produces cellulose acetate of the present invention.Kind for hemp dissolving pulp does not have special requirement, can use the hemp dissolving pulp in various sources, comprises the hemp dissolving pulp that has been used for papermaking and viscose fibre industry at present.According to the present invention, acetic acid synthesized cellulosic raw material hemp dissolving pulp possesses following index:
(1)R-10：60％～99.5％
(2) viscosity: 4dl/g～10dl/g
R-10 represents to be used for to make the content of the numb oar dregs of rice long chain cellulose of cellulose acetate, and is relevant with alpha-cellulose content.R-10 can measure according to the method among the ASTM D 1696.Testing scheme is as follows: at first pipette the 10%NaOH solution of 100mL, place 20 ℃ thermostatic bath constant temperature 1 hour; The about 1.5g of the hemp dissolving pulp of weighing complete drying is accurate to 0.0001g; The hemp dissolving pulp of accurate weighing is joined in the 10%NaOH solution of 100mL, fully vibrated 1 minute rapidly, placed thermostatic bath then 1 hour; The NaOH solution that pipettes 100mL filters through sand core funnel as blank solution, and sample solution is also filtered through sand core funnel; The sample filtrate and the blank filtrate branch that pipette 15mL are clipped in two Erlenmeyer flasks, the sulphuric acid soln that adds the 0.0833M potassium bichromate solution of 10mL and 30mL respectively gets that a clean 250mL Erlenmeyer flask adds the 10mL potassium bichromate solution and the 30mL sulphuric acid soln is made into standardized solution in sample filtrate and blank filtrate; Place on the hot plate heating after 5-10 minute respectively in sample solution, blank solution, standardized solution, treat its cooling; In 30 minutes, respectively add the 75mL deionized water, and respectively add 3 adjacent coffee sieve quinoline ferrous ammonium sulphate indicator, and carry out titration respectively with the 0.1M ammonium ferric sulfate solution, read titration volume number, be accurate to 0.01mL, and calculate the R-10 value of hemp dissolving pulp by following formula.
In the formula, V0 represents blank titration volume, mL; V1 represents sample titration volume, mL;
V2 represents the volume number of the sulfurous acid iron ammonium that timing signal consumes, mL; N represents the equivalent concentration of potassium bichromate; W represents the dry weight of hemp dissolving pulp, g.
The viscosity index of hemp dissolving pulp has reflected its polymerization degree size, can measure according to following method.Get the 120mL vial, 30mL water is stand-by to wherein adding.The oven dry fiber crops oar dregs of rice of weighing 150mg are accurate to 0.1mg.It is added in the vial, vibrated rapidly 1 minute, place again on the vibrator and vibrated 15 minutes.The mother glass bottle is placed nitrogen chamber, connected nitrogen 3-5 minute.Outward winding in the nitrogen chamber spiral cover of mother glass bottle is to 1M copper second two ammonium solutions that wherein add 30mL.Be statically placed in the nitrogen chamber after 1-2 minute, screw lid.After the quick oscillation 30 seconds, place on the vibrator, vibrated 10 minutes.(CANNON, 150mL 133A), swing to and draw sample solution to the second scale marks to get special-purpose viscometer.The viscometer forward is vertically put into 25 ± 0.05 ℃ thermostatic bath, left standstill 10 minutes.Sample solution is drawn to first scale marks, it is freely fallen.Drop to the time t (second) of second scale marks from first scale marks with stopwatch statistics liquid level.According to following formula calculated characteristics viscosity.
Degree of acetylation is represented the binding capacity of acetate in the cellulose acetate product, and is expressed as the weight percent of every Mierocrystalline cellulose unit weight bonded acetate.Degree of acetylation can be measured according to the method that is used to measure degree of acetylation among the ASTM D 871-96 (testing method of cellulose acetate etc.).Measurement scheme is as follows: at first accurate weighing 1.9 gram exsiccant cellulose acetates, be dissolved in 150ml acetone-dimethyl sulfoxide (DMSO) (4: 1, in mixture v/v), add the aqueous sodium hydroxide solution of 30ml 1N, and saponification 2 hours under 25 ℃ of conditions.Add 2～3 phenolphthalein indicators, and with the sodium hydroxide of the sulfuric acid overtitration of 1N.Carry out blank test with above-mentioned same method, and calculate degree of acetylation by following equation:
Degree of acetylation (%)=(6.5 * (B-A) * F)/W
In the formula, A represents to add to 1N vitriolic consumption (ml) in the sample, and B represents to add to 1N vitriolic consumption (ml) in the check sample, and F represents 1N vitriolic concentration factor, and W is the weight (g) of sample.
With the viscometric degree of polymerization is unit, and the polymerization degree of cellulose acetate is from 200～600, preferably from 250～400.Mean polymerisation degree can be measured (KazuoUda﹠amp by people's such as Uda limiting viscosity method; Hideo Saito:Journal of the Society of Fiber Science andTechnology, Japan, Vol.18, No.1 105-120,1962).In the method, can come selective solvent according to the degree of acetylation of cellulose acetate.For example, in the occasion of cellulosetri-acetate, testing program is as follows:
Cellulosetri-acetate is dissolved in the mixture of methylene chloride-methanol (9: 1 weight ratios) of finite concentration c (2.00g/l), then this solution is injected Ostward viscometer and measure this solution mobile time t between the viscometer scale at 25 ℃.On the other hand, measure blank flowing time (second), and calculate viscometric degree of polymerization by means of following formula with above-mentioned solvent mixture:
η
rel＝t/t
0
[η]＝(lnη
rel)/c
Dp＝[η]/(6×10
-4)
T represents the flowing time (second) of solution, t in the formula
0The flowing time (second) of expression solvent, c represents the strength of solution (g/l) of cellulosetri-acetate, η
RelThe expression relative viscosity, [η] representation feature viscosity, Dp is a mean polymerisation degree.
The cellulose acetate of the present invention's preparation is raw material with the hemp dissolving pulp; raw material is easy to get; manufacture method is simple, easy to operate; good product quality is applicable to and produces cigarette with materials such as cellulose acetate, weaving acetate fibre filament, film (polarizer protective membrane, colour filter, be used for the film of photochromics), semipermeable partition, sensitive films.
The invention will be further described below in conjunction with embodiment:
Embodiment:
Embodiment 1:
With the hemp dissolving pulp that R-10 is 87%, viscosity is 4.2dl/g is raw material, through following prepared cellulose acetate:
(1) hemp dissolving pulp is pulverized: tabular hemp dissolving pulp finished product is ground into velvet-like outward appearance by shredder.
(2) activation: acetic acid is sprayed on the hemp dissolving pulp after the pulverizing.The consumption of acetic acid is 30% of a hemp dissolving pulp weight, and the activatory temperature is 25 ℃, soak time 70 minutes.
(3) acetylize: with hemp dissolving pulp weight is benchmark; acetic acid with 200%, 15% sulfuric acid, 200% aceticanhydride and hemp dissolving pulp add in the acetify reactor; the initial temperature of reaction is from-10 ℃, and temperature rise rate is controlled to be 0.6 ℃/min, and the time of acetylization reaction is 30 minutes.
(4) hydrolysis: adopt mass concentration be 20% the magnesium acetate aqueous solution as hydrolytic reagent, begin to add at twice in back 1 hour, 1.5 hours in hydrolysis.The temperature of hydrolytic process is controlled at 70 ℃.After 2 hours, end hydrolysis reaction.
(5) precipitating: the slurry dilution after adopting the dilute acid soln of 10% concentration that acetylize is finished, and make it precipitating.
(6) washing: adopt softening water that the cellulose acetate that separates out is washed, washing temperature is 80 ℃, and the washing time is 100min.
(7) drying: under 105 ℃ of conditions the cellulose acetate after the washing is being carried out warm air drying, the moisture controlled of final cellulose acetate product is 4%.
The degree of acetylation that present embodiment finally prepares cellulose acetate is 58.7%, and mean polymerisation degree is 380.Can be applicable to the preparation of materials such as film (polarizer protective membrane, colour filter, be used for the film of photochromics), semipermeable partition, sensitive film.
Embodiment 2:
With the hemp dissolving pulp that R-10 is 97%, viscosity is 8.2dl/g is raw material, through following prepared cellulose acetate:
(1) hemp dissolving pulp is pulverized: cotton-shaped hemp dissolving pulp finished product is ground into velvet-like outward appearance by shredder.
(2) activation: acetic acid is sprayed on the hemp dissolving pulp after the pulverizing.The consumption of acetic acid is 35% of a hemp dissolving pulp weight, and the activatory temperature is 30 ℃, soak time 40 minutes.
(3) acetylize: with hemp dissolving pulp weight is benchmark; acetic acid with 300%, 10% sulfuric acid, 220% aceticanhydride and hemp dissolving pulp add in the acetify reactor; the initial temperature of reaction is since 4 ℃, and temperature rise rate is controlled to be 0.8 ℃/min, and the time of acetylization reaction is 49 minutes.
(4) hydrolysis: adopt mass concentration be 20% the magnesium acetate aqueous solution as hydrolytic reagent, begin back 1 hour, 2.5 hours, 5 little time-divisions in hydrolysis and add for three times.The temperature of hydrolytic process is controlled at 78 ℃.After 5 hours, end hydrolysis reaction.
(5) precipitating: the slurry dilution after adopting the dilute acid soln of 10% concentration that acetylize is finished, and make it precipitating.
(6) washing: adopt softening water that the cellulose acetate that separates out is washed, washing temperature is 80 ℃, and the washing time is 100min.
(7) drying: under 105 ℃ of conditions the cellulose acetate after the washing is being carried out warm air drying, the moisture controlled of final cellulose acetate product is 3%.
The degree of acetylation that present embodiment finally prepares cellulose acetate is 55.3%, and mean polymerisation degree is 440.Can be applicable to the preparation of cigarette with cellulose acetate, weaving acetate fibre filament.
Embodiment 3:
With the hemp dissolving pulp that R-10 is 62%, viscosity is 10dl/g is raw material, through following prepared cellulose acetate:
(1) hemp dissolving pulp is pulverized: tabular hemp dissolving pulp finished product is ground into velvet-like outward appearance by shredder.
(2) activation: acetic acid is sprayed on the hemp dissolving pulp after the pulverizing.The consumption of acetic acid is 200% of a hemp dissolving pulp weight, and the activatory temperature is 40 ℃, soak time 300 minutes.
(3) acetylize: with hemp dissolving pulp weight is benchmark; acetic acid with 800%, 20% sulfuric acid, 400% aceticanhydride and hemp dissolving pulp add in the acetify reactor; the initial temperature of reaction is since 20 ℃, and temperature rise rate is controlled to be 0.5 ℃/min, and the time of acetylization reaction is 40 minutes.
(4) hydrolysis: adopt mass concentration be 10% the magnesium acetate aqueous solution as hydrolytic reagent, begin to add at twice in back 1 hour, 1.5 hours in hydrolysis.The temperature of hydrolytic process is controlled at 150 ℃.After 1.5 hours, end hydrolysis reaction.
(5) precipitating: the slurry dilution after adopting the dilute acid soln of 6% concentration that acetylize is finished, and make it precipitating.
(6) washing: adopt softening water that the cellulose acetate that separates out is washed, washing temperature is 50 ℃, and the washing time is 120min.
(7) drying: under 118 ℃ of conditions the cellulose acetate after the washing is being carried out warm air drying, the moisture controlled of final cellulose acetate product is 3%.
Present embodiment finally prepares cellulose acetate and can be applicable to the preparation with cellulose acetate, weaving acetate fibre filament of film (polarizer protective membrane, colour filter, be used for the film of photochromics), semi-permeable, cigarette.
Claims (7)
1, a kind of hemp dissolving pulp that adopts is the cellulose acetate that raw material is made, and it is characterized in that: be to be raw material with the hemp dissolving pulp, and the product that makes through pulverizing, activation, acetylize, hydrolysis, precipitating, washing, drying.
2, employing hemp dissolving pulp according to claim 1 is the cellulose acetate that raw material is made, and it is characterized in that: the R-10 value of raw material hemp dissolving pulp is 60%～99.5%, and viscosity is 4dl/g～10dl/g.
3, a kind of hemp dissolving pulp that adopts is the manufacture method of the cellulose acetate made of raw material, it is characterized in that: comprise the following steps: successively
(1) hemp dissolving pulp is pulverized: with the R-10 value is 60%～99.5%, and viscosity is that the tabular or cotton-shaped hemp dissolving pulp finished product of 4dl/g～10dl/g is ground into velvet-like by shredder;
(2) activation: acetic acid or aqueous acetic acid are sprayed on the hemp dissolving pulp after the pulverizing, perhaps hemp dissolving pulp are immersed in acetic acid or the aqueous acetic acid, carry out activation treatment; The consumption of acetic acid is 20%～300% of a hemp dissolving pulp weight during activation treatment, and the activatory temperature is 20～50 ℃, soak time 30～300 minutes;
(3) acetylize: acetylation is that solvent, aceticanhydride are that acetylizing agent, sulfuric acid are catalyzer with acetic acid, with hemp dissolving pulp weight is benchmark, the aceticanhydride of the sulfuric acid of the acetic acid of 40～800% weight, 1～20% weight, 20～400% weight and hemp dissolving pulp is added in the reactor carry out acetylization reaction;
(4) hydrolysis: to adopt mass concentration be 10～40% the magnesium acetate aqueous solution as the hydrolytic reagent reaction that is hydrolyzed;
(5) precipitating: the slurry dilution after the dilute acetic acid solution of employing 3～10% concentration is finished acetylize, and make it precipitating;
(6) washing: adopt softening water that the cellulose acetate that separates out is washed processing;
(7) drying: under 90 ℃～120 ℃ conditions cellulose acetate after the washing is being carried out drying treatment, with the moisture controlled of cellulose acetate product 1～5%, product.
4, employing hemp dissolving pulp according to claim 3 is the manufacture method of the cellulose acetate made of raw material; it is characterized in that: the initial temperature of acetylization reaction is from-10 ℃～35 ℃; temperature rise rate is controlled at 0.5 ℃/min～3.0 ℃/min, and the time of acetylization reaction was controlled at 20～90 minutes.
5, be the manufacture method of the cellulose acetate made of raw material according to claim 3 or 4 described employing hemp dissolving pulps, it is characterized in that: during hydrolysis, hydrolytic reagent divides 2～4 addings, and the temperature of hydrolytic process is controlled at 50～200 ℃.
6, be the manufacture method of the cellulose acetate made of raw material according to claim 3 or 4 described employing hemp dissolving pulps, it is characterized in that: when washing was handled, washing temperature was controlled at 40～90 ℃, and the washing time is 20～120 minutes.
7, the described employing hemp dissolving pulp of a kind of claim 1 is the application of the cellulose acetate made of raw material at preparation weaving acetate fibre filament, polarizer protective membrane, colour filter, the film that is used for photochromics, semipermeable partition or sensitive film.
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| CN102021859A (en) * | 2010-09-10 | 2011-04-20 | 上海众伟生化有限公司 | Paper-making pulping method by using kenaf aggregate |
| CN102153660A (en) * | 2011-04-07 | 2011-08-17 | 泸州北方化学工业有限公司 | Process for producing cellulose acetate |
| CN102153659A (en) * | 2011-04-07 | 2011-08-17 | 泸州北方化学工业有限公司 | Preparation method of cellulose acetate |
| CN102180976A (en) * | 2011-04-07 | 2011-09-14 | 泸州北方化学工业有限公司 | Production method of cellulose acetate |
| CN102180975A (en) * | 2011-04-07 | 2011-09-14 | 泸州北方化学工业有限公司 | Preparation process of cellulose acetate |
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| TWI404844B (en) * | 2012-02-17 | 2013-08-11 | Univ Southern Taiwan | Method of preparing cellulose acetate |
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| CN102021859A (en) * | 2010-09-10 | 2011-04-20 | 上海众伟生化有限公司 | Paper-making pulping method by using kenaf aggregate |
| CN102153660A (en) * | 2011-04-07 | 2011-08-17 | 泸州北方化学工业有限公司 | Process for producing cellulose acetate |
| CN102153659A (en) * | 2011-04-07 | 2011-08-17 | 泸州北方化学工业有限公司 | Preparation method of cellulose acetate |
| CN102180976A (en) * | 2011-04-07 | 2011-09-14 | 泸州北方化学工业有限公司 | Production method of cellulose acetate |
| CN102180975A (en) * | 2011-04-07 | 2011-09-14 | 泸州北方化学工业有限公司 | Preparation process of cellulose acetate |
| CN102180976B (en) * | 2011-04-07 | 2012-08-29 | 泸州北方化学工业有限公司 | Production method of cellulose acetate |
| CN102153660B (en) * | 2011-04-07 | 2013-01-02 | 泸州北方化学工业有限公司 | Process for producing cellulose acetate |
| CN102180975B (en) * | 2011-04-07 | 2013-01-02 | 泸州北方化学工业有限公司 | Preparation process of cellulose acetate |
| TWI404844B (en) * | 2012-02-17 | 2013-08-11 | Univ Southern Taiwan | Method of preparing cellulose acetate |
| CN103131233A (en) * | 2013-03-06 | 2013-06-05 | 北京林业大学 | Ultraviolet screening agent and preparation method and application thereof |
| CN103131233B (en) * | 2013-03-06 | 2014-08-06 | 北京林业大学 | Ultraviolet screening agent and preparation method and application thereof |
| CN103923414A (en) * | 2014-04-16 | 2014-07-16 | 潍坊胜达科技股份有限公司 | Strippable protective film as well as preparation method and application thereof |
| CN106046178A (en) * | 2016-07-14 | 2016-10-26 | 岭南师范学院 | Method for preparing cellulose acetate from sisal fiber |
| CN106046178B (en) * | 2016-07-14 | 2019-04-26 | 岭南师范学院 | A method of cellulose acetate is prepared by raw material of sisal fiber |
| CN106317229A (en) * | 2016-08-22 | 2017-01-11 | 四川北方硝化棉股份有限公司 | Production method for preparing low-substituted cellulose acetate |
| CN111171337A (en) * | 2020-02-20 | 2020-05-19 | 广州楹鼎生物科技有限公司 | Preparation method of acetylated lignocellulose |
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