CN109627348B - Method for extracting microcrystalline cellulose from taxus media branch residues - Google Patents

Method for extracting microcrystalline cellulose from taxus media branch residues Download PDF

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CN109627348B
CN109627348B CN201811622636.4A CN201811622636A CN109627348B CN 109627348 B CN109627348 B CN 109627348B CN 201811622636 A CN201811622636 A CN 201811622636A CN 109627348 B CN109627348 B CN 109627348B
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acid
filter residue
microcrystalline cellulose
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solid
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CN109627348A (en
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夏涛
桂铭阳
曾国进
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Wuhan University of Technology WUT
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials

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Abstract

The invention discloses a method for extracting microcrystalline cellulose from taxus media branch residues. The method comprises removing water soluble substances from residue with boiled distilled water; then extracting with toluene-ethanol mixed solvent to remove lipid, and removing lignin with acidic bleaching agent; then soaking with an alkali reagent to remove hemicellulose, bleaching again, and finally hydrolyzing with an acid reagent to finally obtain the microcrystalline cellulose. The method has the advantages of simple process, easy control of reaction conditions, strong processing capacity, industrial large-scale production and the like, and the prepared microcrystalline cellulose product has high yield, proper polymerization degree and wide application.

Description

Method for extracting microcrystalline cellulose from taxus media branch residues
Technical Field
The invention relates to the technical field of biological medicines and waste resource recycling, in particular to a method for extracting microcrystalline cellulose from taxus media branch residues.
Background
Taxus media was introduced from Canada in the middle of 90 s in the 20 th century, and is cultivated in Sichuan, Guangxi, Shandong, and the like. The anticancer drug taxol can be extracted from branches, leaves and roots of Taxus media. The paclitaxel has excellent anticancer effect, and clinical experiments prove that the paclitaxel has curative effects on various cancers such as late ovarian cancer, breast cancer, esophagus cancer, nasopharyngeal cancer, bladder cancer, lymph cancer and the like, has a unique antitumor mechanism and a remarkable tumor inhibition effect, is a most popular novel natural organic anticancer drug in the international market at present, and has special effects on treating complications of various diseases and diminishing inflammation and arteriosclerosis after a heart bypass operation.
Cellulose is the most important component of plant cell walls, accounts for about 40% of cell wall components, and is widely found in plants such as wood, grass, cotton, and the like. Cellulose is a chain-like high molecular compound composed of glucose, and comprises three elements of carbon, hydrogen and oxygen, and the molecular formula is (C)6H10O5)nWherein n is the degree of polymerization of cellulose. Microcrystalline cellulose is a purified, partially depolymerized cellulose, a linear polysaccharide material formed by binding beta-1, 4-glucosidic bonds, and has a particle size of 20-80um and a degree of polymerization generally of 15-375. The preparation method, properties and structure of microcrystalline cellulose have been continuously carried outDiscussing and researching, and widely applying the method in the industries of pharmacy, cosmetics, food and the like.
Taxus chinensis belongs to a lignocellulose material, and contains higher cellulose. If the taxus chinensis residue can be fully utilized, and high-quality microcrystalline cellulose is extracted from the taxus chinensis residue, the economic value of waste recycling can be realized, the economic cost increase caused by waste treatment can be avoided, and multiple purposes can be achieved.
At present, the residue of the branches of the taxus chinensis left after extracting the paclitaxel is not effectively utilized and is generally treated as waste by incineration. Recognizing this problem and making corresponding attempts, Chenjianmi et al (CN1398859A0) disclosed a method for preparing 10-deacetylbaccatin III from Taxus chinensis leaf and branch residues, and Zhoujingjiang et al (CN104140689A) disclosed a method for extracting natural pigments from Taxus chinensis pharmaceutical residues. Although the methods realize the recycling of the taxus chinensis pharmaceutical residues to a certain extent, the extracted target product and the extraction method are completely different from the method. At present, no literature discloses and reports a case of extracting microcrystalline cellulose from taxus chinensis branch residues.
Disclosure of Invention
The invention aims to solve the problem that the existing taxus pharmaceutical residues cannot be effectively utilized, and develops a method for extracting microcrystalline cellulose from taxus media branch residues. The method has the advantages of simple process, easy control, environmental protection and no toxicity, and can realize the purpose of changing waste into valuable and generate better economic benefit. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the method for extracting the microcrystalline cellulose from the taxus media branch residues specifically comprises the following steps:
(a) mixing the residue of the taxus media branches with water, boiling, and carrying out solid-liquid separation to obtain filter residue A. The aim of this step is to remove as much as possible the water-soluble substances in the residue.
(b) And extracting the filter residue A by using at least one of an aromatic hydrocarbon solvent and an alcohol solvent to obtain a filter residue B. The aim of this step is to remove as much lipid material as possible from the residue.
(c) And bleaching the filter residue B by using a bleaching agent to obtain filter residue C. The aim of this step is to remove as much lignin as possible from the residue.
(d) And (3) sequentially treating the filter residue C with an alkali reagent, a bleaching agent and an acid reagent, and finally carrying out solid-liquid separation to obtain the microcrystalline cellulose.
Further, the residue of the Taxus media branches in step (a) is pulverized and sieved in advance to obtain powder, and the powder is mixed with water and boiled and filtered, and the boiling-filtering operation is repeated for 3-5 times. Wherein the ratio of the residue powder of Taxus media branch to water is 1g:30-50mL, and the boiling time is 20-30 min.
Further, the organic solvent used for extracting the filter residue a in the step (b) is specifically a toluene-ethanol mixed solution with a volume ratio of 2: 1.
Further, the specific process of step (b) is as follows: mixing the filter residue A with an organic solvent, stirring and extracting at the constant temperature of 80-100 ℃ for 4-8h, and drying after solid-liquid separation to obtain filter residue B. Wherein the ratio of the filter residue A to the organic solvent is 1g:3-10 mL.
Further, in the step (c), the bleaching agent is an acidic sodium chlorite solution, wherein the acidity is provided by glacial acetic acid, the mass fraction of sodium chlorite in the bleaching agent is 0.5% -3%, and the volume fraction of glacial acetic acid is 1% -5%.
Further, the specific process in step (c) is as follows: mixing the filter residue B with a bleaching agent, reacting at the constant temperature of 50-80 ℃ for 0.5-3h, filtering, repeatedly bleaching for multiple times until the color of the wood flour is changed from dark brown to light gray, washing the obtained solid with water until the filtrate is colorless, and then placing the solid in an environment at the temperature of 30-60 ℃ to dry to constant weight to obtain filter residue C. The proportion of the filter residue B mixed with the bleaching agent is 1g:10-40 mL.
Further, the alkali reagent in the step (d) is selected from one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, barium hydroxide aqueous solution, calcium hydroxide aqueous solution and ammonia water, and the mass fraction of the alkali reagent is 2-18%; the acid reagent is selected from one or more of dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, acetic acid, hydrofluoric acid, phosphoric acid, trichloroacetic acid and trifluoroacetic acid, and the mass fraction of the acid reagent is 1-10%.
Further, the specific process in step (d) is as follows: mixing the filter residue C with an alkali reagent, stirring and reacting at 20-90 ℃ for 30-120min, carrying out solid-liquid separation, and washing the filter residue to be neutral by using water; then, bleaching the filter residue obtained by alkali treatment by using a bleaching agent in a reverse way according to the same method; drying the filter residue obtained by bleaching, mixing with an acid reagent, stirring at 50-100 ℃ for reaction for 0.5-4h, carrying out solid-liquid separation after the reaction is finished, washing with water to obtain a suspension, and freeze-drying at-100 ℃ to-20 ℃ for 6-24h in a 10-100Pa environment to obtain the microcrystalline cellulose.
Further, the ratio of the filter residue C to the alkali reagent is 1g:10-30mL, the ratio of the filter residue obtained by alkali treatment to the bleaching agent is 1g:10-40mL, and the ratio of the filter residue obtained by bleaching to the acid reagent is 1g:20-50 mL.
The invention realizes the recycling of the taxus media branch residues by adopting a simpler process and cheap and easily-obtained raw materials, and removes water-soluble substances, lipid substances, lignin and hemicellulose contained in the residues sequentially and efficiently through a series of reactions in the process to finally obtain cellulose, and then hydrolyzes the cellulose into microcrystalline cellulose. Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects: (1) the high-efficiency resource utilization of the taxol extraction residues of the taxus chinensis is realized, the waste is changed into valuable, and the good economic benefit is realized; (2) the process is simple, the reaction conditions are easy to control and automate, the processing capacity is strong, and the method is beneficial to industrial large-scale production; (3) the microcrystalline cellulose product has high yield, proper polymerization degree and wide application.
Drawings
FIG. 1 is a graph of IR spectra of microcrystalline cellulose produced in accordance with example 1 of the present invention versus a commercial grade microcrystalline cellulose product.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
The taxus media residue in each embodiment of the invention is derived from waste after taxol is extracted by a certain company in China, mainly branches, leaves and stems of the taxus media, and the color is dark brown. Commercial grade microcrystalline cellulose for infrared contrast analysis was purchased from trapa chemical ltd, lazhou, model number PH 101. Other reagents are commonly commercially available.
Example 1
a. Pulverizing residue of Taxus media branches with pulverizer, and sieving the obtained powder with 60 mesh sieve;
b. weighing 20g of sieved Taxus media branch residue powder, mixing the powder with distilled water according to a solid-to-liquid ratio of 1g to 30mL (namely adding 30mL of distilled water into 1g of powder), heating and boiling for 20min, and performing suction filtration to obtain filter residue. Repeating the step for 4 times to obtain filter residue;
c. adding a toluene-ethanol mixed solution (the volume ratio of toluene to ethanol is 2:1, namely 5.33mL of toluene and 2.67mL of ethanol are added into 1g of filter residue) into the filter residue obtained in the step b according to a solid-to-liquid ratio of 1g to 8mL, heating the mixed solution in a constant-temperature oil bath at 100 ℃, mechanically stirring and reacting for 6 hours, carrying out suction filtration to obtain filter residue, and putting the filter residue into an oven for drying;
d. and c, adding bleaching liquid into the filter residue obtained in the step c according to a solid-liquid ratio of 1g to 20mL, wherein the mass fraction of sodium chlorite in the bleaching liquid is 1%, the volume fraction of acetic acid is 2%, and the solvent is water. Placing the mixture in an oil bath at 80 ℃ for constant-temperature reaction for 1h, carrying out solid-liquid separation, repeating the step d 6 times until the color of the wood powder is changed from dark brown to light gray, carrying out suction filtration and water washing until the filtrate is colorless and neutral, and placing the filtrate in a 50 ℃ drying oven to be dried to constant weight to obtain filter residue;
e. d, adding a sodium hydroxide solution with the mass fraction of 17.5% into the filter residue obtained in the step d according to the solid-liquid ratio of 1g to 20mL, stirring and reacting for 30min at normal temperature, performing solid-liquid separation, performing suction filtration, washing with water, and collecting the filter residue after the filtrate is colorless and neutral;
f. bleaching the filter residue obtained in the step e for 1h according to the method in the step d, washing and filtering after solid-liquid separation, collecting the filter residue after the filtrate is neutral, and drying the filter residue in a 50 ℃ drying oven to constant weight to obtain cellulose;
g. and f, adding a hydrochloric acid solution with the mass fraction of 3% into the cellulose powder obtained in the step f according to the solid-to-liquid ratio of 1g to 25mL, placing the mixture in an oil bath at 80 ℃ for reaction for 2h, centrifuging, washing with water to obtain a suspension, placing the suspension in a refrigerator for freezing into ice, and finally drying at 25Pa and-55 ℃ for 12h by using a freeze dryer to obtain the microcrystalline cellulose powder.
To verify whether the final product was microcrystalline cellulose, infrared spectroscopy was performed under the same conditions as compared to commercially available grades of microcrystalline cellulose, and the results are shown in FIG. 1. As can be seen from FIG. 1, the characteristic peaks (1654, 1160 cm) of the target product and commercial grade microcrystalline cellulose-1) The positions were consistent, confirming that the resulting product was indeed microcrystalline cellulose.
According to analysis calculation, the yield of the cellulose in the embodiment is 21.7%, and the polymerization degree is 331.92; the yield of the microcrystalline cellulose was 18.88%, and the degree of polymerization was 146.34.
Example 2
The present embodiment is substantially the same as embodiment 1 in other parameters, except that: in the step e, the mass fraction of sodium hydroxide is 2%, the reaction temperature of alkali treatment is 80 ℃, and the reaction time is 2 hours; and g, in the step g, the reaction temperature of acid treatment is 80 ℃, and the reaction time is 2 hours.
The cellulose obtained in this example had a yield of 15.52% and a degree of polymerization of 233.48; the yield of the microcrystalline cellulose was 12.88%, and the degree of polymerization was 148.34.
Example 3
The present embodiment is substantially the same as embodiment 1 in other parameters, except that: and g, during acid treatment, the mass fraction of hydrochloric acid is 6%, the reaction temperature is 80 ℃, and the reaction time is 2 hours.
The cellulose obtained in this example had a yield of 21.7% and a degree of polymerization of 331.92; the microcrystalline cellulose yield was 17.79% and the degree of polymerization was 140.51.
Example 4
The present embodiment is substantially the same as embodiment 1 in other parameters, except that: and g, during acid treatment, the mass fraction of hydrochloric acid is 3%, the reaction temperature is 90 ℃, and the reaction time is 2 hours.
The cellulose obtained in this example had a yield of 21.7% and a degree of polymerization of 331.92; the yield of the microcrystalline cellulose was 17.36%, and the degree of polymerization was 135.26.
Example 5
The present embodiment is substantially the same as embodiment 1 in other parameters, except that: in the step e, the mass fraction of sodium hydroxide is 2%, the reaction temperature of alkali treatment is 80 ℃, and the reaction time is 2 hours; in the step g, the mass fraction of the acid-treated hydrochloric acid is 3%, the reaction temperature is 90 ℃, and the reaction time is 2 hours.
The cellulose obtained in this example had a yield of 15.52% and a degree of polymerization of 233.48; the yield of the microcrystalline cellulose was 11.36%, and the degree of polymerization was 135.26.
Example 6
The present embodiment is substantially the same as embodiment 1 in other parameters, except that: and e, performing alkali treatment for 30min at normal temperature, wherein the mass fraction of the potassium hydroxide in the step e is 10%.
The cellulose obtained in this example had a yield of 18.5% and a degree of polymerization of 385.32; the yield of the microcrystalline cellulose was 14.32%, and the degree of polymerization was 159.32.
Example 7
The present embodiment is substantially the same as embodiment 1 in other parameters, except that: in the step g, the mass fraction of the sulfuric acid subjected to acid treatment is 10%, the reaction temperature is 80 ℃, and the reaction time is 2 hours.
The cellulose obtained in this example had a yield of 21.7% and a degree of polymerization of 331.92; the yield of the microcrystalline cellulose was 13.23%, and the degree of polymerization was 125.03.

Claims (2)

1. The method for extracting the microcrystalline cellulose from the taxus media branch residues is characterized by comprising the following steps:
(a) mixing the taxus media branch residues with water, boiling, and carrying out solid-liquid separation to obtain filter residues A;
(b) mixing a toluene-ethanol mixed solution with a volume ratio of 2:1 with the filter residue A, stirring and extracting at a constant temperature of 80-100 ℃ for 4-8h, performing solid-liquid separation, and drying to obtain a filter residue B, wherein the solid-liquid ratio of the filter residue A to the toluene-ethanol mixed solution is 1g:3-10 mL;
(c) mixing the filter residue B with a bleaching agent, reacting at the constant temperature of 50-80 ℃ for 0.5-3h, filtering, repeatedly bleaching for multiple times, washing the obtained solid with water until the filtrate is colorless, and drying at the temperature of 30-60 ℃ to constant weight to obtain a filter residue C, wherein the solid-to-liquid ratio of the filter residue B to the bleaching agent is 1g:10-40 mL;
(d) mixing the filter residue C with an alkali reagent according to the proportion of 1g:10-30mL, stirring and reacting at 20-90 ℃ for 30-120min, carrying out solid-liquid separation, and washing the filter residue to be neutral by using water; then, repeatedly bleaching the filter residue obtained by alkali treatment by using a bleaching agent according to the method in the step (c); drying filter residues obtained by bleaching, and mixing the filter residues with an acid reagent according to the ratio of 1g: mixing in a proportion of 20-50mL, stirring at 50-100 ℃ for reaction for 0.5-4h, carrying out solid-liquid separation after the reaction is finished, washing with water to obtain a suspension, and finally carrying out freeze drying to obtain microcrystalline cellulose;
the residue of the taxus media branches in the step (a) is waste after paclitaxel extraction; the bleaching agent in the steps (c) and (d) is an aqueous solution containing glacial acetic acid and sodium chlorite, wherein the mass fraction of the sodium chlorite is 0.5-3%, and the volume fraction of the glacial acetic acid is 1-5%; the alkali reagent in the step (d) is selected from one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, barium hydroxide aqueous solution, calcium hydroxide aqueous solution and ammonia water, and the mass fraction of the alkali reagent is 2-18%; the acid reagent is selected from one or more of dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, acetic acid, hydrofluoric acid, phosphoric acid, trichloroacetic acid and trifluoroacetic acid, and the mass fraction of the acid reagent is 1-10%; the freeze drying temperature is-100 deg.C to-20 deg.C, vacuum degree is 10-100Pa, and freeze drying time is 6-24 h.
2. The method of claim 1, wherein: pulverizing and sieving the residue of the taxus media branches in the step (a) to prepare powder before use, mixing the powder with water, boiling, and filtering for multiple times, wherein the solid-to-liquid ratio of the residue powder of the taxus media branches to the water is 1 g/30-50 mL, and the boiling time is 20-30 min.
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