RU2203995C1 - Method for producing microcrystalline cellulose - Google Patents

Method for producing microcrystalline cellulose Download PDF

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RU2203995C1
RU2203995C1 RU2002118498/12A RU2002118498A RU2203995C1 RU 2203995 C1 RU2203995 C1 RU 2203995C1 RU 2002118498/12 A RU2002118498/12 A RU 2002118498/12A RU 2002118498 A RU2002118498 A RU 2002118498A RU 2203995 C1 RU2203995 C1 RU 2203995C1
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characterized
method according
wood waste
hydrogen peroxide
acetic acid
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RU2002118498/12A
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Russian (ru)
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В.Г. Данилов
О.В. Яценкова
С.А. Кузнецова
Б.Н. Кузнецов
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Институт химии и химической технологии СО РАН
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Abstract

FIELD: pharmaceutical, food-processing, perfume and other branches of industry. SUBSTANCE: method involves processing wood wastes, such as sawdust, with mixture of 35% hydrogen peroxide and 30% acetic acid in the presence of sulfuric acid at liquor ratio of 10-15:1, temperature of 120-140 C and process duration of 1-3 hours. EFFECT: wider raw material stock, simplified process, improved quality, reduced cost of base product, and improved ecology control. 7 cl, 2 tbl

Description

 The invention relates to the chemical processing of cellulose-containing raw materials, specifically to a method for producing microcrystalline cellulose (MCC), which is widely used as a filler in the pharmaceutical, food and perfume industries, a stabilizer for water-latex paints and emulsions, and a sorbent for chromatography. MCC can be used in medicine as a physiologically active substance that improves metabolic processes in the body.

 Known methods for producing microcrystalline cellulose are based on the processing by mineral acids (hydrochloric, sulfuric, nitric, etc.) of high-quality raw materials with a low lignin content (cotton, linter, cotton wool, cellulose, cotton and textile waste). Low-grade raw materials (wood waste, sawdust) are used only for the production of powdered celluloses of low quality due to the high degree of polymerization and a significant content of residual lignin.

So, there is a known method of producing powdered cellulose, which consists in processing wood sawdust by boiling them in hydrochloric or sulfuric acids in a mixture with an aqueous solution of nitric acid salt Na, K, NH 4 , Ni, Cu (II) or Cd with a volume ratio of acid and salt solutions 2.5-3.5: 1, for 6-8 hours and a water module 20-30 (SU 1699142, 07.20.1989).

 The disadvantages of this method are: non-environmental process, which is due to the prolonged boiling of sawdust in toxic substances such as hydrochloric or sulfuric acid, in the presence of salts of alkali and heavy metals, which are carcinogens; low quality of the resulting product due to the significant content of residual lignin (1.7-7.9%) and a high average degree of polymerization (295-630); significant consumption of chemicals, which creates certain difficulties in the purification of wash water from salts of heavy metals and waste disposal.

 A known method of producing microcrystalline and powder cellulose, in which lignocellulosic material (wood chips) is crushed by explosive autohydrolysis, followed by repeated extraction of lignin with water and a solvent (0.41% NaOH, acetone, dioxane, ethyl alcohol, etc.). Next, the selected cellulose is bleached with a solution of a complex composition followed by acid hydrolysis (SU 1792942, 02/07/1993).

 The disadvantages of this method are its complexity and multi-stage, which is due to the requirement of special equipment for explosive autohydrolysis (the operation is used to grind lignocellulosic material), multiple and lengthy (24-hour) extraction, using toxic solvents (acetone, dioxane). In addition, the disadvantage of this method is the use of a bleaching solution of complex composition, as well as the low quality of the resulting product.

Closest to the proposed method in terms of physical nature and the final result is a method for producing microcrystalline cellulose by treating fibrous waste from the ginning and textile industries with a mixture of 3.5% hydrochloric and 0.6% nitric acids in the presence of a catalyst of 10% phosphor-molybdenum acid when heated to 80 o C for 1 h with a liquid module 1:10 (RU 2155192.27.08.2000).

 The disadvantages of this method include the use of high quality raw materials with a low lignin content (fibrous waste from the ginning and textile industries), poor quality of the obtained MCC due to the wide range of polymerization degree (150-400). The process is complex and environmentally friendly due to the use of environmentally hazardous mineral acids (hydrochloric, nitric, phosphorus-molybdenum), additional costs are required to remove them.

The objective of the invention is:
- expansion of the raw material base for obtaining MCC through the use of wood waste (sawdust);
- simplification of the process of obtaining the MCC;
- improving the quality of the target product;
- reduction of its cost due to the use of wood waste and simplification of the process;
- improving the environmental friendliness of the process.

The goal is achieved in that in the method for producing microcrystalline cellulose by acid treatment of cellulose-containing raw materials, according to the invention, wood waste (sawdust) is used as raw material, which is treated with a mixture of 35% hydrogen peroxide and 30% acetic acid taken in molar the ratio of 0.3-0.5, in the presence of sulfuric acid in an amount of 1.5-2.0% by weight of absolutely dry wood with a water module of 10-15: 1; a temperature of 120-140 o C and a duration of 1-3 hours, followed by solvolysis of the fibrous product. Solvolysis is carried out in a solution of a similar composition (a mixture of hydrogen peroxide and acetic acid with a molar ratio of 0.3-0.5), but without sulfuric acid catalyst at a temperature of 110-130 o C, a hydraulic module of 10-15: 1 and a duration of 1-2 hours. Sawdust of birch, fir, larch is used as wood waste.

 A comparative analysis of the proposed method with the prototype shows that the invention allows to significantly expand the raw material base for obtaining the MCC, and therefore, to utilize the huge reserves of wood waste from the timber industry.

 The use of delignification processes (treatment with hydrogen peroxide and acetic acid in the presence of sulfuric acid as a catalyst) and subsequent solvolysis allows to obtain higher quality microcrystalline cellulose: Cr = 0.66-0.74, SP = 100-248 (in the prototype 150-400) . The proposed method allows to reduce the cost of the obtained MCC through the use of cheap raw materials. The replacement of environmentally harmful mineral acids (in the prototype) with hydrogen peroxide and acetic acid makes the proposed process more environmentally friendly.

 The proposed method is confirmed by specific examples.

Example 1. 10 g of sawdust wood fractions mm 2 <d <5 mm with a lignin content of 21.8%, dried at a temperature of 105 o C to constant weight, placed in a reactor, add 27 ml of hydrogen peroxide, 123 ml of an aqueous solution of acetic acid (molar ratio of H 2 O 2 / CH 3 COOH = 0.5) and 0.12 ml of sulfuric acid (2 wt.% of absolutely dry wood). The hydraulic unit is 15: 1. The reactor is placed in a heat chamber and kept at a temperature of 120 o C for 2 hours. After which the mixture is cooled by filtration, the solution is separated from the fibrous product and washed with water until neutral. The washed product is subjected to solvolysis with a 15: 1 hydromodule in a mixed solution containing hydrogen peroxide and an aqueous solution of acetic acid (molar ratio of H 2 O 2 / CH 3 COOH = 0.5), a temperature of 120 ° C. and a duration of 1 hour. Then the resulting product is separated from the solution by filtration, washed with water until neutral and dried at a temperature of 105 o C to constant weight. The yield of the MCC is 3.05 g (30.5% of the mass of absolutely dry wood or 90.9% of the mass of absolutely dry fibrous product). The degree of polymerization (SP) 217.

 Examples 2-17. Perform analogously to example 1, but vary the composition of the working solutions.

 The main characteristics of microcrystalline cellulose obtained from wood waste are given in Table 2. The quality of the MCC are the degree of polymerization (SP), crystallinity index (Cr), crystallite size normal to the (002) plane.

Thus, the proposed method for producing microcrystalline cellulose allows you to:
- expand its raw material base through the use of wood waste (sawdust);
- improve the quality of the target product;
- simplify the process of obtaining the MCC;
- reduce its cost through the use of wood waste and simplify the process;
- increase the environmental friendliness of the process.

Claims (7)

 1. A method of producing microcrystalline cellulose by acid treatment of cellulose-containing raw materials, characterized in that wood waste is used as raw material, which is treated with a mixture of 35% hydrogen peroxide and 30% acetic acid in the presence of sulfuric acid, followed by solvolysis of the fibrous product.
 2. The method according to p. 1, characterized in that the wood waste is treated with a molar ratio of hydrogen peroxide and acetic acid of 0.3-0.5.
 3. The method according to p. 1, characterized in that the wood waste is treated in the presence of sulfuric acid in an amount of 1.5-2.0% by weight of absolutely dry wood.
4. The method according to p. 1, characterized in that the wood waste is treated with a hydraulic module of 10-15: 1, a temperature of 120-140 o C and a duration of 1-3 hours
 5. The method according to p. 1, characterized in that the solvolysis of the fibrous product is carried out in a mixture of 35% hydrogen peroxide and 30% acetic acid in a molar ratio of 0.3-0.5.
6. The method according to p. 1, characterized in that the solvolysis of the fibrous product is carried out at a temperature of 110-130 o C, a hydraulic module of 10-15: 1 and a duration of 1-2 hours
 7. The method according to claim 1, characterized in that sawdust of birch, fir, larch is used as wood waste.
RU2002118498/12A 2002-07-09 2002-07-09 Method for producing microcrystalline cellulose RU2203995C1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2627435C1 (en) * 2016-06-16 2017-08-08 Федеральное государственное бюджетное учреждение "Гематологический научный центр" Министерства здравоохранения Российской Федерации (ФГБУ ГНЦ Минздрава России) Agent with antithrombotic activity
RU2682625C1 (en) * 2018-03-20 2019-03-19 Федеральное Государственное Бюджетное Учреждение Науки Институт Химии Коми Научного Центра Уральского Отделения Российской Академии Наук Method for production of nanocrystalline particles of cellulose by catalytic solvolysis in an organic medium
RU2689753C1 (en) * 2018-11-21 2019-05-28 Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "КОМИ научный центр Уральского отделения Российской академии наук" Nanocrystal, nanocrystal cellulose hydrosol and method for production thereof
RU2705957C1 (en) * 2019-06-15 2019-11-12 Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "КОМИ научный центр Уральского отделения Российской академии наук" METHOD OF PRODUCING NANOCRYSTALLINE CELLULOSE USING A Cu (II) CATALYST

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2627435C1 (en) * 2016-06-16 2017-08-08 Федеральное государственное бюджетное учреждение "Гематологический научный центр" Министерства здравоохранения Российской Федерации (ФГБУ ГНЦ Минздрава России) Agent with antithrombotic activity
RU2682625C1 (en) * 2018-03-20 2019-03-19 Федеральное Государственное Бюджетное Учреждение Науки Институт Химии Коми Научного Центра Уральского Отделения Российской Академии Наук Method for production of nanocrystalline particles of cellulose by catalytic solvolysis in an organic medium
RU2689753C1 (en) * 2018-11-21 2019-05-28 Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "КОМИ научный центр Уральского отделения Российской академии наук" Nanocrystal, nanocrystal cellulose hydrosol and method for production thereof
RU2705957C1 (en) * 2019-06-15 2019-11-12 Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "КОМИ научный центр Уральского отделения Российской академии наук" METHOD OF PRODUCING NANOCRYSTALLINE CELLULOSE USING A Cu (II) CATALYST

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Effective date: 20060710