EP0153182A2 - Verfahren zur Herstellung von feinteiligen Cellulosepartikeln - Google Patents

Verfahren zur Herstellung von feinteiligen Cellulosepartikeln Download PDF

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Publication number
EP0153182A2
EP0153182A2 EP85301079A EP85301079A EP0153182A2 EP 0153182 A2 EP0153182 A2 EP 0153182A2 EP 85301079 A EP85301079 A EP 85301079A EP 85301079 A EP85301079 A EP 85301079A EP 0153182 A2 EP0153182 A2 EP 0153182A2
Authority
EP
European Patent Office
Prior art keywords
cellulose fibers
fibers
cellulose
finely divided
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85301079A
Other languages
English (en)
French (fr)
Other versions
EP0153182B1 (de
EP0153182A3 (en
Inventor
Takayoshi Higuchi
Kingo Yokota
Mitsuhiko Tanahashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akita Jujo Chemicals Co Ltd
Original Assignee
AKITA JUJO CHEMICALS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AKITA JUJO CHEMICALS Co Ltd filed Critical AKITA JUJO CHEMICALS Co Ltd
Publication of EP0153182A2 publication Critical patent/EP0153182A2/de
Publication of EP0153182A3 publication Critical patent/EP0153182A3/en
Application granted granted Critical
Publication of EP0153182B1 publication Critical patent/EP0153182B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/30—Defibrating by other means
    • D21B1/36—Explosive disintegration by sudden pressure reduction

Definitions

  • This invention relates to a process for producing finely divided cellulose particles in which substantially lignin-free cellulose fibers are chemically and physically reduced to fine particles by the partial hydrolysis with activated water and by the utilization of the force resulting from instantaneous vaporization of water.
  • Finely divided cellulose particles have a large specific surface area and have excellent characteristics of adsorptivity, colloidal disperisibility and reactivity. Accordingly, they are widely used as absorbents, thickeners, excipients, adsorbents and other industrial materials and as dietary food materials in the field of pharmaceutical industry, food industry and other manufacturing industries.
  • microstructure of cellulose fibers is believed to be such that microcrystals having molecular chains of cellulose highly oriented by means of hydrogen bonds and amorphous regions having a low degree of orientation are alternately arranged in the lengthwise direction to form elementary fibrils, a plurality of elementary fibrils are joined to constitute a fibril, and such fibrils are further combined to form a higher order of fibrous structure.
  • the size, polymerization degree, crystallinity and shape of finely divided cellulose particles produced by these conventional methods vary according to the particular process employed.
  • mechanical processes are simple in operation and, in particular, dry processes are characterized in that the microstructure of cellulose fibers is disintegrated by the action of direct impact to yield a powder having low crystallinity and polymerization degree.
  • a vibration mill is used according to common practice, the size of the resulting particles is limited to as large as several tens of microns and their size reduction requires much energy.
  • Well-known wet processes include the beating process commonly used in the making of paper pulp and the process in which cellulose fibers are broken by passing them through an orifice under high pressure to effect rapid deceleration.
  • the finely divided cellulose particles produced by these processes have the disadvantage that they consist of extremely fibrillated fiber particles varying in shape and having very high water retention properties and the fibrous structure has not been disintegrated down to the level of microcrystals.
  • the cellulose fibers in the form of a suspension need to be agitated or transferred at high speed, resulting in a large consumption of energy.
  • the cellulose fibers so treated are reduced to fine particles by subjecting them to the mechanical treatment.
  • the amorphous regions of the cellulose fibers are decomposed and dissolved away, resulting in a low yield of the finely divided cellulose particles.
  • the yield is of the order of 30 to 50% based on the starting material.
  • the cellulose fibers used as the starting material in the process of the present invention are substantially lignin-free cellulose fibers which are obtained by subjecting a cellulosic material such as wood fibers (e.g., wood chips), bast fibers or seed fibers (e.g., linters) to a treatment for the removal of lignin.
  • a cellulosic material such as wood fibers (e.g., wood chips), bast fibers or seed fibers (e.g., linters) to a treatment for the removal of lignin.
  • the process of the present invention uses, as the starting material, cellulose fibers which have been made substantially lignin-free by subjecting a raw cellulosic material to a treatment for the removal of lignin.
  • cellulose fibers examples include commercial products of chemical pulp for paper-making use, chemical pulp for dissolving use, and the like.
  • pulp comprising highly purified cellulose should preferably be used to enhance the yield of the resulting finely divided cellulose particles.
  • chemical pulp for paper-mkaing use having a high hemicellulose content the hemicellulose tends to undergo hydrolysis and dissolve out during the application of high pressure and high temperature, resulting in a reduced yield of the product.
  • the cellulose fibers used as the starting material should preferably have a water content of 10% or greater.
  • the application of pressure and heat to the cellulose fibers is carried out by blowing in saturated steam, the drain resulting from condensation of the saturated steam brings the whole cellulose fibers into a hydrous condition. Accordingly, the cellulose fibers may be used as they are, unless they are in an excessively dry condition.
  • mineral acids such as sulfuric acid, hydrochloric acid, sulfurous acid, etc., organic acids such as acetic acid, formic acid, etc., or alkalis such as sodium hydroxide, magnesium hydroxide, calcium hydroxide, etc. may be added to the cellulose fibers for the purpose of promoting the disintegration thereof.
  • alkalis such as sodium hydroxide, magnesium hydroxide, calcium hydroxide, etc.
  • the application of pressure and heat to the cellulose fibers is carried out by placing the cellulose fibers in a pressure vessel having a jacket, introducing low- pressure steam having a gauge pressure of about 1 to 2 kg/cm 2 into the vessel to expel the air contained therein, and then heating the entire vessel and simultaneously blowing saturated steam into the vessel up to a predetermined pressure so as to bring the cellulose fibers into a hydrous condition.
  • the amorphous regions of the cellulose fibers is partially hydrolyzed by activated water, resulting in a reduction in the degree of polymerization of cellulose.
  • its decomposition to lower-molecular-weight compounds can hardly proceed in contrast to the case of conventional acid hydrolysis in a heterogeneous system. Rather, the hot water promotes the rearrangement of molecular chains in the amorphous regions and thereby enhances the degree of crystallinity.
  • the cellulose may undergo partial decomposition. Accordingly, in the process of the present invention, the application of pressure and heat may be carried out for a very short period of time which is of the order of minutes.
  • the hydrous cellulose fibers obtained by the above-described application of pressure and heat are instantaneously and explosively discharged through a small tube into a receiver tank at atmospheric pressure.
  • a device having excellent sealability e.g., a ball valve or a rotary valve
  • the resulting finely divided cellulose particles in hydrous form are suspended in water to form a thick slurry.
  • this slurry may be subjected to a simple bleaching treatment using a chlorine-containing bleaching compound (such as sodium hypochlorite, calcium hypoclorite or chlorine dioxide), hydrogen peroxide or ozone. Then, the slurry is filtered, washed and, if necessary, sieved to obtain a product. Furthermore, this product may be dried according to such techniques as heating, spray drying, freeze-drying and the like.
  • cellulose has a very strong affinity for water because it possesses hydroxyl groups in the molecular chain. Accordingly, when cellulose fibers are exposed to water, the water penetrates into higher order tissues such as cell walls, cell cavities (lumen), etc. and, further, into their microstructure. However, the water becomes adsorbed by the amorphous regions having randomly oriented hydroxyl groups and on the surfaces of the crystals, and does not penetrate into the crystals, so that the force resulting from vaporization of the water acts effectively on the cellulose fibers and thereby reduces them to fine particles.
  • the water contained in the cellulose fibers and the water adsorbed in the cell walls and cell cavities, between fibrils, between microfibrils, by the amorphous regions and on the crystal surfaces vaporize instantaneously.
  • the strong expansion force so generated acts uniformly, efficiently and concentratedly on the weak portions of the fibrous structure to loosen and break the bonds present in the fibrous structure and thereby disintegrate the fibrous structure.
  • the degree of disintegration of the fibrous structure can be arbitrarily controlled by varying the conditions under which pressure and heat are applied to the cellulose fibers in the above-described manner.
  • saturated steam having a gauge pressure of 5 kg/cm 2 or higher.
  • saturated steam having a gauge pressure of 25 to 30 kg/cm 2 .
  • the resulting cellulose particles consist of small fiber pieces or fibril aggregates in which the bonds between fibrils, between microfibrils, in the microcrystalline regions, and in the non-crystalline regions have not been fully broken as yet.
  • the fibrous structure is loosened, the aforesaid cellulose particles can be reduced to fine particles of smaller size by subjecting them to a post-treatment selected from relatively simple mechanical treatment such as beating, defibration and the like.
  • the present invention permits finely divided cellulose particles having a relatively wide range of sizes and consisting of highly purified, homogeneous cellulose to be economically produced according to a relatively simple procedure and by use of equipment including a discharge device composed of an ordinary pressure vessel and a small tube.
  • the finely divided cellulose particles obtained according to the present invention have been disintegrated down to the level of microfibrils or amorphous regions by the action of the force resulting from vaporization of pressurized water. Therefore, they are excellent in such properties as adsorptivity, colloidal dispersibility and reactivity, as compared with the finely divided cellulose particles produced by conventional chemical processes based on acid hydrolysis in a heterogeneous system or by conventional mechanical processes based on wet grinding.
  • An aqueous suspension of second-cut crude linters was prepared, passed through a screen to remove any dust, and then dewatered.
  • To the resulting wet material was added an aqueous solution of sodium hydroxide. After being stirred well, the mixture was placed in an autoclave and steam was blown thereinto to cook the linters at 160°C for 2 hours.
  • the cooked linters were washed with water, dewatered and then treated in one stage with sodium hydrochlorite to obtain bleached linter pulp having a brightness of 85.2%.
  • This bleached linter pulp was dewatered by means of a centrifuge to obtain hydrous pulp consisting of substantially lignin-free cellulose fibers and having a water content of 71.8%.
  • This hydrous pulp was suitably broken into pieces, which were enclosed in the same pressure vessel as used in Example 1.
  • saturated steam having a gauge pressure of 20 kg/cm 2 and following the same procedure as described in Example 1, the application of pressure and heat to the pulp was carried out under such conditions that a maximum temperature of about 200°C was held for 3 minutes.
  • a slurry of bleached dissolving grade pulp was prepared according to the same procedure as described in Example 3, and adjusted to pH 2.5 by the addition of dilute sulfuric acid. This slurry was dewatered by compression and the resulting cake was crushed to obtain granules having a water content of 57.0%. Using saturated steam having a gauge pressure of 18 kg/cm 2 and following the same procedure as described in Example 1, these granules were treated under such conditions that a maximum temperature of about 202°C was held for 10 minutes. Thus, there was obtained a slurry of finely divided cellulose particles having a pale-yellow color. This slurry was formed into an aqueous suspension having a solid content of 10%.
  • these finely divided cellulose particles were formed into an aqueous suspension having a solid content of 12%.
  • This suspension was treated in a spray dryer (Model L-12; Oogawara Kakoki Co.) to obtain finely divided cellulose particles in dry form.
  • the conditions under which this spray drying was carried out included a feed rate of 10 kg/hour, an atomizer speed of 25,700 rpm, an inlet gas temperature of 150°C and an exhaust gas temperature of 90°C.

Landscapes

  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paper (AREA)
EP19850301079 1984-02-20 1985-02-19 Verfahren zur Herstellung von feinteiligen Cellulosepartikeln Expired EP0153182B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2993784A JPS60173001A (ja) 1984-02-20 1984-02-20 セルロ−ス微粒子体の製造方法
JP29937/84 1984-02-20

Publications (3)

Publication Number Publication Date
EP0153182A2 true EP0153182A2 (de) 1985-08-28
EP0153182A3 EP0153182A3 (en) 1986-12-17
EP0153182B1 EP0153182B1 (de) 1990-01-03

Family

ID=12289901

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850301079 Expired EP0153182B1 (de) 1984-02-20 1985-02-19 Verfahren zur Herstellung von feinteiligen Cellulosepartikeln

Country Status (3)

Country Link
EP (1) EP0153182B1 (de)
JP (1) JPS60173001A (de)
DE (1) DE3575173D1 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087324A (en) * 1990-10-31 1992-02-11 James River Corporation Of Virginia Paper towels having bulky inner layer
WO1998027269A1 (en) * 1996-12-17 1998-06-25 Kimberly-Clark Worldwide, Inc. Treatment process for cellulosic fibers
US6413362B1 (en) 1999-11-24 2002-07-02 Kimberly-Clark Worldwide, Inc. Method of steam treating low yield papermaking fibers to produce a permanent curl
US6461472B2 (en) * 1999-03-03 2002-10-08 The Forestry And Forest Products Research Institute Explosively-split fragments obtained by water-vapor explosion of wooden source materials, wooden material containing such fragments as its aggregate, their manufacturing methods and machines
US6506282B2 (en) 1998-12-30 2003-01-14 Kimberly-Clark Worldwide, Inc. Steam explosion treatment with addition of chemicals

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1198703A (en) * 1984-08-02 1985-12-31 Edward A. De Long Method of producing level off d p microcrystalline cellulose and glucose from lignocellulosic material
JPH0653761B2 (ja) * 1985-10-08 1994-07-20 ダイセル化学工業株式会社 パルプの精製法
JPS62240302A (ja) * 1986-04-10 1987-10-21 Asahi Chem Ind Co Ltd 超低分子量セルロ−スの調製法
JPH0611793B2 (ja) * 1989-08-17 1994-02-16 旭化成工業株式会社 微粒化セルロース系素材の懸濁液及びその製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE420796A (de) *
US1979341A (en) * 1929-04-11 1934-11-06 Cellulose Res Corp Process for preparing cellulose
US1996797A (en) * 1930-11-26 1935-04-09 Dreyfus Henry Production of cellulosic products
US4374702A (en) * 1979-12-26 1983-02-22 International Telephone And Telegraph Corporation Microfibrillated cellulose

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087324A (en) * 1990-10-31 1992-02-11 James River Corporation Of Virginia Paper towels having bulky inner layer
WO1998027269A1 (en) * 1996-12-17 1998-06-25 Kimberly-Clark Worldwide, Inc. Treatment process for cellulosic fibers
US6506282B2 (en) 1998-12-30 2003-01-14 Kimberly-Clark Worldwide, Inc. Steam explosion treatment with addition of chemicals
US6461472B2 (en) * 1999-03-03 2002-10-08 The Forestry And Forest Products Research Institute Explosively-split fragments obtained by water-vapor explosion of wooden source materials, wooden material containing such fragments as its aggregate, their manufacturing methods and machines
US6413362B1 (en) 1999-11-24 2002-07-02 Kimberly-Clark Worldwide, Inc. Method of steam treating low yield papermaking fibers to produce a permanent curl

Also Published As

Publication number Publication date
JPH0212494B2 (de) 1990-03-20
EP0153182B1 (de) 1990-01-03
DE3575173D1 (de) 1990-02-08
EP0153182A3 (en) 1986-12-17
JPS60173001A (ja) 1985-09-06

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