US2541165A - Method for producing globular articles - Google Patents

Method for producing globular articles Download PDF

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US2541165A
US2541165A US6143A US614348A US2541165A US 2541165 A US2541165 A US 2541165A US 6143 A US6143 A US 6143A US 614348 A US614348 A US 614348A US 2541165 A US2541165 A US 2541165A
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Prior art keywords
bath
viscose
granules
globules
superficially
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US6143A
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Maurice P Kulp
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Akzo Nobel UK PLC
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American Viscose Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/06—Cellulose hydrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
    • B01J2/08—Gelation of a colloidal solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/14—Dipping a core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S425/00—Plastic article or earthenware shaping or treating: apparatus
    • Y10S425/101—Aggregate and pellet

Definitions

  • these difiiculties are substantially completely avoided. This is accomplished by allowing droplets of viscose to form in a gaseous atmosphere and fall into a substantially non-regenerating bath from a height which is suificient to allow the droplet to assume a substantially spherical shape prior to entering the bath.
  • the height required depends upon the size of droplet which can be varied by varying the size of orifice, the temperature of the viscose, or the pressure exerted on the viscose passing through the orifice.
  • a droplet of a size which forms a particle of inch diameter requires a drop of at least 6 feet
  • the superficially coagulated structure is introduced into a heated liquid of non-solvent, non-softening and nonacid character in which coagulation and regeneration of the globules are completed.
  • Suitable liquids for this purpose are hot aqueous salt solutions at a temperature below the boiling point of water.
  • the by-products of regeneration such as alkaline and sulfur compounds
  • the globules are in a watersoluble state and are merely leached out by introducing the globules into water, preferably hot, for the desired period of time.
  • the globules may be dried or, before drying, they may be soaked in a, plasticizer, such as glycerine, when a softened product is desired. Shrinkage to any substantial extent can only occur during the drying step of this procedure since the contact of the globules with acid is restricted to a minimum and the globules are maintained in water-swelled condition thereafter until the drying stage. It has been found that the shrinkage that occurs during the drying of the globules formed in accordance with the procedure of this invention is remarkably uniform in character and substantially iso-tropic so that they undergo little change in their original shape other than a diminution in during the drying.
  • the original shape of the globules formed de pends upon the height from which the viscose droplets are allowed to fall into the acid bath. if dropping heights are used which are considerably greater (more than about 20% greater) than the minimum needed to obtain sphericity, the size of the droplet falling from the dropping orifice or jet does not determine the ultimate size of the product as in such cases, they tend to disrupt into numerou smaller particles which may have various sizes, and, in the extreme of conditicns, a powdered product results.
  • the viscose solution in a vessel 2 which may be provided with a plunger 3 for exerting pressure thereon passes through a dropping tube terminating in an orifice i.
  • a receptacle 5 for the coagulating bath is arranged beneath the hopper to receive the droplets and preferably has a sloped bottom 6 to facilitate removal of the particles roughly in their order of production.
  • the bath in the receptacle 5 may advantageously be an aqueous solution containing 3 to 6% acetic acid and 15 to 20% sodium sulfate at 40 to 0., and the particles are allowed sufficient contact therein to form a thin coagulated skin thereon. Then they are removed and placed in a 20% sodium sulfate solution in water at to C. or up to the boiling point of water. This bath is agitated and the treatment is carried on for about an hour. Finally, the pellets or granules are removed from the salt bath and introduced into a leaching vessel in which they are subjected for 8 to 12 hours or longer to a fiow of hot water at 60 to- 7G G. or higher.
  • the particles may remain in this bath an indefinite period or they may be stored in cold or hot water for an indefinite period before ultimate drying. However, if convenient, drying may be performed directly after the leaching period of 8 to 12 hours mentioned. Preferably, the humidity is controlled to prevent irregular shrinkage.
  • the final products which may be of any size up to the order of inch in diameter approach true sphericity and are substantially free of checks, fissures, bubbles, creases and wrinkles.
  • the unplasticized products are hard: and have a high dielectric constant. Because of this characteristic and the fact that the products are highly resistant to hydrocarbon oils'they may be used in conjunction with such oils for cooling electrical equipment, such as transformers.
  • a substantially non-regenerating aqueous saltcontaining dilute acid bath removingthe formed granules of viscose from the bath' after a supericial coagulation thereof, and introducing the superficially coagulated granules into a heated non-acid aqueous salt-containing bath incapable of softening the granules and having a tempera ture of at least 60 C.
  • the method of making granular particles comprising regenerated cellulose comprising the steps of allowing droplets of viscose tov fall through air into a substantially non-regenerating salt-containing bath containing acetic acid, removing the formed granules of viscose from the bath after a thin skin has been formed thereon,
  • the method. of making granular particles comprising regenerated cellulose comprising the steps of allowing droplets of viscose to fall through the. air from asufficient height into a substantially non-regenerating salt-containing bath containing acetic acid to cause the droplets to assume a spherical shape before entering the bath, removing the formed granules of viscose from the bathafter a thinskin has been formed thereon, introducing the superficially coagulated granules into a heated non-acid aqueous saltcontaining bath incapable of softening the granules and having a temperature of at least 60 C.
  • makin granular particles comprising regenerated cellulose comprising the steps of allowing-droplets of viscose to fall into a. non-regenerating bath consisting of sodium sulfate; acetic acid, and water, removing the formed granules of viscose from the bath after av thin skinhaszbeien formed thereon, and introducing, the-superficially coagulated granules into a heated aqueous sodium sulfate solution having atemperature of at least 60 C.
  • the method of making regenerated cellulose comprising the steps of allowing viscosertoifall inthe form of individual drops'into a non-regencrating bath consisting of 10. to 20% sodiumsulfate, 3 to 6% acetic acid; andwater; removing the formed; globules from the bath after. a. thin skin has'been formed thereon, introducing the superficially coagulatedglobules into, a heated bath consisting of sodium sulfate and-water havingatemperature of'at least 60 C;

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Description

Feb. 13, 1951 KULP 2,541,165
METHOD FOR PRODUCING GLOBULAR ARTICLES Original Filed Feb. 15, 1947 INVENTOR. MAUR/CE P. KULP Patented Feb. 13, 1951 METHOD FOR PRODUCING GLOBULAR ARTICLES Maurice P. Kulp, Linwood, Pa., assignor to American Viscose Corporation, Wilmington, Dcl., a
corporation of Delaware Original application February 15, 1947, Serial No. 728,788. Divided and this application February 4, 1948, Serial No. 6,143
7 Claims. (CI. 18-48) This invention relates to the production of globular particles of regenerated cellulose, particularly from viscose. This application is a division of copending application Serial No. 728,788, filed February 15, 1947.
Methods that have heretofore been employed for making globular particles from viscose resulted generally in products which not only were far from sphericity but were marred by numerous checks and fissures resulting from the in ability to prevent the development of gases within the globule during regeneration and the in ability to prevent irregular shrinkage during regeneration, subsequent wet processing, and drying of the globules.
In accordance with the present invention these difiiculties are substantially completely avoided. This is accomplished by allowing droplets of viscose to form in a gaseous atmosphere and fall into a substantially non-regenerating bath from a height which is suificient to allow the droplet to assume a substantially spherical shape prior to entering the bath. The height required depends upon the size of droplet which can be varied by varying the size of orifice, the temperature of the viscose, or the pressure exerted on the viscose passing through the orifice. A droplet of a size which forms a particle of inch diameter requires a drop of at least 6 feet,
.while smaller droplets will require less drop and larger ones a greater drop to allow the surface tension sufficient time to overcome the nonsphericity of a droplet of viscose having a viscosity of about 40 (ball fall). After a short period in the non-regenerating bath (between /2 and minutes), the superficially coagulated structure is introduced into a heated liquid of non-solvent, non-softening and nonacid character in which coagulation and regeneration of the globules are completed. Suitable liquids for this purpose are hot aqueous salt solutions at a temperature below the boiling point of water.
After the globules are taken from the heated liquid, the by-products of regeneration, such as alkaline and sulfur compounds, are in a watersoluble state and are merely leached out by introducing the globules into water, preferably hot, for the desired period of time. Thereafter, the globules may be dried or, before drying, they may be soaked in a, plasticizer, such as glycerine, when a softened product is desired. Shrinkage to any substantial extent can only occur during the drying step of this procedure since the contact of the globules with acid is restricted to a minimum and the globules are maintained in water-swelled condition thereafter until the drying stage. It has been found that the shrinkage that occurs during the drying of the globules formed in accordance with the procedure of this invention is remarkably uniform in character and substantially iso-tropic so that they undergo little change in their original shape other than a diminution in during the drying.
The original shape of the globules formed de pends upon the height from which the viscose droplets are allowed to fall into the acid bath. if dropping heights are used which are considerably greater (more than about 20% greater) than the minimum needed to obtain sphericity, the size of the droplet falling from the dropping orifice or jet does not determine the ultimate size of the product as in such cases, they tend to disrupt into numerou smaller particles which may have various sizes, and, in the extreme of conditicns, a powdered product results.
The sole figure the drawing illustrates one arrangement for executing the invention.
As shown in the drawing, the viscose solution in a vessel 2 which may be provided with a plunger 3 for exerting pressure thereon passes through a dropping tube terminating in an orifice i. A receptacle 5 for the coagulating bath is arranged beneath the hopper to receive the droplets and preferably has a sloped bottom 6 to facilitate removal of the particles roughly in their order of production.
The bath in the receptacle 5 may advantageously be an aqueous solution containing 3 to 6% acetic acid and 15 to 20% sodium sulfate at 40 to 0., and the particles are allowed sufficient contact therein to form a thin coagulated skin thereon. Then they are removed and placed in a 20% sodium sulfate solution in water at to C. or up to the boiling point of water. This bath is agitated and the treatment is carried on for about an hour. Finally, the pellets or granules are removed from the salt bath and introduced into a leaching vessel in which they are subjected for 8 to 12 hours or longer to a fiow of hot water at 60 to- 7G G. or higher. This completes the purification of the pellets while substantially preventing any irregular shrinkage. The particles may remain in this bath an indefinite period or they may be stored in cold or hot water for an indefinite period before ultimate drying. However, if convenient, drying may be performed directly after the leaching period of 8 to 12 hours mentioned. Preferably, the humidity is controlled to prevent irregular shrinkage.
The final products which may be of any size up to the order of inch in diameter approach true sphericity and are substantially free of checks, fissures, bubbles, creases and wrinkles. The unplasticized products are hard: and have a high dielectric constant. Because of this characteristic and the fact that the products are highly resistant to hydrocarbon oils'they may be used in conjunction with such oils for cooling electrical equipment, such as transformers. The
a substantially non-regenerating aqueous saltcontaining dilute acid bath, removingthe formed granules of viscose from the bath' after a supericial coagulation thereof, and introducing the superficially coagulated granules into a heated non-acid aqueous salt-containing bath incapable of softening the granules and having a tempera ture of at least 60 C.
2. The method of making granular particles comprising regenerated cellulose comprising the steps of allowing droplets of viscose tov fall through air into a substantially non-regenerating salt-containing bath containing acetic acid, removing the formed granules of viscose from the bath after a thin skin has been formed thereon,
introducing the superficially coagulated granules into a heated non-acid aqueous salt-containing bath incapable of softening the granules and having. a temperature of at least 60 C, and then leaching the granules;
3. The method. of making granular particles comprising regenerated cellulose comprising the steps of allowing droplets of viscose to fall through the. air from asufficient height into a substantially non-regenerating salt-containing bath containing acetic acid to cause the droplets to assume a spherical shape before entering the bath, removing the formed granules of viscose from the bathafter a thinskin has been formed thereon, introducing the superficially coagulated granules into a heated non-acid aqueous saltcontaining bath incapable of softening the granules and having a temperature of at least 60 C.
4: The method of makin granular particles comprising regenerated cellulose comprising the steps of allowing-droplets of viscose to fall into a. non-regenerating bath consisting of sodium sulfate; acetic acid, and water, removing the formed granules of viscose from the bath after av thin skinhaszbeien formed thereon, and introducing, the-superficially coagulated granules into a heated aqueous sodium sulfate solution having atemperature of at least 60 C.
5. The method of making regenerated cellulose: globules: approaching sphericity in: shape comprising the steps of allowing viscosertoifall inthe form of individual drops'into a non-regencrating bath consisting of 10. to 20% sodiumsulfate, 3 to 6% acetic acid; andwater; removing the formed; globules from the bath after. a. thin skin has'been formed thereon, introducing the superficially coagulatedglobules into, a heated bath consisting of sodium sulfate and-water havingatemperature of'at least 60 C;
6; Themethod of claim 5- followed-by thestep of leaching. theparticles in hot water, and drying: them.
'7'. The. method of" claim Gin which the-first bath is at about 40 to 50C; andthe. subsequent paths are at temperatures of. 60 1301 99. 6.
MAURICE "P: KULP:
REFERENCES CITED I The following references are of record in the file of this patent:
UNITED STATES .PATENTS Number Name Date 2,249,745 Charch et a1 J'ul y 222-1941 2,413,123 Underwood Dec. 24, 1946 2,465,343 Battista Mar. 29 1949

Claims (1)

1. THE METHOD OF MAKING GRANULAR PARTICLES COMPRISING REGENERATED CELLULOSE COMPRISING THE STEPS OF ALLOWING DROPLETS OF VISCOSE TO FALL INTO A SUBSTANTIALLY NON-REGENERATING AQUEOUS SALTCONTAINING DILUTE ACID BATH, REMOVING THE FORMED GRANULES OF VISCOSE FROM THE BATH AFTER A SUPERFICIAL COAGULATION THEREOF, AND INTRODUCING THE SUPERFICIALLY COAGULATED GRANULES INTO A HEATED NON-ACID AQUEOUS SALT-CONTAINING BATH INCAPABLE OF SOFTENING THE GRANULES AND HAVING A TEMPERATURE OF AT LEAST 60* C.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2820984A (en) * 1951-07-27 1958-01-28 Skenandoa Rayon Corp Method and apparatus for producing regenerated cellulose pellets
US3171159A (en) * 1961-08-09 1965-03-02 Nopco Chem Co Pelletized water insoluble metallic soaps and methods and apparatus for producing them
US3233011A (en) * 1961-04-06 1966-02-01 Kurz Fredrik Wilhelm Anton Methods of making a porous concrete structure
US3247292A (en) * 1963-04-11 1966-04-19 Rhone Poulenc Sa Manufacture of polyvinyl alcohol granules
US3395055A (en) * 1959-03-26 1968-07-30 Exxon Research Engineering Co Method of making a hybrid liquid-solid propellant system with encapsulated oxidizingagent and metallic fuel
FR2573674A1 (en) * 1984-11-26 1986-05-30 Leuna Werke Veb Process and device for the production of spherical catalyst blanks.
FR2573675A1 (en) * 1984-11-26 1986-05-30 Leuna Werke Veb Process for the preparation of spherical aromatisation catalysts.
US5484559A (en) * 1994-04-14 1996-01-16 Zircoa Inc. Apparatus and process for manufacturing balls made of a ceramic material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2249745A (en) * 1937-12-21 1941-07-22 Du Pont Cellulosic structures and method of producing same
US2413123A (en) * 1944-06-29 1946-12-24 Du Pont Production of rayon
US2465343A (en) * 1947-02-15 1949-03-29 American Viscose Corp Production of globular regenerated cellulose particles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2249745A (en) * 1937-12-21 1941-07-22 Du Pont Cellulosic structures and method of producing same
US2413123A (en) * 1944-06-29 1946-12-24 Du Pont Production of rayon
US2465343A (en) * 1947-02-15 1949-03-29 American Viscose Corp Production of globular regenerated cellulose particles

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2820984A (en) * 1951-07-27 1958-01-28 Skenandoa Rayon Corp Method and apparatus for producing regenerated cellulose pellets
US3395055A (en) * 1959-03-26 1968-07-30 Exxon Research Engineering Co Method of making a hybrid liquid-solid propellant system with encapsulated oxidizingagent and metallic fuel
US3233011A (en) * 1961-04-06 1966-02-01 Kurz Fredrik Wilhelm Anton Methods of making a porous concrete structure
US3171159A (en) * 1961-08-09 1965-03-02 Nopco Chem Co Pelletized water insoluble metallic soaps and methods and apparatus for producing them
US3247292A (en) * 1963-04-11 1966-04-19 Rhone Poulenc Sa Manufacture of polyvinyl alcohol granules
FR2573674A1 (en) * 1984-11-26 1986-05-30 Leuna Werke Veb Process and device for the production of spherical catalyst blanks.
FR2573675A1 (en) * 1984-11-26 1986-05-30 Leuna Werke Veb Process for the preparation of spherical aromatisation catalysts.
US5484559A (en) * 1994-04-14 1996-01-16 Zircoa Inc. Apparatus and process for manufacturing balls made of a ceramic material

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