EP0355816A2 - Alumine colloidale comme agent de rétention en papeterie - Google Patents

Alumine colloidale comme agent de rétention en papeterie Download PDF

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Publication number
EP0355816A2
EP0355816A2 EP89115581A EP89115581A EP0355816A2 EP 0355816 A2 EP0355816 A2 EP 0355816A2 EP 89115581 A EP89115581 A EP 89115581A EP 89115581 A EP89115581 A EP 89115581A EP 0355816 A2 EP0355816 A2 EP 0355816A2
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EP
European Patent Office
Prior art keywords
furnish
added
colloidal alumina
process according
binder
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.)
Withdrawn
Application number
EP89115581A
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German (de)
English (en)
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EP0355816A3 (fr
Inventor
James H. Smith
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.)
ChampionX LLC
Original Assignee
Nalco Chemical Co
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 Nalco Chemical Co filed Critical Nalco Chemical Co
Publication of EP0355816A2 publication Critical patent/EP0355816A2/fr
Publication of EP0355816A3 publication Critical patent/EP0355816A3/fr
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers

Definitions

  • the invention dramatically improves the drainage and retention characteristics of a paper-making furnish by the addition of colloidal alumina.
  • a furnish containing pulp, filler and water is added to the head box of a paper-making machine.
  • the pulp and filler are typically admixed with a binder.
  • the present invention provides a novel binder of a colloidal alumina sol and an anionic polymer flocculant.
  • binders have been developed for use in paper-making to increase the drainage of liquids from pulp fibers while increasing the retention characteristics between the fibers.
  • the use of a binder allows the paper-maker to operate at higher speeds because the paper sheet formed is more easily dewatered.
  • retention of added mineral materials used in paper-making processes is also enhanced by the addition of appropriate binders to the furnish.
  • U.S. Patent No. 4,643,801 (K. Johnson), issued February 17, 1987.
  • the Johnson patent provides a binder comprising a cationic starch having a degree of substitution ranging between about 0.01 to about 0.20, a high molecular weight anionic polymer having a molecular weight of at least 500,000 and degree of anionic substitution of at least 0.01, and dispersed silica having a particle size ranging from between about 1-50 nanometers.
  • the dispersed silica has a negative surface charge.
  • an untreated furnish will have an overall negative charge due to the anionic nature of pulp fibers, fines, and calcium carbonate filler particles in water.
  • Anionic polymers are not very effective as flocculants unless the anionic charge of the furnish is first neutralized by a cationic source.
  • the cationic source used in neutralizing the anionic furnish is a cationic starch.
  • the binder constituents used in accordance with the Johnson patent are added to the furnish in the following sequence: cationic starch, followed by anionic polymer, and finally dispersed silica.
  • an alumina source e.g., paper-maker's alum, sodium aluminate or polyhydroxyaluminum chloride, may be added to the furnish subsequent to the addition of the aforementioned binder.
  • the alumina source is added in an amount from 0.01-10 pounds of active Al2O3 per ton of paper (dried) manufactured.
  • the present inventor has discovered through laboratory experimentation that the drainage and retention characteristics of a paper-making furnish may be dramatically improved if instead of using the binder set forth in the Johnson patent, i.e., a cationic starch, anionic flocculant, and colloidal silica, a binder comprising a colloidal alumina sol and an anionic flocculant is used.
  • the colloidal alumina used in accordance with the present invention has a positive surface charge, as compared to the negative surface charge of the colloidal silica, which enhances the electroneutrality of the furnish, enhances adhesion by the positively charged alumina to negatively charged pulp fibers, and increases flocculation due to the interaction between the cationic alumina attached to pulp fibers and the anionic polymer flocculant. It has also been discovered by the present inventor that the use of very small particles with a positive surface charge, such as a colloidal alumina sol, can be very advantageous in the paper-making process as will be described below.
  • the present invention provides for the use of an alumina sol as the cationic source which can be used alone or in conjunction with the cationic starch of the Johnson patent.
  • the colloidal alumina sol of the present invention offers an increase in flocculation and drainage efficiency that cannot be obtained by cationic starches alone, presumably because of the geometry with which the charge is carried, i.e., the charge is contained on the alumina particle rather than in the polymeric form as provided by cationic starches.
  • the use of a colloidal alumina sol does not require the use of dispersed silica in the binder, thus decreasing the overall cost of the binder used in the paper-making process.
  • Japanese Patent No. 87/125096 discloses a binder which includes:
  • Japanese Patent No. 87/125096 has a number of disadvantages. Initially, the sequence of binder addition in Japanese Patent No. 87/125096 provides for the addition of anionic flocculant followed by a colloidal alumina solution. Since the pulp fibers have an anionic charge, the addition of anionic flocculant is very ineffective in flocculating the pulp due to the lack of electroneutrality in the furnish. The addition of a colloidal alumina solution after anionic flocculant results in poor adhesion between the colloidal alumina particles and the pulp fibers.
  • Japanese Patent No. 87/125096 makes use of colloidal alumina having very large particle size, i.e., 5-200 micrometers.
  • Use of large colloidal alumina particles is disadvantageous due to their poor adhesion with pulp fibers, reduced surface area and lower particle charge.
  • the use of such large alumina particles requires a much greater total mass to obtain the needed charge for electroneutrality of the furnish which is economically undesirable.
  • the Alince et al. article discloses the deposition of positively charged quaternized polystyrene and colloidal Al2O3 on negatively charged kraft pulp fibers.
  • Russian Patent No. 538084 describes a method of processing cellulose pulp by adding: 0.5-35% filler; 0.5-1.5% rosin adhesive; 2.5-3% Al2O3 and 0.1-0.5% copolymer of (diethylamino) ethyl methacrylate-­methacrylamide as flocculant.
  • Japanese Patent No. 76/35712 discloses a pulp slurry mix with: 10% calcium carbonate filler; 0.5% colloidal alumina; 0.5% epichlorohydrin-modified polyamide; and then 0.3% Na perfluorheptanoate.
  • Russian Patent No. 471412 discloses a pulp used for the production of drawing and drafting paper which contains: 91.8-96% cellulose; 1-1.2% rosin; 0.5-4% modified starch; and 2.5-3% precipitating agent, such as alumina.
  • the present inventor has discovered that the sequential use of a colloidal alumina sol followed by an anionic polymer flocculant provides a much improved paper-making furnish, wherein the drainage and retention characteristics are enhanced.
  • the binder of the present invention provides better electroneutrality in the furnish, enhanced adhesion between positively charged colloidal alumina and negatively charged pulp fiber, and increased flocculation due to the interaction between the anionic flocculant and the alumina particles attached to the pulp fibers.
  • the use of much smaller alumina particles provides greater surface area for interaction with the anionic fibers and flocculants, rendering a furnish having improved drainage and retention characteristics. Since charge is proportional to surface area, smaller particles of equal total mass result in a higher particle charge than larger particles. Additional advantages of the present invention shall become apparent as described below.
  • a furnish containing pulp and fillers is added to the head box of a paper-making machine, wherein a binder is admixed with the furnish in the following order: a colloidal alumina sol having a colloidal alumina concentration in the range between 0.1-1%, the colloidal alumina having a particle size in the range between 1-50 nanometers and is added to the furnish in an amount between about 0.025-0.5% by weight; and an anionic polymer flocculant which is added to the furnish in an amount between about 0.01-0.1% by weight.
  • the anionic polymer flocculant is a polymer inverted in water at from about 0.2 0.6% polymer solids and thereafter diluted to about 0.02-0.04% polymer solids.
  • a preferred anionic polymer flocculant is a copolymer of sodium acrylate and acrylamide with a mole ratio of about 31:69.
  • the colloidal alumina sol has a pH in the range between about 4.8-5.2, and a preferred particle size in the range between about 2-4 nanometers.
  • the anionic polymer flocculant and colloidal alumina are added to the furnish in a ratio between about 1:10 to 3:1. That is, the colloidal alumina is added in an amount of about 0.5-10 pounds per ton of dry paper manufactured and the anionic polymer flocculant is added in an amount of about 0.15-1.5 pounds per ton of dry paper manufactured.
  • Additional cationic sources may be those selected from the group consisting of cationic starches, low molecular weight organic coagulants, alum, and combinations thereof.
  • the cationic starches are those having a degree of substitution ranging from between about 0.01-0.20, such as, potato starch, corn starch, or waxy maize.
  • the low molecular weight organic coagulant is typically a 50% active solution of ammonia crosslinked with dimethylamine-epichlorohydrin diluted to between about 0.1-1%.
  • Alum compositions suitable for use as additional cationic sources are paper-maker's alum, sodium aluminate, and polyhydroxyaluminum chloride.
  • the cationic starch is added to the furnish in an amount between about 0-1.25% by weight, and the low molecular weight organic coagulant is added in an amount between about 0-0.25% by weight.
  • the colloidal alumina sol is replaced with either an alum (aluminum sulfate), or a 30% aluminum acetate coated silica sol having a particle size in the range between about 1-50 nanometers and a positive surface charge.
  • the colloidal alumina sol is typically dissolved in water to a concentration in the range between about 0.1% to 1.0% prior to admixing with the furnish.
  • Aluminum acetate coated silica is added to the furnish in an amount between about 0.025 to 0.5% by weight.
  • the present invention may also include many additional features which shall be further described below.
  • Paper-making furnish typically includes pulp, filler, binder, and water.
  • the furnish is added to the head box of a paper-making machine wherein the pulp fibers are flocculated, dewatered and formed into paper.
  • the binder assists in the flocculation of the pulp fibers and also aids in the drainage of water from the furnish resulting in a dry paper product.
  • the novel binder set forth herein is admixed with the pulp, filler and water to form a furnish having improved drainage and retention characteristics.
  • the components of the binder are added to the furnish in the following order: a colloidal alumina sol having a colloidal alumina concentration in the range between 0.1-1%, the colloidal alumina having a particle size in the range between 1-50 nanometers and is added to the furnish in an amount between about 0.025-0.5% by weight; and an anionic polymer flocculant is subsequently added to the furnish in an amount between about 0.01-0.1% by weight.
  • anionic polymer flocculant and colloidal alumina be added to the furnish in a ratio of between about 1:10 to 3:1.
  • the colloidal alumina sol is approximately 10% colloidal alumina by weight diluted to 0.1-1% with water.
  • the colloidal alumina sol has a pH in the range between about 4.8-5.2.
  • the colloidal alumina used in this solution has a particle size in the range between about 1-50 nanometers, preferably 2-4 nanometers.
  • the colloidal alumina sol is added to the furnish such that the colloidal alumina represents between about 0.025-0.5% by weight of total solids in the furnish. That is, colloidal alumina is present in an amount of about 0.5-10 pounds per ton of dry paper manufactured.
  • the anionic polymer flocculant is typically a polymer inverted in water at from about 0.2-0.6% polymer solids and thereafter diluted to about 0.02-0.04% polymer solids.
  • One preferred anionic polymer flocculant is a copolymer of sodium acrylate and acrylamide.
  • the anionic polymer represents between 0.01-0.1% by weight of the total solids in the furnish, and also between about 0.15-­1.5 pounds per ton of dry paper produced.
  • the anionic polymer flocculants used in accordance with the present invention are preferably water-soluble vinylic polymers containing monomers from the group acrylamide, acrylic acid, AMPS and/or admixtures thereof, and may also be either hydrolyzed acrylamide polymers or copolymers of acrylamide or its homologues, such as methacrylamide, with acrylic acid or its homologues, such as methacrylic acid, or perhaps even with monomers, such as maleic acid, itaconic acid, or even monomers such as vinyl sulfonic acid, AMPS, and other sulfonate containing monomers.
  • the anionic polymer flocculant may be homopolymers, copolymers, terpolymers or multiple monomeric repeating units.
  • the anionic polymers may also be sulfonate or phosphonate containing polymers which have been synthesized by modifying acrylamide polymers by such a way as to obtain sulfonate or phosphonate substi­tution, or admixtures thereof.
  • the anionic polymers may be used in solid, powder form, after dilution in water, or may be used as water-in-oil emulsions, wherein the polymer is dissolved in the dispersed water phase of these emulsions.
  • the anionic polymers have a molecular weight of at least 500,000.
  • the preferred molecular weight is at least 1,000,000, and most preferably having a molecular weight ranging from between 5-25 million.
  • the anionic polymers have a degree of substitution of at least 0.01, preferably a degree of substitution of at least 0.05, and most preferably a degree of substitution in the range between about 0.01-0.95.
  • degree of substitution it is meant that the polymers contain randomly repeating monomer units containing chemical functionality which when dissolved in water become anionically charged, such as carboxylate groups, sulfonate groups, phosphonate groups, and the like.
  • a copolymer of acrylamide and acrylic acid wherein the monomer mole ratio is 90:10 would have a degree of substitution of 0.10.
  • a copolymer with a monomer mole ratio of 50:50 would have a degree of anionic substitution of 0.5.
  • the anionic polymer flocculant to colloidal alumina ratio of between about 1:10-3:1 is based on an anionic polymer flocculant dose of 0.5-1.5 pounds of polymer solids per ton of dry paper manufactured and a colloidal alumina dose of 0.5-5 pounds per ton of dry paper manufactured.
  • aluminum sulfate (alum) may be substituted for the colloidal alumina sol as the cationic source used in the furnish.
  • a 30% aluminum acetate coated silica sol having a particle size in the range between about 1-50 nanometers may be used as the cationic source in the furnish.
  • the aluminum acetate coated silica is added to the furnish in an amount between about 0.025 to 0.5% by weight.
  • a suitable aluminum acetate coated silica is a 30%, 20 nanometer aluminum acetate coated silica sol with a positive surface charge.
  • This aluminum acetate coated silica sol is typically made from a silica sol having a particle size of approximately 20 nanometers.
  • the cationic source may be one selected from the group consisting of cationic starches, low molecular weight organic coagulants, alum and combinations thereof.
  • Cationic starches such as those set forth in U.S. Patent No. 4,643,801, which is incorporated herein by reference, are satisfactory for use as additional cationic sources.
  • a cationic starch having a degree of substitution ranging from about 0.01-­0.20 is particularly desirable.
  • Such cationic starches are potato starches, corn starches, and waxy maize.
  • the cationic starch may be a potato starch derivatized to a quaternary amine structure with a degree of substitution of about 0.01.
  • a cationic coaqulant may be used instead of using a cationic starch.
  • a low molecular weight organic coagulant having a 50% active solution of ammonia crosslinked with dimethylamine-epichlorohydrin.
  • Cationic starch is added to the furnish is an amount between about 0-1.25% by weight of total solids in the furnish.
  • the low molecular weight organic coagulant is added to the furnish in an amount between about 0-0.25% by weight of total solids in the furnish. That is, cationic starch is present in an amount between about 0-25 pounds per ton of dry paper manufactured, and organic coagulant is present in an amount between about 0-5 pounds per ton of dry paper manufactured.
  • an additional cationic source such as alum may be added to the furnish prior to the step of colloidal alumina addition.
  • the alum may be one selected from the group consisting of paper-maker's alum, sodium aluminate, and polyhydroxyaluminum chloride.
  • the addition sequence when using additional cationic sources is preferentially treating the furnish first with the additional cationic source, followed by the colloidal alumina sol, and lastly adding the anionic polymer flocculant.
  • the test was performed on a 50/50 Hardwood Kraft/Softwood Kraft furnish, i.e., pulp fiber, filler, binder and water, with 20-30% calcium carbonate filler.
  • the pH of the furnish was adjusted to between 8.0-8.1.
  • the standard alkaline furnish containing 20-30% calcium carbonate filler was treated by addition of the following:
  • the amount of cationic starch was constant at 15 pounds per ton of dry paper produced, whereas the amount of anionic polymer flocculant was increased from about 0-3 pounds per ton of dry paper produced.
  • Figure 1 six (6) samples were run adding various cationic or anionic binder additives to the standard alkaline furnish set forth above to determine the percent drainage improvement as the dose of anionic polymer flocculant was increased from 0 to 3 pounds per ton of dry paper.
  • the colloidal alumina can be used where pH or deposit problems preclude the use of alum.
  • a low molecular weight organic coagulant having a positive charge was added to the furnish. Thereafter, four (4) samples containing either no sol, silica sol, alum, or colloidal alumina, were added to the furnish. The anionic polymer flocculant was increased from 0-3 pounds per ton of dry paper produced. Using the low molecular weight organic coaqulant, alum, silica sol and colloidal alumina all showed similar improvement in Alchem drainage as depicted in Figure 4, but the colloidal alumina showed a slight adverse effect on retention (turbidity) when an organic coagulant was added as demonstrated in Figure 5.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
EP19890115581 1988-08-26 1989-08-23 Alumine colloidale comme agent de rétention en papeterie Withdrawn EP0355816A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US23681688A 1988-08-26 1988-08-26
US236816 1988-08-26

Publications (2)

Publication Number Publication Date
EP0355816A2 true EP0355816A2 (fr) 1990-02-28
EP0355816A3 EP0355816A3 (fr) 1992-09-09

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EP19890115581 Withdrawn EP0355816A3 (fr) 1988-08-26 1989-08-23 Alumine colloidale comme agent de rétention en papeterie

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EP (1) EP0355816A3 (fr)
JP (1) JPH02259196A (fr)
BR (1) BR8903325A (fr)
DE (1) DE355816T1 (fr)
ES (1) ES2014959A4 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2366576A (en) * 2000-09-07 2002-03-13 Ass Octel Flocculent system
WO2008052844A1 (fr) * 2006-11-02 2008-05-08 Evonik Degussa Gmbh Préparation destinée à produire des matériaux réfractaires

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0111359B1 (pt) * 2000-05-17 2012-03-20 ômétodo para fabricar papel e cartonagem e papel ou cartonagem feita de uma folha de papel contínua drenadaö.
US9017649B2 (en) * 2006-03-27 2015-04-28 Nalco Company Method of stabilizing silica-containing anionic microparticles in hard water

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57205597A (en) * 1981-06-09 1982-12-16 Shikoku Paper Mfg Production of internally sized paper
JPS5891897A (ja) * 1981-11-25 1983-05-31 神崎製紙株式会社 紙の抄造方法
WO1986000100A1 (fr) * 1984-06-07 1986-01-03 Eka Ab Procede de fabrication de papier
US4643801A (en) * 1986-02-24 1987-02-17 Nalco Chemical Company Papermaking aid
JPS62125096A (ja) * 1985-11-21 1987-06-06 星光化学工業株式会社 填料の歩留り向上方法
US4798653A (en) * 1988-03-08 1989-01-17 Procomp, Inc. Retention and drainage aid for papermaking
JPH01183598A (ja) * 1988-01-18 1989-07-21 Showa Denko Kk 紙・板紙の抄造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62206099A (ja) * 1986-03-05 1987-09-10 星光化学工業株式会社 高圧縮強度紙の製造法
JP2729792B2 (ja) * 1987-09-24 1998-03-18 日本ピー・エム・シー株式会社 紙の製造法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57205597A (en) * 1981-06-09 1982-12-16 Shikoku Paper Mfg Production of internally sized paper
JPS5891897A (ja) * 1981-11-25 1983-05-31 神崎製紙株式会社 紙の抄造方法
WO1986000100A1 (fr) * 1984-06-07 1986-01-03 Eka Ab Procede de fabrication de papier
JPS62125096A (ja) * 1985-11-21 1987-06-06 星光化学工業株式会社 填料の歩留り向上方法
US4643801A (en) * 1986-02-24 1987-02-17 Nalco Chemical Company Papermaking aid
JPH01183598A (ja) * 1988-01-18 1989-07-21 Showa Denko Kk 紙・板紙の抄造方法
US4798653A (en) * 1988-03-08 1989-01-17 Procomp, Inc. Retention and drainage aid for papermaking

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL, no. 87-195623, Derwent Publications Ltd, London, GB; & JP-A-62 125 096 (SEIKO CHEM IND. K.K. et al.), The whole article. *
TAPPI, vol 61, no. 11, November 1978, pages 111-114, Atlanta, US; B. ALINCE et al.: "Colloidal aspects of the retention of positively charged additives", The whole article. *
WORLD PATENTS INDEX LATEST, Week 8305, Derwent Publ. Ltd., London, GB, AN-83-10668k; & JP-A-57 205 597 (SHIKOKU SEISHI K.K.) 16-12-1982, Abstract. *
WORLD PATENTS INDEX LATEST, Week 8327, Derwent Publ. Ltd, LONDON, GB, AN-83-703588; & JP-A-58 091 897 (KANZANI PAPER MFG K.K. et al.) 31-05-1983, Abstract. *
WORLD PATENTS INDEX LATEST, Week 8935, Derwent Publ. Ltd, London, GB, AN-89-252471; & JP-A-01 183 598 (SHOWA DENKO K.K.) 21-07-1989, Abstract. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2366576A (en) * 2000-09-07 2002-03-13 Ass Octel Flocculent system
WO2008052844A1 (fr) * 2006-11-02 2008-05-08 Evonik Degussa Gmbh Préparation destinée à produire des matériaux réfractaires
US8303702B2 (en) 2006-11-02 2012-11-06 Evonik Degussa Gmbh Preparation for producing refractory materials

Also Published As

Publication number Publication date
JPH02259196A (ja) 1990-10-19
DE355816T1 (de) 1990-09-27
EP0355816A3 (fr) 1992-09-09
ES2014959A4 (es) 1990-08-01
BR8903325A (pt) 1990-03-13

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