US3528929A - Defoaming,deaerating,and drainage aid compositions - Google Patents

Defoaming,deaerating,and drainage aid compositions Download PDF

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Publication number
US3528929A
US3528929A US640853A US3528929DA US3528929A US 3528929 A US3528929 A US 3528929A US 640853 A US640853 A US 640853A US 3528929D A US3528929D A US 3528929DA US 3528929 A US3528929 A US 3528929A
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United States
Prior art keywords
silica
defoaming
compositions
oil
foam
Prior art date
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Expired - Lifetime
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US640853A
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English (en)
Inventor
Stanley J Buckman
John D Buckman
John D Pera
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Buckman Laboratories International Inc
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Buckman Labor Inc
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Assigned to BUCKMAN LABORATORIES INTERNATIONAL, INC. reassignment BUCKMAN LABORATORIES INTERNATIONAL, INC. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BULAB HOLDINGS, INC.
Assigned to BULAB HOLDINGS, INC. reassignment BULAB HOLDINGS, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: BUCKMAN LABORATORIES, INC.,
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D21H21/12—Defoamers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
    • 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
    • D21H17/60—Waxes
    • 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
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays

Definitions

  • This invention relates to chemical compositions comprising a finely divided silica made hydrophobic and capable of forming particularly stable suspensions in oil by reacting the silica with alkoxysilicon chlorides.
  • the present invention relates to the use of such compositions in preventing or controlling foam in aqueous systems and as chemical deaerators and drainage aids in pulp and paper mills.
  • foam in the headbox causes froth spots in the finished paper
  • foam in the tub sizing bath causes nonuniformity in the application of sizing
  • foam in the white Water tank causes overflowing, thus carrying away appreciable quantities of fiber to Waste.
  • the presence of foam in the papermaking process produces two results-one, an increase in operating costs and, two, an inferior product. Since, as pointed out above, the presence of foam and the troublesome results caused thereby are not limited to papermaking processes, but are common to many other industrial processes, particularly those involving aqueous systems, numerous investigations have been directed to the study of foam and more specifically to methods for its control.
  • the methods proposed for controlling foam may be divided into two groups, mechanical and chemical.
  • Chemical type defoamers which have been used include higher alcohols, polyalkylene glycols, fatty acids, fatty acid esters, amines, amides, organic phosphates, metallic soaps, and silicones.
  • a high air content in the headbox stock can complicate operation and control of the paper machine.
  • tiny gas bubbles are present in the fiber lumen or when they 3,528,929 Patented Sept. 15,, 1970 become attached to the surface of the fibers, the effective density of the fibers is reduced; and there is a tendency for the stock to float.
  • Such flotation leads to increased flocculation and the formation of stock lumps.
  • These lumps pick up air-floated dirt, pitch, filler, pigments, etc., and frequently accumulate at various places throughout the pulp and paper machine systems, including such critical areas as headboxes. Subsequent release of the lumps will produce spots in the paper and will often cause the sheet to break.
  • the combined effects of the air in the stock can result in a lower wet-web strength and an increase in porosity (air permeability), a reduction in smoothness, and a decrease in strength properties of the finished sheet.
  • Another etfect of entrained air is a lower density wet web and a lower density final sheet.
  • Air in the stock has been shown to be the cause of many other operating problems. Accumulation of pockets of air in the stock-handling system causes irregular surges that upset the normal operation of pumps, flow distributors, and headboxes. Excess quantities of air promote slime and nonmicrobiological deposit formation in the stock and white water systems, and in the stock has been found to be a source of pinholes in the finished paper.
  • compositions of our invention can effect the deaeration of papermaking stocks by chemical means and thus provide the papermaker the substantial benefits of deaerated stocks without the necessity for the large capital outlay required for mechanical deaeration facilities.
  • the same compositions have proved to be effective drainage aids for both Fourdrinier and cylinder paper machines, by producing substantial increases in drainage rates and have enabled greater production on many machines and grades where drainage was a limiting factor.
  • Yet another object of our invention is to provide a composition that is effective in deaerating papermaking stocks.
  • Yet another object of this invention is to provide an effective drainage aid for use in papermaking processes.
  • composition prepared as follows: A finely divided silica is dispersed into a mixture comprising an oil and alkoxysilicon chlorides. The resulting mixture is then heated under reduced pressure to remove substantially all the hydrogen chloride. Finally, an alkylene oxide may be added to react with any residual hydrogen chloride remaining in the system.
  • compositions of the invention may be utilized as such by merely adding a small amount, i.e., from about 1 to about 500 parts per million parts of the aqueous systems in which control of foam, deaeration, or an improvement drainage is desired.
  • suitable oils are those meeting the following criteria: Are insoluble in Water, possess a low-vapor pressure, have a viscosity varying from 20-200 S.U.S. at 100 F., possess a specific gravity of less than one, and are nonreactive in respect to the silica and to the hydrophobing agent.
  • specific mineral oils which may be used include both parafiinic and naphthenic mineral oils, cutting oils, kerosene, and similar petroleum fractions including food-grade mineral oils and halogenated hydrocarbons.
  • a preferred mineral oil is the product known as mineral seal oil which is defined by R. E. Kirk and D. F. Othmer, Encyclopedia of Chemical Technology, The Interscience Encyclopedia, Inc., New York, N.Y., vol. 10, page 167 (1953), as a straightrun treated petroleum distillate from paraflinic or mixedbased crudes.
  • a synthetic oil for the mineral oil.
  • suitable synthetic oils include aliphatic diesters (such as diisooctyl azelate), silicate esters (such as hexa-Z-ethyl butoxy disiloxane), and polyalkylene glycols or their derivatives.
  • SILICA Suitable types of silica are those of colloidal dimensions including the well known forms of silica such as:
  • (l) Silica aerogel usually having an acid pH value, a colloidal silica which may be prepared by displacing the water from a silica hydrogel by a low-boiling watermiscible organic liquid; heating in an autoclave or the like above the critical temperature of the liquid; and then venting the autoclave.
  • fume silica a colloidal silica obtained by burning silicon tetrachloride and collecting the resulting silica smoke.
  • a precipitated silica prepared under conditions which do not permit the formation of a gel structure, but rather cause the flocculation of silica particles into coherent aggregates.
  • Colloidal precipitated silica sold under the trademark QUSO is an example of this type of silica.
  • silica Regardless of which form of silica is used, it must be an active silica containing at least some hydroxyl groups to react with the alkoxysilicon chlorides.
  • the diameter of the average ultimate particle should be less than about 100 millimicrons, preferably less than 50 millimicrons.
  • Suitable alkoxysilicon chlorides have the formula: Cl Si(OR) COMPOSITIONS
  • the amount of the various components making up our defoaming compositions in respect to suitable and preferred quantities in parts by weight are as follows:
  • Component Suitable Preferred Mineral oil 55-93 69-86 Alkoxys lllcon chloride 4-20 8-16 Silica 3-25 6-15 Alkylene oxide 0. 0 0. 3-1. 0
  • organo-silicon halides including alkyl(methyl), aryl(phenyl), alkaryl(tolyl), and aralkyl (phenyl methyl) silicon halides. These organo-silicon halides are capable of reacting with the hydroxyl groups of the silica only by eliminating hydrogen chloride. The amount of hydrogen chloride produced is large in comparison to the amounts liberated in preparing the compositions of our invention.
  • compositions of our invention obviate the disadvantages of compositions described in various patents by utilizing cheap starting materials, such as alcohols and silicon tetrachloride, eliminating the need for surface active agents, reducing the corrosive nature of the products containing hydrogen chloride, and by utilizing a wide variety of silica products.
  • EXAMPLE 1 Preparation of a mixture of bisand tris(decyloxy)silicon chlorides
  • a 2,000-gal. glass-lined reactor was charged with 2,800 lb. (16.48 pound moles) of silicon tetrachloride, which was then agitated and cooled to 50 F. by circulating icewater through the jacket of the reactor.
  • Decyl alcohol was then added to the reactor at the rate of 30 lb. per minute until 7,120 lb. (44.98 pound moles) had been added.
  • the temperature was kept at 50 F. or lower and the hydrogen chloride formed was vented to a scrubber.
  • Example 2 of the mixture of bisand tris(decyloxy)silicon chlorides prepared in Example 1.
  • the contents of the reactor were agitated and 1,700 lb. of silica was added slowly to the mixture. This silica had an ultimate particle size of about 13 millimicrons and a pH of 8.5.
  • the reactor was then vented to a scrubber and the contents heated to 200 F. and maintained at this temperature for 1 hr. A 20-25 in. Hg vacuum was applied to the reactor as the batch was cooled to F.
  • the batch was then treated with lb. of butylene oxide and homogenized.
  • the final product contained a total silicon content, calculated as SiO of 12.5 pct. and a defoaming eifectiveness of 89 pct.
  • EXAMPLE 3 A 250ml. three-necked round bottom flask equipped with a thermometer, reflux condenser, dropping funnel, and a magnetically driven stirring bar was charged with 17.0 g. (0.1 mole) of silicon tetrachloride and cooled to below 20 C. The temperature was maintained below 20 C. while 39.1 g. (0.3 mole) of isooctyl alcohol was added over a period of 2 hr. The reaction mixture was then slowly warmed to 100 C. and a 30-40 mm. Hg vacuum was applied for 1 hr. after which the reaction was cooled. The tris(isooctyloxy)silicon chloride obtained was then reacted with silica as described in Example 4.
  • reaction described above was repeated using 0.3 mole quantities of n-butanol, sec-butanol, decyl alcohol, tridecanol, a mixture of C to C straight chain alcohols, a mixture of C to C straight chain alcohols, and a mixture of C to C straight chain alcohols.
  • EXAMPLE 4 A 250-ml. three-necked flask equipped with agitator and thermometer was charged with 74.0 g. of mineral seal oil, 14.0 g. of the tris(isooctyloxy)silicon chloride prepared in Example 3 and 12.0 g. of a silica having an ultimate particle size of about 13 millimicrons and a pH of 8.5. The mixture was heated to 100 C. and the temperature was maintained at 100 C. for 1 hr. while a vacuum of about 30 mm. Hg was applied to remove hydrogen chloride. The reaction mixture was then cooled to 25 0., treated with 0.1 g. of butylene oxide and homogenized in a Waring Blender for 3 minutes.
  • a 0.1 molar tall oil soap solution (stock solution) was prepared by adding sodium hydroxide in an amount equal to 102 pct. of the stoichiometric quantity required for complete neutralization of tall oil fatty acids, followed by diluting the neutralized tall oil fatty acid solution to volume with demineralized water.
  • a working solution was prepared by diluting 25 ml. of the stock solution to 2 liters with demineralized water, allowing the solution to stand for 24 hr. and adjusting the pH to 8.7. Eighty-five milliliters of the Working solution was transferred to a 250-ml.
  • a method of preparing a defoaming composition which comprises dispersing 3 to 25 parts by weight of finely divided silica into a mixture consisting of 55 to 93 parts by weight of a mineral oil or a synthetic oil that is nonreactive in respect to the silica and the hydrophobic agent having a viscosity varying from to 200 S.U. S. at 100 F. and 4 to 20 parts by weight of an alkoxysilicon chloride having the formula:
  • m varies from 1 to 2
  • n varies from 2 to 3
  • R is a straight or branched chain alkyl group containing from 2 to 22 carbpn atoms
  • silica is a precipitated silica
  • the oil is a mineral seal oil
  • the alkoxysilicon chloride is a mixture of bisand tris-(decyloxy)silicon chlorides.
  • a defoaming composition prepared by the process of claim 1.
  • a defoaming composition prepared by the process of claim 1 in which the alkoxysilicon chloride is a mixture of bisand tris-(decyloxy)silicon chlorides.
  • a defoaming composition prepared by the process of claim 1 in which the silica is a precipitated silica.
  • a defoaming composition prepared by the process of claim 1 in which the silica is a fume silica prepared by oxidizing silicon tetrachloride.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)
US640853A 1967-05-24 1967-05-24 Defoaming,deaerating,and drainage aid compositions Expired - Lifetime US3528929A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US64085367A 1967-05-24 1967-05-24

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US3528929A true US3528929A (en) 1970-09-15

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US (1) US3528929A (en:Method)
AT (1) AT287656B (en:Method)
BE (1) BE714079A (en:Method)
BR (1) BR6794918D0 (en:Method)
CH (1) CH525698A (en:Method)
DE (1) DE1769362A1 (en:Method)
ES (1) ES348505A1 (en:Method)
FR (1) FR1566848A (en:Method)
GB (1) GB1166877A (en:Method)
NL (1) NL6807286A (en:Method)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957705A (en) * 1973-04-30 1976-05-18 Henkel & Cie G.M.B.H. Anti-foaming agent compositions
US4198267A (en) * 1978-01-03 1980-04-15 Dorset Industrial Chemicals Ltd. Improved pulp sheet formation
US6162330A (en) * 1997-11-14 2000-12-19 Dow Corning S.A. Method for restricting air entrapment in a paper making process
EP1181243A4 (en) * 1999-03-26 2010-12-22 Cognis Ip Man Gmbh ANTI-MOSS COMPOSITIONS

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3218676C2 (de) * 1982-05-18 1985-08-01 Th. Goldschmidt Ag, 4300 Essen Mittel zum Entlüften von Beschichtungssystemen
US5275822A (en) * 1989-10-19 1994-01-04 Valentine Enterprises, Inc. Defoaming composition
USRE35893E (en) * 1989-10-19 1998-09-08 Valentine Enterprises, Inc. Defoaming composition
US5073384A (en) * 1989-10-19 1991-12-17 Valentine Enterprises, Inc. Maltodextrin/defoaming composition combinate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2736668A (en) * 1952-05-09 1956-02-28 Du Pont Process of methoxylating the surface of a siliceous material, and the resulting product
US3076768A (en) * 1959-07-20 1963-02-05 Hercules Powder Co Ltd Defoamer
US3207698A (en) * 1963-02-13 1965-09-21 Nopco Chem Co Composition and method for defoaming aqueous systems

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2736668A (en) * 1952-05-09 1956-02-28 Du Pont Process of methoxylating the surface of a siliceous material, and the resulting product
US3076768A (en) * 1959-07-20 1963-02-05 Hercules Powder Co Ltd Defoamer
US3207698A (en) * 1963-02-13 1965-09-21 Nopco Chem Co Composition and method for defoaming aqueous systems

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957705A (en) * 1973-04-30 1976-05-18 Henkel & Cie G.M.B.H. Anti-foaming agent compositions
US4198267A (en) * 1978-01-03 1980-04-15 Dorset Industrial Chemicals Ltd. Improved pulp sheet formation
US6162330A (en) * 1997-11-14 2000-12-19 Dow Corning S.A. Method for restricting air entrapment in a paper making process
EP1181243A4 (en) * 1999-03-26 2010-12-22 Cognis Ip Man Gmbh ANTI-MOSS COMPOSITIONS

Also Published As

Publication number Publication date
ES348505A1 (es) 1971-06-16
BE714079A (en:Method) 1968-09-16
FR1566848A (en:Method) 1969-05-09
DE1769362A1 (de) 1971-09-02
BR6794918D0 (pt) 1973-02-27
CH525698A (de) 1972-07-31
AT287656B (de) 1971-02-10
GB1166877A (en) 1969-10-15
NL6807286A (en:Method) 1968-11-25

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Owner name: BULAB HOLDINGS, INC., DISTRICT OF COLUMBIA

Free format text: CHANGE OF NAME;ASSIGNOR:BUCKMAN LABORATORIES, INC.,;REEL/FRAME:004800/0892

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Owner name: BULAB HOLDINGS, INC.

Free format text: CHANGE OF NAME;ASSIGNOR:BUCKMAN LABORATORIES, INC.,;REEL/FRAME:004800/0892

Effective date: 19870924

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BULAB HOLDINGS, INC.;REEL/FRAME:004772/0269

Effective date: 19871016