EP0672213B1 - Process for the preparation of a hydrophobic sizing agent dispersion - Google Patents

Process for the preparation of a hydrophobic sizing agent dispersion Download PDF

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Publication number
EP0672213B1
EP0672213B1 EP94900166A EP94900166A EP0672213B1 EP 0672213 B1 EP0672213 B1 EP 0672213B1 EP 94900166 A EP94900166 A EP 94900166A EP 94900166 A EP94900166 A EP 94900166A EP 0672213 B1 EP0672213 B1 EP 0672213B1
Authority
EP
European Patent Office
Prior art keywords
sizing agent
premixture
pressure
hydrophobic sizing
preparation
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.)
Expired - Lifetime
Application number
EP94900166A
Other languages
German (de)
French (fr)
Other versions
EP0672213A1 (en
Inventor
Claes Zetter
Markku Nurminen
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.)
BASF Schweiz AG
Ciba Specialty Chemicals Oy
Original Assignee
Raisio Chemicals Oy
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Filing date
Publication date
Application filed by Raisio Chemicals Oy filed Critical Raisio Chemicals Oy
Publication of EP0672213A1 publication Critical patent/EP0672213A1/en
Application granted granted Critical
Publication of EP0672213B1 publication Critical patent/EP0672213B1/en
Anticipated expiration legal-status Critical
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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers
    • 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
    • D21H21/14—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 characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • Hydrophobic sizing refers to the making of paper or board more or less water repellant. This property may be measured e.g. by the so-called Cobb test, in which the penetration of water into paper or board is measured as a function of time. The result is indicated as an absorption g/m 2 . In a properly hydrophobically sized product, the value is generally ⁇ 25 g/m 2 , whereas in a product, which has not been treated with sizing agents increasing the hydrophobicity, the value may be > 100 g/m 2 .
  • Conventional compounds used as a hydrophobic sizing agent include wood-based resin acids and their derivatives.
  • neutral sizing agents which generally are compounds based on alkyl-ketene-dimer (AKD) or alkenyl-succinic-acid-anhydride (ASA).
  • Hydrophobic sizing agents are generally delivered to the paper and board mills as a water dispersion, in which the share of the active agent (AKD, ASA, resin) of the product is within the range of 5-50%.
  • the sizing agent dispersion is primarily prepared at a paper or board mill.
  • Hydrophobic sizing agents are added to a pulp at the paper or board machine at the starting step of the manufacturing process. In certain cases, these sizing agents may be added also at a later step of the manufacturing process, e.g. at the size press.
  • the quantities of the hydrophobic sizing agents to be used generally amount to 0.05-2.0% of the dry weight of the paper or board.
  • a hydrophobic sizing agent dispersion contains stabilizers, surfactants and other additional chemicals.
  • a stabilizer e.g. cationic starch, cationic polyethylene imines, cationic polyacryl amides, gelatin or casein are used.
  • surfactants e.g. sodium lignosulphonate or alkyl sulphonates are used.
  • Typical additional chemicals include biocides, alum and pH adjusting chemicals.
  • a conventional way of preparing a hydrophobic sizing agent dispersion from these components is to prepare, by mixing and heating in a reactor, a homogenous premixture containing in a suitable ratio water, an active agent, a stabilizer, surfactants and other potential additional chemicals.
  • the homogenous premixture After obtaining the homogenous premixture, it is circulated via a high-pressure homogenizer, a colloid mill or a high-revolution centrifugal pump generally several times, until a sufficiently small particle size has been obtained (generally 0.1 - 10 ⁇ m).
  • the pressure varies within the range of 50 - 500 bar and the temperature within 50 - 100°C.
  • the dispersion obtained is thereafter run via a heat exchanger into a product container. In the heat exchanger, the temperature of the dispersion is decreased to ⁇ 30°C.
  • a high-pressure digester a steam jet digester, primarily designed for cooking starch acts as an extremely good dispersing device in the preparation of a hydrophobic sizing agent dispersion.
  • a steam jet digester process acts as follows:
  • a premixture is prepared in a reactor 1 according to the same principle as in the afore-mentioned conventional process. After this, the mixture is pumped into a digester portion 2 itself, wherein the mixture contacts a high-pressure steam flow 3 and the temperature and the pressure increase (the pressure generally to 2 - 15 bar and the temperature to 100 - 200°C). The dispersion formed is thereafter run into a tubular reactor 4, after which the pressure and the temperature are decreased in an expander device 5 and the excess of steam may be separated by means of a steam condenser 6. The homogenous product formed is then run via a heat exchanger into a product container.
  • This premixture was divided into two portions, one of which was run 3 times through the laboratory high-pressure homogenizer (Rannie). The pressure was 200 bar, the temperature 70°C. The other portion was run once through a laboratory-scale steam-jet digester, the temperature being 120°C and the pressure 3 bar. Both emulsions were diluted into a solids content of 12,5% and cooled into room temperature.
  • alkenyl succinic-acid anhydride* (ASA) premixture was prepared having the following composition: water 900 g ASA 50 g Orotan SN 0.5 g Raisamyl 150E 100 g *
  • alkenyl succinic-acid anhydride anhydrides derived from straight-chain C 13 - C 20 ⁇ -olefines were used.
  • This premixture was divided into two portions as well, one of which was run through a high-pressure homogenizer (pressure 200 bar, temperature 50°C) and the other portion was run through a steam-jet digester, the temperature being 110°C and the pressure 1.5 bar.
  • a high-pressure homogenizer pressure 200 bar, temperature 50°C
  • a steam-jet digester the temperature being 110°C and the pressure 1.5 bar.
  • the dispersions produced were diluted into a solids content of 7.5%, and their viscosity and average particle size were measured.
  • a value ⁇ 1 ⁇ m is regarded as a generally accepted particle size in products of this type.

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  • Paper (AREA)
  • Colloid Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Steroid Compounds (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention relates to a process for the preparation of hydrophobic sizing agent dispersions used in the paper and board industry. The invention is both a simple and an economical way of preparing a hydrophobic sizing agent dispersion either in the premises of a sizing agent supplier or a paper maker. The invention is based on a usage of a so-called high-pressure digester in the preparation of a hydrophobic sizing agent dispersion.

Description

  • Hydrophobic sizing refers to the making of paper or board more or less water repellant. This property may be measured e.g. by the so-called Cobb test, in which the penetration of water into paper or board is measured as a function of time. The result is indicated as an absorption g/m2. In a properly hydrophobically sized product, the value is generally < 25 g/m2, whereas in a product, which has not been treated with sizing agents increasing the hydrophobicity, the value may be > 100 g/m2.
  • Conventional compounds used as a hydrophobic sizing agent include wood-based resin acids and their derivatives.
  • Nowadays, the paper and board industry has increasingly transferred to using for hydrophobic sizing so-called neutral sizing agents, which generally are compounds based on alkyl-ketene-dimer (AKD) or alkenyl-succinic-acid-anhydride (ASA).
  • Hydrophobic sizing agents are generally delivered to the paper and board mills as a water dispersion, in which the share of the active agent (AKD, ASA, resin) of the product is within the range of 5-50%. when a sizing agent of the ASA type is concerned, the sizing agent dispersion is primarily prepared at a paper or board mill.
  • Hydrophobic sizing agents are added to a pulp at the paper or board machine at the starting step of the manufacturing process. In certain cases, these sizing agents may be added also at a later step of the manufacturing process, e.g. at the size press. The quantities of the hydrophobic sizing agents to be used generally amount to 0.05-2.0% of the dry weight of the paper or board.
  • In addition to the active agent (AKD, ASA or wood resin), a hydrophobic sizing agent dispersion contains stabilizers, surfactants and other additional chemicals. As a stabilizer e.g. cationic starch, cationic polyethylene imines, cationic polyacryl amides, gelatin or casein are used.
  • As surfactants e.g. sodium lignosulphonate or alkyl sulphonates are used.
  • Typical additional chemicals include biocides, alum and pH adjusting chemicals.
  • A conventional way of preparing a hydrophobic sizing agent dispersion from these components is to prepare, by mixing and heating in a reactor, a homogenous premixture containing in a suitable ratio water, an active agent, a stabilizer, surfactants and other potential additional chemicals.
  • After obtaining the homogenous premixture, it is circulated via a high-pressure homogenizer, a colloid mill or a high-revolution centrifugal pump generally several times, until a sufficiently small particle size has been obtained (generally 0.1 - 10 µm). The pressure varies within the range of 50 - 500 bar and the temperature within 50 - 100°C. The dispersion obtained is thereafter run via a heat exchanger into a product container. In the heat exchanger, the temperature of the dispersion is decreased to < 30°C.
  • Surprisingly, it has now been found that a high-pressure digester, a steam jet digester, primarily designed for cooking starch acts as an extremely good dispersing device in the preparation of a hydrophobic sizing agent dispersion.
  • The invention will be explained more detailed with reference to the enclosed drawing. A steam jet digester process acts as follows:
  • A premixture is prepared in a reactor 1 according to the same principle as in the afore-mentioned conventional process. After this, the mixture is pumped into a digester portion 2 itself, wherein the mixture contacts a high-pressure steam flow 3 and the temperature and the pressure increase (the pressure generally to 2 - 15 bar and the temperature to 100 - 200°C). The dispersion formed is thereafter run into a tubular reactor 4, after which the pressure and the temperature are decreased in an expander device 5 and the excess of steam may be separated by means of a steam condenser 6. The homogenous product formed is then run via a heat exchanger into a product container.
  • This process deviates from a conventional process as follows:
    • Conventional process:
      • Pressure 50 - 500 bar
      • Temperature 50 - 100°C
    • Steam jet digester process
      • Pressure 2 - 15 bar
      • Temperature 100 - 200°C
  • The preparation of a hydrophobic sizing agent dispersion in a process of a steam jet digester type makes it possible to use high solids contents during the processing, and since the delay in the digester and reactor tubes is extremely short, usually < 2 minutes, this makes it possible to use very small units having a large production capacity.
    • Example 1
  • In a laboratory scale a stearine/palmitine alkyl ketene dimer (AKD) premixture was prepared having the following composition:
    water 800 g
    AKD 200 g
    Orotan SN* 3.0 g
    Raisamyl 150E** 22 g
    * Naphthalene formaldehyde sulphonate condensate, sodium salt
    ** Cationic potato starch (DS = 0.05).
    The starch was cooked before adding.
  • This premixture was divided into two portions, one of which was run 3 times through the laboratory high-pressure homogenizer (Rannie). The pressure was 200 bar, the temperature 70°C. The other portion was run once through a laboratory-scale steam-jet digester, the temperature being 120°C and the pressure 3 bar. Both emulsions were diluted into a solids content of 12,5% and cooled into room temperature.
  • The following characteristics were measured from each of the dispersions: viscosity (Brookfield) and average particle size.
    • High-pressure homogenizer/Steam-jet digester
  • Viscosity 10 cP 8 cP
    Average particle size 0.56 µm 0.60 µm
  • The results show that the dispersions are by their characteristics nearly identical.
  • The dispersions were kept at room temperature for one month, and the same measurements were performed again, whereby the result was as follows:
    • High-pressure homogenizer/Steam-jet digester
  • Viscosity 15 cP 16 cP
    Average particle size 0.86 µm 0.95 µm
  • The results show that the storage stabilities of the two dispersions are of the same order.
    • Example 2
  • In a laboratory scale an alkenyl succinic-acid anhydride* (ASA) premixture was prepared having the following composition:
    water 900 g
    ASA 50 g
    Orotan SN 0.5 g
    Raisamyl 150E 100 g

    * As an alkenyl succinic-acid anhydride anhydrides derived from straight-chain C 13 - C 20 α-olefines were used.
  • This premixture was divided into two portions as well, one of which was run through a high-pressure homogenizer (pressure 200 bar, temperature 50°C) and the other portion was run through a steam-jet digester, the temperature being 110°C and the pressure 1.5 bar.
  • The dispersions produced were diluted into a solids content of 7.5%, and their viscosity and average particle size were measured.
    • High-pressure homogenizer/Steam-jet digester
  • Viscosity 600 cP 520 cP
    Average particle size 0.50 µm 0.65 µm
  • The results show that the dispersions are nearly identical.
  • A value < 1 µm is regarded as a generally accepted particle size in products of this type.

Claims (1)

  1. A method for preparing a hydrophobic sizing agent especially for a paper making process, wherein from basic sizing agent components based on an alkenyl succinic acid anhydride (ASA), an alkyl ketene dimer (AKD) or a resin and from additives preferably added thereto a sizing agent premixture is prepared by heating and mixing and this premixture is subjected to a pressurized thermal and mechanical treatment for obtaining a sizing agent dispersion, characterized in that the pressurized treatment is performed at a pressure of 2 - 15 bar and at a temperature of 100 - 200°C during a period of less than 2 minutes by subjecting the sizing agent premixture to a high-pressure water steam directed at a high speed.
EP94900166A 1992-12-04 1993-11-15 Process for the preparation of a hydrophobic sizing agent dispersion Expired - Lifetime EP0672213B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI925535A FI94535C (en) 1992-12-04 1992-12-04 Process for preparing a hydrophobic dispersion
FI925535 1992-12-04
PCT/FI1993/000481 WO1994013883A1 (en) 1992-12-04 1993-11-15 Process for the preparation of a hydrophobic sizing agent dispersion

Publications (2)

Publication Number Publication Date
EP0672213A1 EP0672213A1 (en) 1995-09-20
EP0672213B1 true EP0672213B1 (en) 1997-02-05

Family

ID=8536338

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94900166A Expired - Lifetime EP0672213B1 (en) 1992-12-04 1993-11-15 Process for the preparation of a hydrophobic sizing agent dispersion

Country Status (9)

Country Link
EP (1) EP0672213B1 (en)
CN (1) CN1050165C (en)
AT (1) ATE148752T1 (en)
AU (1) AU5466894A (en)
DE (1) DE69308035T2 (en)
FI (1) FI94535C (en)
TW (1) TW281637B (en)
WO (1) WO1994013883A1 (en)
ZA (1) ZA938796B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045216C (en) * 1994-09-10 1999-09-22 朱国华 Manufacture of neutral adhesive-applied fiber of alkyl ketene dipolymer
US5766417A (en) * 1996-03-06 1998-06-16 Hercules Incorporated Process for using alkaline sized paper in high speed converting or reprographics operations
FI109218B (en) * 1998-09-04 2002-06-14 Kemira Chemicals Oy A bonding compound used for neutral gluing of paper or paperboard and a method of making paper or paperboard
FI113874B (en) 2002-09-27 2004-06-30 Valtion Teknillinen Polymer solutions and dispersions and process for their preparation
AU2003286658B8 (en) * 2002-10-24 2009-07-16 Spectra-Kote Corporation Coating compositions comprising alkyl ketene dimers and alkyl succinic anhydrides for use in paper making
CN101693927B (en) * 2009-10-21 2013-03-20 陕西科技大学 Long-chain alkyl alcohol modified ASA waterproof fatliquoring agent and process for preparing same
CN111569816A (en) * 2020-06-30 2020-08-25 江苏京控装备有限公司 Solid-liquid homogeneous mixing pump matched multi-tube reactor

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8920456D0 (en) * 1989-09-11 1989-10-25 Albright & Wilson Active sizing compositions
DE4001237A1 (en) * 1990-01-18 1991-07-25 Basf Ag STABILIZED AQUEOUS ALKYLDICETE EMULSIONS

Also Published As

Publication number Publication date
DE69308035D1 (en) 1997-03-20
CN1050165C (en) 2000-03-08
WO1994013883A1 (en) 1994-06-23
FI925535A (en) 1994-06-05
ZA938796B (en) 1994-06-30
FI94535B (en) 1995-06-15
ATE148752T1 (en) 1997-02-15
DE69308035T2 (en) 1997-08-28
EP0672213A1 (en) 1995-09-20
FI94535C (en) 1997-04-08
FI925535A0 (en) 1992-12-04
TW281637B (en) 1996-07-21
AU5466894A (en) 1994-07-04
CN1089276A (en) 1994-07-13

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