WO1994013883A1 - 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
WO1994013883A1
WO1994013883A1 PCT/FI1993/000481 FI9300481W WO9413883A1 WO 1994013883 A1 WO1994013883 A1 WO 1994013883A1 FI 9300481 W FI9300481 W FI 9300481W WO 9413883 A1 WO9413883 A1 WO 9413883A1
Authority
WO
WIPO (PCT)
Prior art keywords
sizing agent
premixture
hydrophobic sizing
pressure
preparation
Prior art date
Application number
PCT/FI1993/000481
Other languages
French (fr)
Inventor
Claes Zetter
Markku Nurminen
Original Assignee
Raisio Chemicals Oy
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 Raisio Chemicals Oy filed Critical Raisio Chemicals Oy
Priority to AU54668/94A priority Critical patent/AU5466894A/en
Priority to DE69308035T priority patent/DE69308035T2/en
Priority to EP94900166A priority patent/EP0672213B1/en
Publication of WO1994013883A1 publication Critical patent/WO1994013883A1/en

Links

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 measu ⁇ red 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 absorp ⁇ tion 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 prod ⁇ uct 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 pa ⁇ per or board machine at the starting step of the manufac ⁇ turing process. In certain cases, these sizing agents may be added also at a later step of the manufacturing pro ⁇ cess, 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 stabil ⁇ izers, surfactants and other additional chemicals.
  • a stabilizer e.g. cationic starch, cationic polyethylene i ines, cationic polyacryl amides, gelatin or casein are used.
  • surfactants e.g. sodium lignosulphonate or alkyl sul- phonates 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 circu ⁇ lated 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 de ⁇ vice in the preparation of a hydrophobic sizing agent dispersion.
  • a steam jet digester pro ⁇ cess 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 digest ⁇ er portion 2 itself, wherein the mixture contacts a high- pressure steam flow 3 and the temperature and the pres ⁇ sure 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.
  • stearine/palmitine alkyl ketene dimer (AKD) premixture was prepared having the following composition:
  • This premixture was divided into two portions, one of which was run 3 times through the laboratory high-pres ⁇ sure 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.
  • Average particle size 0.56 ⁇ m 0.60 ⁇
  • Average particle size 0.86 ⁇ m 0.95 ⁇ m
  • ASA alkenyl succinic-acid anhydride*
  • 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 por ⁇ tion was run through a steam-jet digester, the tempera ⁇ ture being 110°C and the pressure 1.5 bar.
  • a high-pressure homogenizer pressure 200 bar, temperature 50°C
  • the other por ⁇ tion was run through a steam-jet digester, the tempera ⁇ ture being 110°C and the pressure 1.5 bar.
  • the dispersions produced were diluted into a solids con ⁇ tent of 7.5%, and their viscosity and average particle size were measured.
  • Average particle size 0.50 ⁇ m 0.65 ⁇ m
  • a value ⁇ 1 ⁇ m is regarded as a generally accepted par ⁇ ticle size in products of this type.

Landscapes

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

Process for the preparation of a hydrophobic sizing agent dispersion
Hydrophobic sizing refers to the making of paper or board more or less water repellant. This property may be measu¬ red 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 absorp¬ tion 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 prod¬ uct 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 pa¬ per or board machine at the starting step of the manufac¬ turing process. In certain cases, these sizing agents may be added also at a later step of the manufacturing pro¬ cess, 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 stabil¬ izers, surfactants and other additional chemicals. As a stabilizer e.g. cationic starch, cationic polyethylene i ines, cationic polyacryl amides, gelatin or casein are used.
As surfactants e.g. sodium lignosulphonate or alkyl sul- phonates 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 circu¬ lated 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 de¬ vice in the preparation of a hydrophobic sizing agent dispersion.
The invention will be explained more detailed with refer- ence to the enclosed drawing. A steam jet digester pro¬ cess 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 digest¬ er portion 2 itself, wherein the mixture contacts a high- pressure steam flow 3 and the temperature and the pres¬ sure 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 fol¬ lows:
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 poss¬ ible 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 poss¬ ible 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-pres¬ sure 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 homocrenizer/Steam-iet digester
Viscosity 10 cP 8 cP
Average particle size 0.56 μm 0.60 μ
The results show that the dispersions are by their char¬ acteristics 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 compo¬ sition:
Figure imgf000007_0001
* As an alkenyl succinic-acid anhydride anhydrides de¬ rived from straight-chain C13 - C20 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 por¬ tion was run through a steam-jet digester, the tempera¬ ture being 110°C and the pressure 1.5 bar.
The dispersions produced were diluted into a solids con¬ tent of 7.5%, and their viscosity and average particle size were measured. High-pressure homogenizer/Steam-iet digester
Viscosity 600 cP 520 cP
Average particle size 0.50 μm 0.65 μm
The results show that the dispersions are nearly ident¬ ical.
A value < 1 μm is regarded as a generally accepted par¬ ticle size in products of this type.

Claims

Claims
1. A method for preparing a hydrophobic sizing agent es¬ pecially for a paper making process, wherein basic sizing agent components based on an alkenyl-succinic-acid anhyd¬ ride (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 disper¬ sion, characterized in that the pressurized treatment is performed at a pressure of 2 - 15 bar and at a tempera¬ ture of 100 - 200°C during a period of less than 2 min¬ utes.
2. A method according to Claim 1, characterized in that the pressurized treatment is performed by subjecting the sizing agent premixture to a high-pressure water steam directed at a high speed.
PCT/FI1993/000481 1992-12-04 1993-11-15 Process for the preparation of a hydrophobic sizing agent dispersion WO1994013883A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU54668/94A AU5466894A (en) 1992-12-04 1993-11-15 Process for the preparation of a hydrophobic sizing agent dispersion
DE69308035T DE69308035T2 (en) 1992-12-04 1993-11-15 METHOD FOR PRODUCING A HYDROPHOBIC SIZE
EP94900166A EP0672213B1 (en) 1992-12-04 1993-11-15 Process for the preparation of a hydrophobic sizing agent dispersion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI925535 1992-12-04
FI925535A FI94535C (en) 1992-12-04 1992-12-04 Process for preparing a hydrophobic dispersion

Publications (1)

Publication Number Publication Date
WO1994013883A1 true WO1994013883A1 (en) 1994-06-23

Family

ID=8536338

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1993/000481 WO1994013883A1 (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)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5766417A (en) * 1996-03-06 1998-06-16 Hercules Incorporated Process for using alkaline sized paper in high speed converting or reprographics operations
EP0984101A1 (en) * 1998-09-04 2000-03-08 Kemira Chemicals Oy A sizing composition usable for the neutral sizing of paper or board, and a process for the manufacture of paper or board
US7687477B2 (en) 2002-09-27 2010-03-30 Valtion Teknillinen Tutkimuskeskus Polymer solution and dispersion and a process for the preparation thereof

Families Citing this family (4)

* 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
WO2004037930A2 (en) * 2002-10-24 2004-05-06 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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0418015A1 (en) * 1989-09-11 1991-03-20 Eka Nobel Landskrona AB Active sizing compositions
EP0437764A1 (en) * 1990-01-18 1991-07-24 BASF Aktiengesellschaft Stable aqueous emulsions of alkyl-keten dimer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0418015A1 (en) * 1989-09-11 1991-03-20 Eka Nobel Landskrona AB Active sizing compositions
EP0437764A1 (en) * 1990-01-18 1991-07-24 BASF Aktiengesellschaft Stable aqueous emulsions of alkyl-keten dimer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5766417A (en) * 1996-03-06 1998-06-16 Hercules Incorporated Process for using alkaline sized paper in high speed converting or reprographics operations
EP0984101A1 (en) * 1998-09-04 2000-03-08 Kemira Chemicals Oy A sizing composition usable for the neutral sizing of paper or board, and a process for the manufacture of paper or board
US7687477B2 (en) 2002-09-27 2010-03-30 Valtion Teknillinen Tutkimuskeskus Polymer solution and dispersion and a process for the preparation thereof

Also Published As

Publication number Publication date
FI925535A (en) 1994-06-05
DE69308035D1 (en) 1997-03-20
DE69308035T2 (en) 1997-08-28
CN1089276A (en) 1994-07-13
FI94535C (en) 1997-04-08
EP0672213A1 (en) 1995-09-20
TW281637B (en) 1996-07-21
AU5466894A (en) 1994-07-04
EP0672213B1 (en) 1997-02-05
FI94535B (en) 1995-06-15
FI925535A0 (en) 1992-12-04
ZA938796B (en) 1994-06-30
ATE148752T1 (en) 1997-02-15
CN1050165C (en) 2000-03-08

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