CA2091272A1 - Methods for controlling the deposition of organic contaminants in pulp and papermaking processes - Google Patents
Methods for controlling the deposition of organic contaminants in pulp and papermaking processesInfo
- Publication number
- CA2091272A1 CA2091272A1 CA002091272A CA2091272A CA2091272A1 CA 2091272 A1 CA2091272 A1 CA 2091272A1 CA 002091272 A CA002091272 A CA 002091272A CA 2091272 A CA2091272 A CA 2091272A CA 2091272 A1 CA2091272 A1 CA 2091272A1
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- Prior art keywords
- polymer
- associative
- hydrophobically
- hydrophobically modified
- polyethylene oxide
- 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.)
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
- D21C9/086—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching with organic compounds or compositions comprising organic compounds
-
- 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
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
Abstract
ABSTRACT
Methods for inhibiting deposition of organic contaminants from pulp in pulp and papermaking systems which comprises treating the pulp and papermaking system with an effective amount of a hydrophobically modified associative polymer.
Methods for inhibiting deposition of organic contaminants from pulp in pulp and papermaking systems which comprises treating the pulp and papermaking system with an effective amount of a hydrophobically modified associative polymer.
Description
20~272 METHODS FOR CONTROLLING THE DEPOSITION OF
ORGANIC CONTAMINANTS IN PULP AND PAPERMAKING PROCESSES
FIELD OF THE INVENTION
The present invention relates to methods for inhibiting the deposition of organic contaminants from pulp in pulp and papermaking systems.
BACKGROUND OF THE INVENTION
The deposition of organic contaminants in the pulp and paper industry can cause both quality and efficiency problems in pulp and papermaking systems. Some components occur naturally in wood and are released during various pulping and papermaking pr~cesses. The term "pitch" can be used to refer to deposits composed of organic constituents which may originate from these natural resins, their salts, as well as coating binders, sizing agents, and defoaming chemicals which may be found in the pulp. In addition, pitch frequently contains inorganic components such as calcium carbonate, talc, clays, titanium, and related materials.
209~27~
Stickies is a term that has become increasingly used to describe deposits that occur in systems using recycled fiber. These deposits often c~ntain the same material found in "pitch" deposits ln add;tion to adhesives, hot melts, waxes, and inks. All of the aforementioned materials have many common characteristics including: hydrophobicity, deformability, tackiness, low surface energy, and the potential to cause problems with deposition, quality, and efficiency in the process. Diagram 1 shows the complex relationsh;p between pitch and stickies discussed here.
Diagram 1 Pitch Stickies Natural Resins (fatty and resin acids, X X
fatty esters, insoluble salts, sterols, etc.) Defoamers (oil, EBS, silicate, X X
silicone oils, ethoxylated compounds, etc.) Sizing Agents (Rosin size, ASA, AKD, X X
hydrolysis products insoluble salts, etc.) Coating Binders (PVAC, SBR) X X
Waxes X
Inks X
Hot Melts (EVA, PVAC, etc.) X
Contact Adhesives X
(SBR, vinyl acrylates, polyisoprene, etc.) 20~127~
The deposition of organic contaminants can be detrimental to the efficiency of a pulp or paper mill caus;ng both reduced quality and reduced operating efficiency. Organic contaminants can deposit on process equipment in papermaking sys-tems resulting in operational difficulties in the systems. The deposition of organic contaminants on consistency regulators and other instrument probes can render these components useless. Deposits on screens can reduce throughput and upset operation of the system. This deposition can occur not only on metal surfaces in the system, but also on plastic and synthetic surfaces such as machine wires, felts, foils, Uhle boxes and headbox components.
~ iistorically, the subsets of the organic deposit problems, "pitch" and "stickies" have manifested themselves separately, dif-ferently and have been treated distinctly and separately. From a physical standpoint, "pitch" deposits have usually formed from microscopic particles of adhesive material (natural or man-made) in the stock which accumulate on papermaking or pulping equip-ment. These deposits can readily be found on stock chest walls, ! paper machine foils, Uhle boxes, paper machine wires, wet press felts, dryer felts, dryer cans, and calendar stacks. The diffi-culties related to these deposits included direct interference w;th the efficiency of the contaminated surface, therefore, reduced production, as well as holes, dirt, and other sheet defects that reduce the quality and usefulness of the paper for operations that follow like coating, converting, or printing.
ORGANIC CONTAMINANTS IN PULP AND PAPERMAKING PROCESSES
FIELD OF THE INVENTION
The present invention relates to methods for inhibiting the deposition of organic contaminants from pulp in pulp and papermaking systems.
BACKGROUND OF THE INVENTION
The deposition of organic contaminants in the pulp and paper industry can cause both quality and efficiency problems in pulp and papermaking systems. Some components occur naturally in wood and are released during various pulping and papermaking pr~cesses. The term "pitch" can be used to refer to deposits composed of organic constituents which may originate from these natural resins, their salts, as well as coating binders, sizing agents, and defoaming chemicals which may be found in the pulp. In addition, pitch frequently contains inorganic components such as calcium carbonate, talc, clays, titanium, and related materials.
209~27~
Stickies is a term that has become increasingly used to describe deposits that occur in systems using recycled fiber. These deposits often c~ntain the same material found in "pitch" deposits ln add;tion to adhesives, hot melts, waxes, and inks. All of the aforementioned materials have many common characteristics including: hydrophobicity, deformability, tackiness, low surface energy, and the potential to cause problems with deposition, quality, and efficiency in the process. Diagram 1 shows the complex relationsh;p between pitch and stickies discussed here.
Diagram 1 Pitch Stickies Natural Resins (fatty and resin acids, X X
fatty esters, insoluble salts, sterols, etc.) Defoamers (oil, EBS, silicate, X X
silicone oils, ethoxylated compounds, etc.) Sizing Agents (Rosin size, ASA, AKD, X X
hydrolysis products insoluble salts, etc.) Coating Binders (PVAC, SBR) X X
Waxes X
Inks X
Hot Melts (EVA, PVAC, etc.) X
Contact Adhesives X
(SBR, vinyl acrylates, polyisoprene, etc.) 20~127~
The deposition of organic contaminants can be detrimental to the efficiency of a pulp or paper mill caus;ng both reduced quality and reduced operating efficiency. Organic contaminants can deposit on process equipment in papermaking sys-tems resulting in operational difficulties in the systems. The deposition of organic contaminants on consistency regulators and other instrument probes can render these components useless. Deposits on screens can reduce throughput and upset operation of the system. This deposition can occur not only on metal surfaces in the system, but also on plastic and synthetic surfaces such as machine wires, felts, foils, Uhle boxes and headbox components.
~ iistorically, the subsets of the organic deposit problems, "pitch" and "stickies" have manifested themselves separately, dif-ferently and have been treated distinctly and separately. From a physical standpoint, "pitch" deposits have usually formed from microscopic particles of adhesive material (natural or man-made) in the stock which accumulate on papermaking or pulping equip-ment. These deposits can readily be found on stock chest walls, ! paper machine foils, Uhle boxes, paper machine wires, wet press felts, dryer felts, dryer cans, and calendar stacks. The diffi-culties related to these deposits included direct interference w;th the efficiency of the contaminated surface, therefore, reduced production, as well as holes, dirt, and other sheet defects that reduce the quality and usefulness of the paper for operations that follow like coating, converting, or printing.
2 ~ 7 ~
From a physical standpoint, "stickies" have usually been particles of visible or nearly visible size in the stock which originate from the recycled fiber. These deposits tend to accumu-late on many of the same surfaces that "pitch" can be found on and cause many of the same difficulties that "pitch" can cause.
The most severe "stickies" related deposits however tend to be found on paper machine wires, wet felts, dryer felts, and dryer cans.
Methods of preventing the build up of deposits on the pulp and papermill equipment and surfaces are of great importance to the industry. The paper machines could be shut down for cleaniny, but ceasing operation for cleaning is undesirable because of the consequential loss of productivity, poor quality while partially contaminated and "dirt" which occurs when deposits break off and become incorporated in the sheet. Preventing deposition is thus greatly preferred where it can be effectively practiced.
In the past stickies deposits and pitch deposits have typically manifested themselves in different systems. This was true because mills usually used only virgin fiber or only recycled fiber. Often very different treatment chemicals and strategies were used to control these separate problems.
Current trends are for increased mandatory use of recycled fiber in all systems. This is resulting in a co-occurance of stickies and pitch problems in a given mill. It is desirable to find treatment chemicals and strategies which will be highly 2~9~ ~72 effective at eliminating both of these problems without having to feed two or more separate chemicals. The materials of this invent;on have clearly shown their ab;lity to ach;eve this goal.
Pitch control agents of commerce have historically included surfactants, which when added to the system, can stabilize the dispersion of the pitch in the furnish and white water. Stabilization can help prevent the pitch from precipitating out on wires and felts.
Mineral additives such as talc have also found use and can reduce the tacky nature of pitch by adsorbing finely dispersed pitch particles on their surfaces. This will reduce the degree to which the particles coagulate or agglomerate.
Polyphosphates have been used to try to maintain the pitch in a finely dispersed state. Alum has also been widely used to reduce deposition of pitch and related problems.
Both chemical and non-chemical approaches to stickies control are employed by papermakers. Non-chemical approaches include furnish selection, screening and cleaning, and thermal/mechanical dispersion units.
Chemical treatment techniques for stickies control include dispersion, detackification, wire passiYation and cat;onic fixation. Chemicals used included talc, polymers, dispersants and surfactants.
20~1272 SUMMARY OF THE INVENTION
The present invention pertains to methods for inhibiting the deposition o~ organic contaminants from pulp ;n pulp and papermaking systems comprising treating said systems wlth an effective amount for the purpose of a hydrophobically modified associative polymer.
Common organic contaminants include constituents which occur in the pulp (virgin, recycled or combinations) having the potential to deposit and reduce paper machine performance or paper quality. This will include natural resins such as fatty acids, resin acids, their insoluble salts, fatty esters, sterols and other organic constituents, like ethylene bis-stearamide, waxes, sizing agents, adhesives, hot me7ts, inks, defoamers, and latexes that may be found to deposit in papermaking systems.
DESCRIPTION OF THE RELATED ART
Surfactants, anionic polymers and copolymers of anionic monomers and hydrophobic monomers have been used extensively to prevent pitch deposition of metal soap and other resinous pitch components. See "Pulp and Paper", by James P. Casey, ~ol. II, 2nd Edition, pp. 1096-7.
United States Patent No. 4,871,424~ Dreisbach et al., October 1989 teaches the use of polyvinyl alcohol and copolymers of vinyl alcohol to inh;bit pitch deposition from pulp in paper-making systems.
2~272 United States Patent No. 3,081,219, Drennan et al., March 1963 teaches the use of a polymeric N-vinyl lactam to control pitch in the making of paper for sulfite pulps.
United States Patent No. 3,154,466, Nothum, October 196~, teaches the use of xylene sulfonic acid-formaldehyde condensates and salts thereof as pitch dispersants in papermaking.
United States Patent No. 3,992,249, Farley, November 1976 discloses the use of certain anionic vinyl polymers carrying hydro-phobic-oleophilic and anionic hydrophilic substituents when added prior to the beating operation in the range of about 0.5 parts to 100 parts by weight of the fibrous suspension to inhibit the depo-sition of adhesive pitch particles on the surfaces of pulp-mill equipment.
United States Patent No. 4,846,933, Dreisbach et al., July 1989 teaches the use of a water soluble polymer containing polymerized units of methyl vinyl ether having methyl ether groups to control pitch deposition from pulp.
United States Patent No. 4,822, 452, Tse et al., April 1989 teaches the use of urethane block copolymers, as nonionic associative thickeners. These copolymers act as thickeners in the preparation of a fibrous web of textile lenyth fibers.
~ 0 ~
"The Influences of washing, defoamers and d;spersants on pitch deposition from unbleached Kraft pulps," N. Dunlop-Jones and L.H. Allen, Journal of Pulp and Paper Science: Vol. 15 No. 6, November 1989 teaches the use of nonylphenol ethoxylate compounds to inhibit pitch deposition in papermaking systems.
U.S. Patent No. 4,781,794, Moreland, November 1988 teaches methods for detackifying adhesive materials contained in secondary fiber. The metnods comprise adding an unsubstituted methyl ether cellulose derivative to the secondary fiber. Methyl cellulose is a representative compound.
U.S. Patent No. 4,886,575, Moreland, December 1989 teaches the use of polyvinyl alcohol to inhibit the deposition and adherence of stickies to the repulping equipment.
U.S. Patent No. 4,886,575, Moreland, December 1989 teaches the use of polyvinyl alcohol to inhibit the deposition and adherence of stickies to the repulping equipment.
U.S. Patent No. 4,923,S66, Shawki et al., May 1990 teaches methods for pacifying stickies by applying urea between the drying rolls and the fin1shed produce reel.
U.S. Patent No. 4,643.800, Maloney et al., February 1987 teaches removing and dispersing contaminant from secondary fiber during repulping. Nonionic surfactants and dispersants are used to separate the contaminant from the fiber.
20~1~72 DETAILED DESCRIPTION OF THE INVENTION
The present inventors have discovered that the deposition of organic contam;nants ~rom pulp in pulp and papermaking systems can be inhibited by treating said pulp and papermaking systems with an effective amount of a hydrophobically modified associ~tive polymer.
These associative polymers act to inhibit khe deposition when adsorbed onto contaminants or contaminant prone surfaces.
This may be achieved by continuous or batch addition to the stock (virgin, recycled and/or combination~ prior to the site of concern or by continuous application directly to the site of primary contamination (i.e. the wire~ prior to the accumulation of the deposit. The term hydrophobically associative polymer relates to polymers which have two or more hydrophobic regions giving them the capacity to form associative networks by the attraction/inter-action of the hydrophobic regions.
Hydrophobically associating water-soluble polymers possess unusual rheological characteristics which are thought to arise from the intermolecular association of ne;ghboring hydrophobic sub-20- stituents. The hydrophobic substituents are incorporated onto the polymer through chemical grafting or a suitable co-polymerization - procedure. The hydrophobic groups are incorporated to a level so as to not render the final modified polymer water insoluble. These polymers have found use in industrial fields such as enhanced oil 209~272 --lo--recovery and in the formulation of latex based paints. See Carbohydrate Polymers 12 (1990) 4~3-459, R. Tanaka et al., the contents of wh;ch are wholly ;ncorporated here;n.
These polymers are widely used as rheology modifiers where their unique assoc;ative capab;lities are very important. In th;s application they are often referred to as "associat;ve thickeners".
They are very d;fferent in behav;or from typ;cal high molecular weight water-soluble polymers. They also behave very d;fferently from dispersants which are low molecular we;ght and highly charged.
Associative thickeners are water-soluble polymers containing hydrophobic groups wh;ch are capable of non-special hydrophobic association, s;m;lar to surfactants. See Polymers as Rheology Modifiers, Chapter 12. page 207, Systems Approach to Rheology Control, P.R. Howard, E.L. Leafure, S.T.
Rosier and E.J. Schaller.
One group of these ~ydrophobically modified associative polymers are the hydrophob;cally mod;fied hydroxyethyl cellulose assoc;ative polymers. These polymers are ava;lable from Aqualon Company as Natroso ~ Plus 330 and Plus ~30 and previously from Hercules as WSP-D-330. The hydrophobically modified hydroxyethyl cellulose associative polymers are described by K.G. Shaw and D.P.
Liepold, Journal of Coatings Technology 57, No. 727, pp.
63-72(August, 1985), incorporated herein by reference.
2 ~ 72 Another family of hydrophobically modified associat;ve polymers are the hydrophobically modified associative water-soluble anion;c polymers which are derived from ethylenically unsaturated acids such as acrylic acid and methyacrylic acid; ethylenically unsaturated monomers such as 2-acrylamido-2-propane sulfonic acid(AMPS~ and I-allyloxy-2-hydroxypropyl sulfonate and unsaturated acid monomers in general. Acrylate-based monomers are the preferred monomers in deriving these polymers. Representatives of these polymers are available from Rohm & Haas as Acryso ~ TT615, Acryso ~ ICS l; Polyphobe 107 available from Union Carbide and the Alcogum SL70 and 296W polymers available from Alco Chemical Corporation. Polymers based on maleic acid copolymers and naphthalene sulfonate condensates have not been effective in this invention. It is thought that this is due to their inability to achieve high enough molecular weight to be effective.
Alcogum SL70 is thought to be a terpolymer of methacrylic acid, ethyl acrylate, and a nonionic monomeric surfactant. The nonionic surfactant monomer consisted of a poly(oxyethylene) compound and an alkyl hydrocarbon segment. The components are consistent with the patent literature in an approximate ratio of 40:50:10. The Alcogum 296W polymer is the sodium salt of poly(acrylic acid) prepared by the hydrolysis of poly(methyl acrylate) and was found to contain approximately 16 mole percent residual methyl acrylate units.
~09~272 In another embodiment, the modified associative polymers are hydrophobically substituted acrylamide copolymers. These copolymers result from substitution of an acrylamide monomer to some extent to result ;n a copolymer. These copolymers can possess the comonomers other than acrylamide with the following structures:
IH3 ~l C = C - C - O -(CH2 - CH2 - )24 ~ C22 ~45 (I) IH3 p C = C - C - O -(CH2 - CH2 - )10 ~ ~ (CH2)8 - CH3 (II) c = C e [0 c 1~4~5 -[0 - C - !C]3,6 0H (III) C = C - C - [CH2 - CH2 - O] ~ (CH2)8 - CH3 ~IV) Other representative modified polymers of this invention are hydrophobically substituted polyethylene oxide polymers. These multihydrophobically substituted polymers indicate that two or more hydrophobic groups are desirable for optimum efficiency. These polymers can have hydrophobic groups which are combined to the polyethylene oxide polymer by ester linkages. Preferred poly-ethylene oxide polymers include polyethylene oxide dioleate esters.
Mapa ~ 6000 available from PPG/Mazer is a representative polyethylene oxide polymer.
209~ 272 Other hydrophobically associative thickener polymers based on modified ethylene oxide are also effective deposition control polymers as defined by this invention. PluracolR TH922 and TH916 available from BASF are useful polymers in accordance with this invention.
A further embodiment of this invention utilizes associative water-soluble urethane polymers. These polymers have alter-nating blocks of hydrophobic groups and hydrophilic groups. These polyethylene glycol/ethylene oxide based urethane block polymers may have molecular weights in the range of (10,000 to 2,000,000) and are disclosed in U.S. Patent Nos. 4,079,028 and 4,155,892 as paint thickeners. These references are wholly incorporated by reference herein. Commercial formulations of these copolymers are available as AcrysolR RM-825 and AcrysolR RM-1020 from Rohm and Haas. These polymers comprise urethane block copolymers in different carrier fluids. for instance, AcrysolR RM-825 is a 25 percent solids grade of polymer in a mixture of 25 percent butyl carbitol(a diethylene glycol monobutyl ether) and 75 percent water. Similar copolymers are available from Union ~arbide Corporation as UCARR SCT 200 and UCARR SCT 275. These compounds are discussed in U.S. Patent 4,496,708. Similar compounds are also available from Henkel Corporation under the trade names DSX 1514 and DSX 1550. These compounds are discussed in U.S. Patent 4,438,225.
The polymers of the instant invention are effective at controlling the deposition of organic contaminants in papermaking systems. This may include Kraft, acid sulfite, mechanical pulp and recycled fiber systems. For example, deposition in the brown stock washer, screen room and decker system in Kraft papermaking processes can be controlled. The term "papermaking system" is meant to include all pulp processes. Generally, it is thought that these polymers can be utilized to prevent deposition on all surfaces from the beginning of the pulp mill to the reel of the papermachine under a variety of pH's and conditions. More specifically, these polymers effectively decrease the deposition not only on metal surfaces but also on plastic and synthetic surfaces such as machine wires, felt, foils, Uhle boxes and headbox components.
The polymers may be added to the papermaking system along with other papermaking additives. These can include other polymers, starch and sizing aids.
The polymers of the present invention can be added to the pulp at any stage of the papermaking system. They may be added directly to the pulp furnish or sprayed on wires, felts, press rolls or other deposition-prone surfaces. They may be added to the papermaking system neat, as a powder, slurry or in solution;
the preferred primary solvent being water but is not limited to such. They may be added specifically and only to a furnish identified as contaminated or may be added to blended pulps. The polymers may be added to the stock at any point prior to the manifestation of the deposition problem and at more than one site when more than one deposition site occurs. Combinations of the above additive methods may also be employed by way of feeding the pulp millstock, feeding to the papermachine furnish, and spraying 2~91272 on the wire and felt simultaneously. The effective amount of these polymers to be added to the papermaking system depends on a number of variables, including the pH of the system, hardness of the water, temp~rature of the water, additional additives, and the organic contam;nant type and content of the pulp. Generally, 0.5 parts per million to about 150 parts per million is added to the paper making system. Preferably, from about lO parts per million to about 50 parts per million is added to the system.
There are several advantages anticipated with the present invention as compared to prior processes. These advantages include: an ability to function without being greatly affected by hardness of the water in the system; an ability to function with lower foaming than surfactants, an ability to function while not adversely affecting sizing, fines retention, and an ability to function at very low dosages, reduced environmental impact, and improved biodegradability. Also, the ability of these agents to function in spite of dilution has been clearly shown.
Further these agents have proven effective against both the pitch and stickies manifestation of organic deposition problems providing for an effective reduction of these problems in mills employing a variety of virgin and recycled fiber sources.
The data set forth below were developed to demonstrate the unexpected results occasioned by use of the invention.
~127~
The following examples are included as being illustrations of the invention and should not be construed as limiting the scope thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
It was found that pitch (natural resins, etc.) could be made to deposit from a 0.5% consistency fiber slurry containing approximately 2000 parts per million of a laboratory pltch preparation by placing the slurry into a metal pan suspended in a laboratory ultrasonic cleaner water bath. The slurry contained 0.5% bleached hardwood Kraft fiber, approximately 2000 parts per million of the potassium salt of a fatty acid blend, approximately 200 parts per million calcium from calcium chloride and approxi-mately 300 parts per million sodium carbonate. The slurry was maintained at 50C and at a pH of 11.
It was stirred gently by an overhead stirrer and subjected to ultrasonic energy for 10 minutes. The deposit weight was deter-mined by subtracting the starting weight of the pan from the weight of the pan plus the deposit after completion of the test.
This was converted to percent control of deposit using the formula:
% control of deposit = untreated weight - treated weigLht X 100 untreated weight 2091~7~
A high percent control of deposit is indicative of good deposit inhibiting qualities. Studies of this type were conducted using hydrophobically modified associative polymers of the type described in this invention. Results of this test;ng ;s reported in Table I.
TABLE I
% Control Treatment Aaent 50 ppm 10 ppm Unmodified Hydroxyethyl 60 Cellulose1 Hydrophobically modified 97 23 Hydroxyethyl cellulose2 Hydrophobically modified 96 62 Hydroxyethyl cellulose3 Hydrophobically modified 94 --Hydroxyethyl cellulose4 1 available commercially as Natrosol H4BR
~ available commercially as Natroso ~ lus 330 3 available commercially as Natroso ~Plus 430 4 available commercially as Hercules WSP-D-330 These results indicate that the hydrophobically modified associative polymers are more efficient deposit inhibitors than the unmodified polymers of a related type. These results further indicate that the polymers of this invention are effective at controlling deposition on metal surfaces and under alkaline conditions and specifically referred to typically as "pitch".
2~12~
Further studies of the testing described ;n Table I were conducted using hydrophobically modified associative anionic polymers and anionic dispersants disclosed as being preferred in the prior art. These results appear in Table II.
TABLE II
% Control Treatment Agent 100 ppm 50 ppm10 DDm Hydrolysed Styrene Maleic 82 12 17 Anhydride Copolymer 1 Hydrolysed Diisobutylene Maleic 13 13 0 Anhydride Copolymer 2 Hydrophobically Associative -- 88 28 Anionic Polymer 3 Hydrophobically Associative -- 93 18 Anionic Polymer4 Hydrophobically Associative -- 95 22 Anionic Polymer 5 Hydrophobically Associative -- 98 14 Anionic Polymer5 Hydrophobically Associative -- 93 25 Anionic Polymer 7 1 Available commercially as Alco SMA lQ00, see also U.S.
3,992,24~, Farley 2 Available commercially as Tamol 731, see also U.S. 3,992,249, Farley 3 Available commercially as Alcogum SL70 4 Available commercially as Alcogum~296W
Available commercially as Acryso ~TT615 6 Available commercially as Acryso ~ICS 1 7 Available commercially as Polyphobe 107 These results illustrate that the polymers of this invention are surprisingly more effective for deposition control than known deposition inhibitors specifically, they show efficacy at controlling pitch deposition.
Further testing as described in Table I was conducted using hydrophobically substituted acrylamide copolymers. The hydrophobic comonomers possess the structures:
209~2~
.1 11 C = C - C - O -(CH2 - CH2 - )24 ~ C22 H45 (I) CIH3 tl C = C - C - O -(CH2 - CH2 - )10 ~ ~ ~H2)8 - CH3 (II) C = C C [o C f~4 5 -Lo - C - C13~ OH
(III) C = C - C - [CH2 - CH2 - ]6 ~ (CH2)8 - CH3 (IV) The results of their testing appear in Table III.
~09~72 TABLE III
TreatmentMole /O Molar Ratio % Control AqentHYdrophobe AMD/IPA 50 ppm 20 ppm10 Ppm I 0.0 11:1 20 0 0 I 0.3 11:1 -- -- --I 0.6 11:1 31 39 --I 1.0 11:1 48 41 --I 2.0 11:1 54 24 --I 2.0 34:1 7~ 49 23 I 2.0 No IPA 68 49 32 I 3.0 11:1 66 45 20 I 4.0 17:1 66 16 16 II 2.0 11:1 72 -- 12 II 3.0 11:1 81 -- 13 II 4.0 11:1 84 -- 35 II 5.0 11:1 87 -- 32 II 0.5 No IPA 15 -- 0 II I.0 No IPA 48 -- 13 Il 2.0 No IPA 77 -- 6 II 3.0 No IPA 75 -- 13 II 4.0 No IPA 83 -- 30 2~91~7~
TABLE ITI (cont'd) TreatmentMole % Molar Ratio% Control Agent Hydrophobe AMD~IPA50 Ppm 2Q ppm 10 ppm IV 2.0 11:1 46 -- 0 IV 3.0 11:1 58 -- 6 IV 4.0 11:1 70 -- 39 IY 5.0 11:1 79 -- 11 IV 0.5 No IPA 16 -- 6 IV 1.0 No IPA 26 -- 5 IV 2.0 No IPA 49 -- 21 IV 3.0 No IPA 60 -- 0 IV 4.0 No IPA 67 -- 25 The results of Table III indicate that the hydrophobically modified associative polymers of the present invention are effective at inhibiting deposition. The results illustrate that substituted acrylamides of this invention are more efficient at inhibiting deposition broadly and pitch deposition speciFically than unsubstituted acrylamides.
Additional testing was performed as described in Table I
using hydrophobically substituted polyethylene oxides. These results are reported in Table IV.
209:1272 TABLE IV
% Control Treatment Aqent 50 ppm 10 ppm Nonyl Phenol Ethoxylate ~Surfonic~ -95) 81 9 Polyethylene oxide dioleate (Map~ ~6000) 85 36 Talloweth-60 Myristal glycol (Dapral 282) 88 46 The results indicated in Table IV are further indicative that the multi-hydrophobically substituted polyethylene oxides are effective for inhibiting deposition. They were also shown to be more effective than the known mono-hydrophobically substituted deposition inhibitors.
Hydrophobically modified ethylene oxide polymers were also tested according to the procedure described in Table I.
The results of this testing appear in Table V.
TABLE V
% nControl Treatment Agent 50 ppm 10 ppm Hydrophobically modified 95 88 Associative Ethylene Oxidel Copolymer Hydrophobically Modified Associative ethylene oxide2 95 86 Copolymer 1 Available commercially as Pluracol ~H922 2 Available commercially as Pluraco H916 209~272 The results presented in Table V further show that the polymers of this invention provide highly effective and efficient deposition control and more specif;cally, pitch control.
Further studies of the testing described in Table I were conducted using commercially available associative water-solub?P
urethane polymers. These testing results appear in Table VI.
TABLE VI
Percent Control of Pitch Treatment Aqent 100 ppm 50 ppm lO ppm Nonylphenol ethoxylate1 81 3 Sodium lignosulfate2 0 4 11 Hydrolyzed styrene maleic anhydride3 82 12 17 Diisobutene maleic anhydride4 13 13 0 Water-soluble urethane polymer5 83 58 Water-soluble urethane polymer6 87 72 Water-soluble urethane polymer7 81 31 Water-soluble urethane polymer8 87 49 Water-soluble urethane polymer9 94 49 Water-soluble urethane polymer10 96 75 1 commercially available as Surfonic~ -9S
2 commercially available as Lignosol XD
3 commercially available as Alco SMA 1000 4 commercially available as Tamol 7~1 5 commercially available as Acryso ~RM 1020 6 commercially available as Acrysol~ M 825 7 commercially available as DSX 1514 B commercially available as DSX 1~50 9 commerc;ally available as UCA ~ CT 200 10 commercially available as UCAR~ CT 275 20~1 272 These results indicate that the associative water-soluble urethane polymers of the present invention were more effective for inhibiting deposition than the known deposition inhibitors. These results further indicate that these polymers are effective at con-trolling deposition on the metal surfaces of papermaking systems.
Further studies of the testing described in Table I were conducted using water-soluble urethane polymers synthesized using a wide variety o~ reactive isocyanates, water-soluble diols, branching agents, and terminating groups. These polymers consti tute polyethylene oxide/polyethylene glycol polymers with urethane linkages. They are synthesized utilizing isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and other dihydroxyl reactive materials. These polymers are also synthesized utilizing water-soluble diol compounds and can be selected from the group consisting of polyethylene glycol compounds with molecular weights from about 400 to about 1450 and ethylene oxide/propylene oxide block copolymers.
The isocyanates included hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate and other dihydroxyl reactive materials. The water-soluble diols included PEG ~olyethylene Glycol) 400, PEG 600, PEG 1000, PEG 1450, PluronicWL-35 and Pluronic~ ORS. The branching agents included glycerol and pentaerythritol. The terminating groups (monohydroxy compounds) included 2-ethyl hexanol, nonyl phenol, nonyl phenol etho~ylates with 40 and 70 moles EO, and secondary alcohol ethoxylates with 30 moles EO.
, ~ U
These testing rcsults appear in Table VII.
TABLE VII
Percent Control Urethane Polymer Oomponents of Deposition Branching Termination 50 10 Diol IsocYanate Aqent Aqent ppm ppm PEG 400 HMDIGlycerol 2-EH 91 21 Pluronic L-35 TDI ---- 2-EH 91 24 PEG 1000 HMDI ---- . N PH -- 9 PEG 1000 HMDI Penta 2-EH -- 23 Pluronic 10R5 HMDI ---- 2-EH -- 54 -------- ISOPHGlycerol NP-40 92 12 -------- ISOPHGlycerol 15-S-30 94 19 PEG 1450 ISOPHGlycerol 15-S-30 78 12 ~09~72 PEG (MW)~- polyethylene Glycol Pluronic~L-35 = EO/PO/EO 3lock Copolymer Pluronic~10R5 = PO/EO/PO Block Copolymer HMDI = Hexamethylene diisocyanate TDI = Toluene Diisocyanate ISOPH = Isophorone Diisocyanate PENTA = Pentaerythritol 2-EH = 2-Ethyl Hexanol N-pH = Nonyl Phenol NP-70 = Nonyl Phenol with 70 moles EO
NP-40 = Nonyl Phenol with 40 moles EO
15-S-30 = Secondary Alcohol w;th 30 moles EO
These results indicate that water-soluble urethane polymers of the present invention having a widely varying character with respect to branching, end groups, and character of the backbone (diols and isocyanates used) can be highly effective for controlling pitch deposition.
209~272 In order to establish the efficacy of the materials of this invention as deposition control agents, on plastic surfaces and specifically for adhesive contaminants of the sort found in recycled fiber, a laboratory test was devised utilizing adhesive-backed tapes as stickie coupons. The stickie coupon can be fabricated from any type nf adhesive tape that will not disinte-grate when placed in water. For the study, tapes made from a styrenebutadiene rubber and vinylic esters were used. Both of these potential organic contaminants are known to cause problems "st;ckies" in secondary fiber utilization. A second coupon was fabricated from polyester film such as the product marketed as MYLAR
by the DuPont Chemical Company. This material was chosen because papermachine forming fabrics are frequently made of polyester which is susceptible to considerable problem caused by stickies.
500 mL of solutions in 600 mL beakers containing various deposit control agents are placed in a water bath heated to 50C. The tape and the polyester film coupons are placed in the test solution so the adhesive side of the coupon faces away from the polyester film coupon. After 1 hour oF immersion, the adhesive side of the stickie coupon is placed in contact with the polyester coupon and pressed to 1000 pound force.
The average peel strength of the bond formed between the tape coupon and the polyester coupon was measured with an Instron tensile tester. The peel strength of the bond formed between the stickie tape coupon and the polyester coupon was 209~272 interpreted as a measure of the tendency for an organic contaminant to attach to components of a paper-machine and cause runnabil1ty or product qual;ty problems. More specifically, this indicates the tendency of a st;ck;es depos;t to form on a plastic surface.
The results of this testing appear in Table YIII.
TABLE VIII
% petackification Treatment Aqent Dosage (ppm) 0.2 0.5 1.0 2.0 5.0 10.0 25.0 1. Octylphenoxy Poly-(ethyleneoxy) ethanol 2.8 9.4 18.7 47.3 93.7 2. Nonylphenolethoxylate - - 4.7 29.1 64.2 86.3 100 3. Dodecylphenoxy Poly (ethyleneoxy) ethanol - - 31.2 56.0 94.7 100 100 4. 8lock Copolymer of Ethyleneoxide/pro-pylene oxide - - 5.027.1 60.0 80.4 83.7 5. Sodium Salt of Con-densed Naphthalene Sulfonic Acid - - O O O 0 1.4 6. Water Soluble Urethane Polymer 67.9 80.989.4 100 100 7. Water Soluble Urethane Polymer 71.1 89.2 100 100 100 - -8. Water Soluble Urethane Polymer 69.0 80.993.9 100 100 9. Water Soluble Urethane Polymer 85.3 95.9 lOO 100 100 2~272 ;s commercially available as Triton ~
is commercially available as Surfoni N-95 3 is commercially available as Igepal ~-520 4 is commercially available as Pluron;c~F-108 5 is commercially available as Tamol ~ I
6 is commercially available as Acryso 'RM 825 7 is commercially available as Acryso QR-708 8 is commercially available as DSX 15 4 9 is commercially available as DSX 1550 The results shown in Table VIII further support the efficacy of the present invention (examples 6-9 of Table YIII) for deposit control on plastic surfaces. They showed better efficacy rPlative to prior art deposit control agents (examples l-5 of Table VIII). This demonstrates the effectiveness of nonionic polymers of the present invention for stickies deposition control.
Further studies of the testing described in Table VIII were conducted using commercially available water-soluble anionic polymers.
These test results appear in Table IX.
TABLE IX
% Detackification Treatment Aqent Dosaqe (ppm) 0.5 1.0 2.0 5.0 10.0 50.0 100.0 1. Hydrolysed diisobutylene maleic anhydride copolymer - 0 - 2.7 8.2 0 3.5 2. Hydrophobically associative anionic polymer 63.1 98.6 98.2 97.8 - - -3. Hydrophobically associative anionic polymer 12.7 97.6 98.5 98.7 - - -4. Hydrophobically associative anionic polymer 80.0 97.9 98.0 98.9 5. Hydrophobically associative anionic polymer 96.4 97.6 97.4 98.7 20~272 1 commercially ava;lable as Tamol 731 2 commercially available as Acrysol TT615 3 commercia11y available as Acrysol6~ICS 1 4 commercially available as Alcogum SL-70 5 commercially available as Alcogum SL-78 These results indicate that water-soluble anionic associative polymers of this invention can be effective for controlling organic contaminant deposition (examples 2-5 of Table IX). They further indicate the efficacy of these anionic polymers I0 at controlling stickies deposition. These results further illustrate how surprisingly more effective this invention is than prior art anionic dispersant deposition control agents (example 1 of table IX).
Papermaking consists of various processes which can be affected by sudden changes in pH, temperature, dilution (i.e., concentration), shear force, etc. Severe changes in these parameters can cause system shock which adversely impact paper production. Deposit control agents that can strongly adsorb onto the organic contaminant surface and res;st the desorbing effects of dilution are highly desirable. Not only will deposit;on control be impraved, but also the required dosage will be reduced, while negative side effects, such as forming and wet-end inter-ferences, will be reduced or eliminated. The procedure outlined in Table VIII was modified to examine the effect of dilut;on on deposition control. Dilution was accomplished by immersing the adhesive tape and MYLAR in distilled water for 30 minutes after the initial immersion. This can be repeated as many times as desired. The results of the testing are tabulated in Table X.
~091272 TABLE X
Sample Concen. No 1st 2nd 3rd 4th ~p~m~ Dilution D;lut;on D;lut;on D;lution D;lut;on 100 95 95. 94 g5 6 10 1~0 100 100 94 95 7 10 100 ~4 93 89 89 8 10 ~00 95 95 95 96 Sample 1 = octylphenoxy poly(ethyleneoxy)ethanol Sample 2 = nonylphenol ethoxylate Sample 3 = dodecylphenoxypoly(ethyleneoxy) ethanol Sample 4 = block copolymers of e$hylene oxide and propylene oxide Sample 5 = water soluble associative polymer available as Acryso Sample 6 = water soluble associative polymer available as QR-708 Sample 7 = water soluble associative polymer available as DSX-1514 Sample 8 = water soluble associative polymer available as DSX-1550 As shown in Table X, the associat;ve polymers of this invent;on (samples 5-8 of Table X) ;n this test were very effective after the fourth dilution. They showed better performance relative to prior art deposit control agents (samples 1-4 of Table X). This demonstrates a strong adsorbing power and good resistance to the desorbing effects of dilution.
2~91272 While this ;nvention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
..
From a physical standpoint, "stickies" have usually been particles of visible or nearly visible size in the stock which originate from the recycled fiber. These deposits tend to accumu-late on many of the same surfaces that "pitch" can be found on and cause many of the same difficulties that "pitch" can cause.
The most severe "stickies" related deposits however tend to be found on paper machine wires, wet felts, dryer felts, and dryer cans.
Methods of preventing the build up of deposits on the pulp and papermill equipment and surfaces are of great importance to the industry. The paper machines could be shut down for cleaniny, but ceasing operation for cleaning is undesirable because of the consequential loss of productivity, poor quality while partially contaminated and "dirt" which occurs when deposits break off and become incorporated in the sheet. Preventing deposition is thus greatly preferred where it can be effectively practiced.
In the past stickies deposits and pitch deposits have typically manifested themselves in different systems. This was true because mills usually used only virgin fiber or only recycled fiber. Often very different treatment chemicals and strategies were used to control these separate problems.
Current trends are for increased mandatory use of recycled fiber in all systems. This is resulting in a co-occurance of stickies and pitch problems in a given mill. It is desirable to find treatment chemicals and strategies which will be highly 2~9~ ~72 effective at eliminating both of these problems without having to feed two or more separate chemicals. The materials of this invent;on have clearly shown their ab;lity to ach;eve this goal.
Pitch control agents of commerce have historically included surfactants, which when added to the system, can stabilize the dispersion of the pitch in the furnish and white water. Stabilization can help prevent the pitch from precipitating out on wires and felts.
Mineral additives such as talc have also found use and can reduce the tacky nature of pitch by adsorbing finely dispersed pitch particles on their surfaces. This will reduce the degree to which the particles coagulate or agglomerate.
Polyphosphates have been used to try to maintain the pitch in a finely dispersed state. Alum has also been widely used to reduce deposition of pitch and related problems.
Both chemical and non-chemical approaches to stickies control are employed by papermakers. Non-chemical approaches include furnish selection, screening and cleaning, and thermal/mechanical dispersion units.
Chemical treatment techniques for stickies control include dispersion, detackification, wire passiYation and cat;onic fixation. Chemicals used included talc, polymers, dispersants and surfactants.
20~1272 SUMMARY OF THE INVENTION
The present invention pertains to methods for inhibiting the deposition o~ organic contaminants from pulp ;n pulp and papermaking systems comprising treating said systems wlth an effective amount for the purpose of a hydrophobically modified associative polymer.
Common organic contaminants include constituents which occur in the pulp (virgin, recycled or combinations) having the potential to deposit and reduce paper machine performance or paper quality. This will include natural resins such as fatty acids, resin acids, their insoluble salts, fatty esters, sterols and other organic constituents, like ethylene bis-stearamide, waxes, sizing agents, adhesives, hot me7ts, inks, defoamers, and latexes that may be found to deposit in papermaking systems.
DESCRIPTION OF THE RELATED ART
Surfactants, anionic polymers and copolymers of anionic monomers and hydrophobic monomers have been used extensively to prevent pitch deposition of metal soap and other resinous pitch components. See "Pulp and Paper", by James P. Casey, ~ol. II, 2nd Edition, pp. 1096-7.
United States Patent No. 4,871,424~ Dreisbach et al., October 1989 teaches the use of polyvinyl alcohol and copolymers of vinyl alcohol to inh;bit pitch deposition from pulp in paper-making systems.
2~272 United States Patent No. 3,081,219, Drennan et al., March 1963 teaches the use of a polymeric N-vinyl lactam to control pitch in the making of paper for sulfite pulps.
United States Patent No. 3,154,466, Nothum, October 196~, teaches the use of xylene sulfonic acid-formaldehyde condensates and salts thereof as pitch dispersants in papermaking.
United States Patent No. 3,992,249, Farley, November 1976 discloses the use of certain anionic vinyl polymers carrying hydro-phobic-oleophilic and anionic hydrophilic substituents when added prior to the beating operation in the range of about 0.5 parts to 100 parts by weight of the fibrous suspension to inhibit the depo-sition of adhesive pitch particles on the surfaces of pulp-mill equipment.
United States Patent No. 4,846,933, Dreisbach et al., July 1989 teaches the use of a water soluble polymer containing polymerized units of methyl vinyl ether having methyl ether groups to control pitch deposition from pulp.
United States Patent No. 4,822, 452, Tse et al., April 1989 teaches the use of urethane block copolymers, as nonionic associative thickeners. These copolymers act as thickeners in the preparation of a fibrous web of textile lenyth fibers.
~ 0 ~
"The Influences of washing, defoamers and d;spersants on pitch deposition from unbleached Kraft pulps," N. Dunlop-Jones and L.H. Allen, Journal of Pulp and Paper Science: Vol. 15 No. 6, November 1989 teaches the use of nonylphenol ethoxylate compounds to inhibit pitch deposition in papermaking systems.
U.S. Patent No. 4,781,794, Moreland, November 1988 teaches methods for detackifying adhesive materials contained in secondary fiber. The metnods comprise adding an unsubstituted methyl ether cellulose derivative to the secondary fiber. Methyl cellulose is a representative compound.
U.S. Patent No. 4,886,575, Moreland, December 1989 teaches the use of polyvinyl alcohol to inhibit the deposition and adherence of stickies to the repulping equipment.
U.S. Patent No. 4,886,575, Moreland, December 1989 teaches the use of polyvinyl alcohol to inhibit the deposition and adherence of stickies to the repulping equipment.
U.S. Patent No. 4,923,S66, Shawki et al., May 1990 teaches methods for pacifying stickies by applying urea between the drying rolls and the fin1shed produce reel.
U.S. Patent No. 4,643.800, Maloney et al., February 1987 teaches removing and dispersing contaminant from secondary fiber during repulping. Nonionic surfactants and dispersants are used to separate the contaminant from the fiber.
20~1~72 DETAILED DESCRIPTION OF THE INVENTION
The present inventors have discovered that the deposition of organic contam;nants ~rom pulp in pulp and papermaking systems can be inhibited by treating said pulp and papermaking systems with an effective amount of a hydrophobically modified associ~tive polymer.
These associative polymers act to inhibit khe deposition when adsorbed onto contaminants or contaminant prone surfaces.
This may be achieved by continuous or batch addition to the stock (virgin, recycled and/or combination~ prior to the site of concern or by continuous application directly to the site of primary contamination (i.e. the wire~ prior to the accumulation of the deposit. The term hydrophobically associative polymer relates to polymers which have two or more hydrophobic regions giving them the capacity to form associative networks by the attraction/inter-action of the hydrophobic regions.
Hydrophobically associating water-soluble polymers possess unusual rheological characteristics which are thought to arise from the intermolecular association of ne;ghboring hydrophobic sub-20- stituents. The hydrophobic substituents are incorporated onto the polymer through chemical grafting or a suitable co-polymerization - procedure. The hydrophobic groups are incorporated to a level so as to not render the final modified polymer water insoluble. These polymers have found use in industrial fields such as enhanced oil 209~272 --lo--recovery and in the formulation of latex based paints. See Carbohydrate Polymers 12 (1990) 4~3-459, R. Tanaka et al., the contents of wh;ch are wholly ;ncorporated here;n.
These polymers are widely used as rheology modifiers where their unique assoc;ative capab;lities are very important. In th;s application they are often referred to as "associat;ve thickeners".
They are very d;fferent in behav;or from typ;cal high molecular weight water-soluble polymers. They also behave very d;fferently from dispersants which are low molecular we;ght and highly charged.
Associative thickeners are water-soluble polymers containing hydrophobic groups wh;ch are capable of non-special hydrophobic association, s;m;lar to surfactants. See Polymers as Rheology Modifiers, Chapter 12. page 207, Systems Approach to Rheology Control, P.R. Howard, E.L. Leafure, S.T.
Rosier and E.J. Schaller.
One group of these ~ydrophobically modified associative polymers are the hydrophob;cally mod;fied hydroxyethyl cellulose assoc;ative polymers. These polymers are ava;lable from Aqualon Company as Natroso ~ Plus 330 and Plus ~30 and previously from Hercules as WSP-D-330. The hydrophobically modified hydroxyethyl cellulose associative polymers are described by K.G. Shaw and D.P.
Liepold, Journal of Coatings Technology 57, No. 727, pp.
63-72(August, 1985), incorporated herein by reference.
2 ~ 72 Another family of hydrophobically modified associat;ve polymers are the hydrophobically modified associative water-soluble anion;c polymers which are derived from ethylenically unsaturated acids such as acrylic acid and methyacrylic acid; ethylenically unsaturated monomers such as 2-acrylamido-2-propane sulfonic acid(AMPS~ and I-allyloxy-2-hydroxypropyl sulfonate and unsaturated acid monomers in general. Acrylate-based monomers are the preferred monomers in deriving these polymers. Representatives of these polymers are available from Rohm & Haas as Acryso ~ TT615, Acryso ~ ICS l; Polyphobe 107 available from Union Carbide and the Alcogum SL70 and 296W polymers available from Alco Chemical Corporation. Polymers based on maleic acid copolymers and naphthalene sulfonate condensates have not been effective in this invention. It is thought that this is due to their inability to achieve high enough molecular weight to be effective.
Alcogum SL70 is thought to be a terpolymer of methacrylic acid, ethyl acrylate, and a nonionic monomeric surfactant. The nonionic surfactant monomer consisted of a poly(oxyethylene) compound and an alkyl hydrocarbon segment. The components are consistent with the patent literature in an approximate ratio of 40:50:10. The Alcogum 296W polymer is the sodium salt of poly(acrylic acid) prepared by the hydrolysis of poly(methyl acrylate) and was found to contain approximately 16 mole percent residual methyl acrylate units.
~09~272 In another embodiment, the modified associative polymers are hydrophobically substituted acrylamide copolymers. These copolymers result from substitution of an acrylamide monomer to some extent to result ;n a copolymer. These copolymers can possess the comonomers other than acrylamide with the following structures:
IH3 ~l C = C - C - O -(CH2 - CH2 - )24 ~ C22 ~45 (I) IH3 p C = C - C - O -(CH2 - CH2 - )10 ~ ~ (CH2)8 - CH3 (II) c = C e [0 c 1~4~5 -[0 - C - !C]3,6 0H (III) C = C - C - [CH2 - CH2 - O] ~ (CH2)8 - CH3 ~IV) Other representative modified polymers of this invention are hydrophobically substituted polyethylene oxide polymers. These multihydrophobically substituted polymers indicate that two or more hydrophobic groups are desirable for optimum efficiency. These polymers can have hydrophobic groups which are combined to the polyethylene oxide polymer by ester linkages. Preferred poly-ethylene oxide polymers include polyethylene oxide dioleate esters.
Mapa ~ 6000 available from PPG/Mazer is a representative polyethylene oxide polymer.
209~ 272 Other hydrophobically associative thickener polymers based on modified ethylene oxide are also effective deposition control polymers as defined by this invention. PluracolR TH922 and TH916 available from BASF are useful polymers in accordance with this invention.
A further embodiment of this invention utilizes associative water-soluble urethane polymers. These polymers have alter-nating blocks of hydrophobic groups and hydrophilic groups. These polyethylene glycol/ethylene oxide based urethane block polymers may have molecular weights in the range of (10,000 to 2,000,000) and are disclosed in U.S. Patent Nos. 4,079,028 and 4,155,892 as paint thickeners. These references are wholly incorporated by reference herein. Commercial formulations of these copolymers are available as AcrysolR RM-825 and AcrysolR RM-1020 from Rohm and Haas. These polymers comprise urethane block copolymers in different carrier fluids. for instance, AcrysolR RM-825 is a 25 percent solids grade of polymer in a mixture of 25 percent butyl carbitol(a diethylene glycol monobutyl ether) and 75 percent water. Similar copolymers are available from Union ~arbide Corporation as UCARR SCT 200 and UCARR SCT 275. These compounds are discussed in U.S. Patent 4,496,708. Similar compounds are also available from Henkel Corporation under the trade names DSX 1514 and DSX 1550. These compounds are discussed in U.S. Patent 4,438,225.
The polymers of the instant invention are effective at controlling the deposition of organic contaminants in papermaking systems. This may include Kraft, acid sulfite, mechanical pulp and recycled fiber systems. For example, deposition in the brown stock washer, screen room and decker system in Kraft papermaking processes can be controlled. The term "papermaking system" is meant to include all pulp processes. Generally, it is thought that these polymers can be utilized to prevent deposition on all surfaces from the beginning of the pulp mill to the reel of the papermachine under a variety of pH's and conditions. More specifically, these polymers effectively decrease the deposition not only on metal surfaces but also on plastic and synthetic surfaces such as machine wires, felt, foils, Uhle boxes and headbox components.
The polymers may be added to the papermaking system along with other papermaking additives. These can include other polymers, starch and sizing aids.
The polymers of the present invention can be added to the pulp at any stage of the papermaking system. They may be added directly to the pulp furnish or sprayed on wires, felts, press rolls or other deposition-prone surfaces. They may be added to the papermaking system neat, as a powder, slurry or in solution;
the preferred primary solvent being water but is not limited to such. They may be added specifically and only to a furnish identified as contaminated or may be added to blended pulps. The polymers may be added to the stock at any point prior to the manifestation of the deposition problem and at more than one site when more than one deposition site occurs. Combinations of the above additive methods may also be employed by way of feeding the pulp millstock, feeding to the papermachine furnish, and spraying 2~91272 on the wire and felt simultaneously. The effective amount of these polymers to be added to the papermaking system depends on a number of variables, including the pH of the system, hardness of the water, temp~rature of the water, additional additives, and the organic contam;nant type and content of the pulp. Generally, 0.5 parts per million to about 150 parts per million is added to the paper making system. Preferably, from about lO parts per million to about 50 parts per million is added to the system.
There are several advantages anticipated with the present invention as compared to prior processes. These advantages include: an ability to function without being greatly affected by hardness of the water in the system; an ability to function with lower foaming than surfactants, an ability to function while not adversely affecting sizing, fines retention, and an ability to function at very low dosages, reduced environmental impact, and improved biodegradability. Also, the ability of these agents to function in spite of dilution has been clearly shown.
Further these agents have proven effective against both the pitch and stickies manifestation of organic deposition problems providing for an effective reduction of these problems in mills employing a variety of virgin and recycled fiber sources.
The data set forth below were developed to demonstrate the unexpected results occasioned by use of the invention.
~127~
The following examples are included as being illustrations of the invention and should not be construed as limiting the scope thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
It was found that pitch (natural resins, etc.) could be made to deposit from a 0.5% consistency fiber slurry containing approximately 2000 parts per million of a laboratory pltch preparation by placing the slurry into a metal pan suspended in a laboratory ultrasonic cleaner water bath. The slurry contained 0.5% bleached hardwood Kraft fiber, approximately 2000 parts per million of the potassium salt of a fatty acid blend, approximately 200 parts per million calcium from calcium chloride and approxi-mately 300 parts per million sodium carbonate. The slurry was maintained at 50C and at a pH of 11.
It was stirred gently by an overhead stirrer and subjected to ultrasonic energy for 10 minutes. The deposit weight was deter-mined by subtracting the starting weight of the pan from the weight of the pan plus the deposit after completion of the test.
This was converted to percent control of deposit using the formula:
% control of deposit = untreated weight - treated weigLht X 100 untreated weight 2091~7~
A high percent control of deposit is indicative of good deposit inhibiting qualities. Studies of this type were conducted using hydrophobically modified associative polymers of the type described in this invention. Results of this test;ng ;s reported in Table I.
TABLE I
% Control Treatment Aaent 50 ppm 10 ppm Unmodified Hydroxyethyl 60 Cellulose1 Hydrophobically modified 97 23 Hydroxyethyl cellulose2 Hydrophobically modified 96 62 Hydroxyethyl cellulose3 Hydrophobically modified 94 --Hydroxyethyl cellulose4 1 available commercially as Natrosol H4BR
~ available commercially as Natroso ~ lus 330 3 available commercially as Natroso ~Plus 430 4 available commercially as Hercules WSP-D-330 These results indicate that the hydrophobically modified associative polymers are more efficient deposit inhibitors than the unmodified polymers of a related type. These results further indicate that the polymers of this invention are effective at controlling deposition on metal surfaces and under alkaline conditions and specifically referred to typically as "pitch".
2~12~
Further studies of the testing described ;n Table I were conducted using hydrophobically modified associative anionic polymers and anionic dispersants disclosed as being preferred in the prior art. These results appear in Table II.
TABLE II
% Control Treatment Agent 100 ppm 50 ppm10 DDm Hydrolysed Styrene Maleic 82 12 17 Anhydride Copolymer 1 Hydrolysed Diisobutylene Maleic 13 13 0 Anhydride Copolymer 2 Hydrophobically Associative -- 88 28 Anionic Polymer 3 Hydrophobically Associative -- 93 18 Anionic Polymer4 Hydrophobically Associative -- 95 22 Anionic Polymer 5 Hydrophobically Associative -- 98 14 Anionic Polymer5 Hydrophobically Associative -- 93 25 Anionic Polymer 7 1 Available commercially as Alco SMA lQ00, see also U.S.
3,992,24~, Farley 2 Available commercially as Tamol 731, see also U.S. 3,992,249, Farley 3 Available commercially as Alcogum SL70 4 Available commercially as Alcogum~296W
Available commercially as Acryso ~TT615 6 Available commercially as Acryso ~ICS 1 7 Available commercially as Polyphobe 107 These results illustrate that the polymers of this invention are surprisingly more effective for deposition control than known deposition inhibitors specifically, they show efficacy at controlling pitch deposition.
Further testing as described in Table I was conducted using hydrophobically substituted acrylamide copolymers. The hydrophobic comonomers possess the structures:
209~2~
.1 11 C = C - C - O -(CH2 - CH2 - )24 ~ C22 H45 (I) CIH3 tl C = C - C - O -(CH2 - CH2 - )10 ~ ~ ~H2)8 - CH3 (II) C = C C [o C f~4 5 -Lo - C - C13~ OH
(III) C = C - C - [CH2 - CH2 - ]6 ~ (CH2)8 - CH3 (IV) The results of their testing appear in Table III.
~09~72 TABLE III
TreatmentMole /O Molar Ratio % Control AqentHYdrophobe AMD/IPA 50 ppm 20 ppm10 Ppm I 0.0 11:1 20 0 0 I 0.3 11:1 -- -- --I 0.6 11:1 31 39 --I 1.0 11:1 48 41 --I 2.0 11:1 54 24 --I 2.0 34:1 7~ 49 23 I 2.0 No IPA 68 49 32 I 3.0 11:1 66 45 20 I 4.0 17:1 66 16 16 II 2.0 11:1 72 -- 12 II 3.0 11:1 81 -- 13 II 4.0 11:1 84 -- 35 II 5.0 11:1 87 -- 32 II 0.5 No IPA 15 -- 0 II I.0 No IPA 48 -- 13 Il 2.0 No IPA 77 -- 6 II 3.0 No IPA 75 -- 13 II 4.0 No IPA 83 -- 30 2~91~7~
TABLE ITI (cont'd) TreatmentMole % Molar Ratio% Control Agent Hydrophobe AMD~IPA50 Ppm 2Q ppm 10 ppm IV 2.0 11:1 46 -- 0 IV 3.0 11:1 58 -- 6 IV 4.0 11:1 70 -- 39 IY 5.0 11:1 79 -- 11 IV 0.5 No IPA 16 -- 6 IV 1.0 No IPA 26 -- 5 IV 2.0 No IPA 49 -- 21 IV 3.0 No IPA 60 -- 0 IV 4.0 No IPA 67 -- 25 The results of Table III indicate that the hydrophobically modified associative polymers of the present invention are effective at inhibiting deposition. The results illustrate that substituted acrylamides of this invention are more efficient at inhibiting deposition broadly and pitch deposition speciFically than unsubstituted acrylamides.
Additional testing was performed as described in Table I
using hydrophobically substituted polyethylene oxides. These results are reported in Table IV.
209:1272 TABLE IV
% Control Treatment Aqent 50 ppm 10 ppm Nonyl Phenol Ethoxylate ~Surfonic~ -95) 81 9 Polyethylene oxide dioleate (Map~ ~6000) 85 36 Talloweth-60 Myristal glycol (Dapral 282) 88 46 The results indicated in Table IV are further indicative that the multi-hydrophobically substituted polyethylene oxides are effective for inhibiting deposition. They were also shown to be more effective than the known mono-hydrophobically substituted deposition inhibitors.
Hydrophobically modified ethylene oxide polymers were also tested according to the procedure described in Table I.
The results of this testing appear in Table V.
TABLE V
% nControl Treatment Agent 50 ppm 10 ppm Hydrophobically modified 95 88 Associative Ethylene Oxidel Copolymer Hydrophobically Modified Associative ethylene oxide2 95 86 Copolymer 1 Available commercially as Pluracol ~H922 2 Available commercially as Pluraco H916 209~272 The results presented in Table V further show that the polymers of this invention provide highly effective and efficient deposition control and more specif;cally, pitch control.
Further studies of the testing described in Table I were conducted using commercially available associative water-solub?P
urethane polymers. These testing results appear in Table VI.
TABLE VI
Percent Control of Pitch Treatment Aqent 100 ppm 50 ppm lO ppm Nonylphenol ethoxylate1 81 3 Sodium lignosulfate2 0 4 11 Hydrolyzed styrene maleic anhydride3 82 12 17 Diisobutene maleic anhydride4 13 13 0 Water-soluble urethane polymer5 83 58 Water-soluble urethane polymer6 87 72 Water-soluble urethane polymer7 81 31 Water-soluble urethane polymer8 87 49 Water-soluble urethane polymer9 94 49 Water-soluble urethane polymer10 96 75 1 commercially available as Surfonic~ -9S
2 commercially available as Lignosol XD
3 commercially available as Alco SMA 1000 4 commercially available as Tamol 7~1 5 commercially available as Acryso ~RM 1020 6 commercially available as Acrysol~ M 825 7 commercially available as DSX 1514 B commercially available as DSX 1~50 9 commerc;ally available as UCA ~ CT 200 10 commercially available as UCAR~ CT 275 20~1 272 These results indicate that the associative water-soluble urethane polymers of the present invention were more effective for inhibiting deposition than the known deposition inhibitors. These results further indicate that these polymers are effective at con-trolling deposition on the metal surfaces of papermaking systems.
Further studies of the testing described in Table I were conducted using water-soluble urethane polymers synthesized using a wide variety o~ reactive isocyanates, water-soluble diols, branching agents, and terminating groups. These polymers consti tute polyethylene oxide/polyethylene glycol polymers with urethane linkages. They are synthesized utilizing isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and other dihydroxyl reactive materials. These polymers are also synthesized utilizing water-soluble diol compounds and can be selected from the group consisting of polyethylene glycol compounds with molecular weights from about 400 to about 1450 and ethylene oxide/propylene oxide block copolymers.
The isocyanates included hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate and other dihydroxyl reactive materials. The water-soluble diols included PEG ~olyethylene Glycol) 400, PEG 600, PEG 1000, PEG 1450, PluronicWL-35 and Pluronic~ ORS. The branching agents included glycerol and pentaerythritol. The terminating groups (monohydroxy compounds) included 2-ethyl hexanol, nonyl phenol, nonyl phenol etho~ylates with 40 and 70 moles EO, and secondary alcohol ethoxylates with 30 moles EO.
, ~ U
These testing rcsults appear in Table VII.
TABLE VII
Percent Control Urethane Polymer Oomponents of Deposition Branching Termination 50 10 Diol IsocYanate Aqent Aqent ppm ppm PEG 400 HMDIGlycerol 2-EH 91 21 Pluronic L-35 TDI ---- 2-EH 91 24 PEG 1000 HMDI ---- . N PH -- 9 PEG 1000 HMDI Penta 2-EH -- 23 Pluronic 10R5 HMDI ---- 2-EH -- 54 -------- ISOPHGlycerol NP-40 92 12 -------- ISOPHGlycerol 15-S-30 94 19 PEG 1450 ISOPHGlycerol 15-S-30 78 12 ~09~72 PEG (MW)~- polyethylene Glycol Pluronic~L-35 = EO/PO/EO 3lock Copolymer Pluronic~10R5 = PO/EO/PO Block Copolymer HMDI = Hexamethylene diisocyanate TDI = Toluene Diisocyanate ISOPH = Isophorone Diisocyanate PENTA = Pentaerythritol 2-EH = 2-Ethyl Hexanol N-pH = Nonyl Phenol NP-70 = Nonyl Phenol with 70 moles EO
NP-40 = Nonyl Phenol with 40 moles EO
15-S-30 = Secondary Alcohol w;th 30 moles EO
These results indicate that water-soluble urethane polymers of the present invention having a widely varying character with respect to branching, end groups, and character of the backbone (diols and isocyanates used) can be highly effective for controlling pitch deposition.
209~272 In order to establish the efficacy of the materials of this invention as deposition control agents, on plastic surfaces and specifically for adhesive contaminants of the sort found in recycled fiber, a laboratory test was devised utilizing adhesive-backed tapes as stickie coupons. The stickie coupon can be fabricated from any type nf adhesive tape that will not disinte-grate when placed in water. For the study, tapes made from a styrenebutadiene rubber and vinylic esters were used. Both of these potential organic contaminants are known to cause problems "st;ckies" in secondary fiber utilization. A second coupon was fabricated from polyester film such as the product marketed as MYLAR
by the DuPont Chemical Company. This material was chosen because papermachine forming fabrics are frequently made of polyester which is susceptible to considerable problem caused by stickies.
500 mL of solutions in 600 mL beakers containing various deposit control agents are placed in a water bath heated to 50C. The tape and the polyester film coupons are placed in the test solution so the adhesive side of the coupon faces away from the polyester film coupon. After 1 hour oF immersion, the adhesive side of the stickie coupon is placed in contact with the polyester coupon and pressed to 1000 pound force.
The average peel strength of the bond formed between the tape coupon and the polyester coupon was measured with an Instron tensile tester. The peel strength of the bond formed between the stickie tape coupon and the polyester coupon was 209~272 interpreted as a measure of the tendency for an organic contaminant to attach to components of a paper-machine and cause runnabil1ty or product qual;ty problems. More specifically, this indicates the tendency of a st;ck;es depos;t to form on a plastic surface.
The results of this testing appear in Table YIII.
TABLE VIII
% petackification Treatment Aqent Dosage (ppm) 0.2 0.5 1.0 2.0 5.0 10.0 25.0 1. Octylphenoxy Poly-(ethyleneoxy) ethanol 2.8 9.4 18.7 47.3 93.7 2. Nonylphenolethoxylate - - 4.7 29.1 64.2 86.3 100 3. Dodecylphenoxy Poly (ethyleneoxy) ethanol - - 31.2 56.0 94.7 100 100 4. 8lock Copolymer of Ethyleneoxide/pro-pylene oxide - - 5.027.1 60.0 80.4 83.7 5. Sodium Salt of Con-densed Naphthalene Sulfonic Acid - - O O O 0 1.4 6. Water Soluble Urethane Polymer 67.9 80.989.4 100 100 7. Water Soluble Urethane Polymer 71.1 89.2 100 100 100 - -8. Water Soluble Urethane Polymer 69.0 80.993.9 100 100 9. Water Soluble Urethane Polymer 85.3 95.9 lOO 100 100 2~272 ;s commercially available as Triton ~
is commercially available as Surfoni N-95 3 is commercially available as Igepal ~-520 4 is commercially available as Pluron;c~F-108 5 is commercially available as Tamol ~ I
6 is commercially available as Acryso 'RM 825 7 is commercially available as Acryso QR-708 8 is commercially available as DSX 15 4 9 is commercially available as DSX 1550 The results shown in Table VIII further support the efficacy of the present invention (examples 6-9 of Table YIII) for deposit control on plastic surfaces. They showed better efficacy rPlative to prior art deposit control agents (examples l-5 of Table VIII). This demonstrates the effectiveness of nonionic polymers of the present invention for stickies deposition control.
Further studies of the testing described in Table VIII were conducted using commercially available water-soluble anionic polymers.
These test results appear in Table IX.
TABLE IX
% Detackification Treatment Aqent Dosaqe (ppm) 0.5 1.0 2.0 5.0 10.0 50.0 100.0 1. Hydrolysed diisobutylene maleic anhydride copolymer - 0 - 2.7 8.2 0 3.5 2. Hydrophobically associative anionic polymer 63.1 98.6 98.2 97.8 - - -3. Hydrophobically associative anionic polymer 12.7 97.6 98.5 98.7 - - -4. Hydrophobically associative anionic polymer 80.0 97.9 98.0 98.9 5. Hydrophobically associative anionic polymer 96.4 97.6 97.4 98.7 20~272 1 commercially ava;lable as Tamol 731 2 commercially available as Acrysol TT615 3 commercia11y available as Acrysol6~ICS 1 4 commercially available as Alcogum SL-70 5 commercially available as Alcogum SL-78 These results indicate that water-soluble anionic associative polymers of this invention can be effective for controlling organic contaminant deposition (examples 2-5 of Table IX). They further indicate the efficacy of these anionic polymers I0 at controlling stickies deposition. These results further illustrate how surprisingly more effective this invention is than prior art anionic dispersant deposition control agents (example 1 of table IX).
Papermaking consists of various processes which can be affected by sudden changes in pH, temperature, dilution (i.e., concentration), shear force, etc. Severe changes in these parameters can cause system shock which adversely impact paper production. Deposit control agents that can strongly adsorb onto the organic contaminant surface and res;st the desorbing effects of dilution are highly desirable. Not only will deposit;on control be impraved, but also the required dosage will be reduced, while negative side effects, such as forming and wet-end inter-ferences, will be reduced or eliminated. The procedure outlined in Table VIII was modified to examine the effect of dilut;on on deposition control. Dilution was accomplished by immersing the adhesive tape and MYLAR in distilled water for 30 minutes after the initial immersion. This can be repeated as many times as desired. The results of the testing are tabulated in Table X.
~091272 TABLE X
Sample Concen. No 1st 2nd 3rd 4th ~p~m~ Dilution D;lut;on D;lut;on D;lution D;lut;on 100 95 95. 94 g5 6 10 1~0 100 100 94 95 7 10 100 ~4 93 89 89 8 10 ~00 95 95 95 96 Sample 1 = octylphenoxy poly(ethyleneoxy)ethanol Sample 2 = nonylphenol ethoxylate Sample 3 = dodecylphenoxypoly(ethyleneoxy) ethanol Sample 4 = block copolymers of e$hylene oxide and propylene oxide Sample 5 = water soluble associative polymer available as Acryso Sample 6 = water soluble associative polymer available as QR-708 Sample 7 = water soluble associative polymer available as DSX-1514 Sample 8 = water soluble associative polymer available as DSX-1550 As shown in Table X, the associat;ve polymers of this invent;on (samples 5-8 of Table X) ;n this test were very effective after the fourth dilution. They showed better performance relative to prior art deposit control agents (samples 1-4 of Table X). This demonstrates a strong adsorbing power and good resistance to the desorbing effects of dilution.
2~91272 While this ;nvention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
..
Claims (67)
1. A method for inhibiting the deposition of organic contaminants from pulp in pulp and papermaking systems comprising treating said pulp and papermaking systems with an effective amount for the purpose of a hydrophobically modified associative polymer.
2. The method as claimed in claim 1 wherein said hydrophobically modified associative polymer is a hydrophobically modified nonionic associative polymer.
3. The method as claimed in claim 1 wherein said hydrophobically modified associative polymer is a hydrophobically modified water-soluble anionic associative polymer which are derived from ethylenically unsaturated acids, ethylenically unsaturated monomers and unsaturated acid monomers in general.
4. The method as claimed in claim 2 wherein said hydrophobically modified nonionic associative polymer is a hydrophobically modified hydroxyethyl cellulose associative polymer.
5. The method as claimed in claim 2 wherein said hydrophobically modified nonionic associative polymer is a hydrophobically substituted acrylamide copolymer.
6. The method as claimed in claim 5 wherein said hydrophobically substituted acrylamide copolymer has the structure:
7. The method as claimed in claim 5 wherein said hydrophobically substituted acrylamide copolymer has the structure:
8. The method as claimed in claim 5 wherein said hydrophobically substituted acrylamide copolymer has the structure:
9. The method as claimed in claim 5 wherein said hydrophobically substituted acrylamide copolymer has the structure:
10. The method as claimed in claim 2 wherein said hydrophobically modified nonionic associative polymer is a hydrophobically substituted polyethylene oxide polymer.
11. The method as claimed in claim 10 wherein said hydrophobically substituted polyethylene oxide polymer has hydrophobic groups which are combined to said polyethylene oxide polymer by ester linkages.
12. The method as claimed in claim 11 wherein said hydrophobically substituted polyethylene oxide polymer is a polyethylene oxide dioleate ester.
13. The method as claimed in claim 10 wherein said hydrophobically substituted polyethylene oxide polymer is an associative water-soluble polyethylene oxide polymer with urethane linkages.
14. The method as claimed in claim 13 wherein said associative water-soluble polyethylene oxide polymer with urethane linkages is synthesized utilizing isocyanate compounds.
15. The method as claimed in claim 14 wherein said isocyanate compounds are selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and other dihydroxyl reactive materials.
16. The method as claimed in claim 13 wherein said associative water-soluble polyethylene oxide polymer is synthesized utilizing water-soluble diol compounds.
17. The method as claimed in claim 16 wherein said water-soluble diols are selected from the group consisting of polyethylene glycol compounds, and ethylene oxide/propylene oxide block copolymers.
18. The method as claimed in claim 17 wherein said polyethylene glycol compounds have the molecular weight from about 400 to about 1450.
19. The method as claimed in claim 13 wherein said associative water-soluble polyethylene oxide polymer further comprises synthesis utilizing a branching agent.
20. The method as claimed in claim 17 wherein said branching agent is selected from the group consisting of glycerol and pentaerythritol.
21. The method as claimed in claim 13 wherein said associative water-soluble polyethylene oxide polymer with urethane linkages has a molecular weight from about 10,000 to about 2,000,000.
22. The method as claimed in claim 1 wherein said hydrophobically modified associative polymer is delivered to said pulp and papermaking system in a carrier solvent.
23. The method as claimed in claim 1 wherein said hydrophobically modified associative polymer is delivered to said pulp and papermaking system as a powder or a slurry.
24. The method as claimed in claim 22 wherein said carrier solvent is water.
25. The method as claimed in claim 1 wherein said hydrophobically modified associative polymer is added to said pulp and papermaking system by spraying.
26. The method as claimed in claim 1 wherein said hydrophobically modified associative polymer is sprayed onto the paper machine wire, paper machine felt, paper machine press roll or other surfaces prone to deposition.
27. The method as claimed in claim 1 wherein said hydrophobically modified associative polymer is added to said pulp and papermaking system with the furnish.
28. The method as claimed in claim 1 wherein said deposition of organic contaminants occurs on the metal surfaces of said pulp and papermaking systems.
29. The method as claimed in claim 1 wherein said depositions of organic contaminants occurs on the plastic surfaces of said pulp and papermaking systems.
30. The method as claimed in claim 1 wherein said hydrophobically modified associative polymer is added to said papermaking systems with other papermaking treatments.
31. The method as claimed in claim 1 wherein said organic contaminant is a pitch deposit.
32. The method as claimed in claim 1 wherein said organic contaminant is a stickies deposit.
33. The method as claimed in claim 1 wherein said polymer is added to the paper machine stock.
34. The method as claimed in claim 1 wherein said polymer is added directly to the contamination prone surface.
35. The method as claimed in claim 34 wherein said surface is selected from the group consisting of paper machine wire and paper machine wet felt.
36. The method as claimed in claim 1 wherein said organic contaminant is a mixture of pitch deposit and stickies deposit.
37. A method for inhibiting the deposition of organic contaminants from secondary fiber during repulping comprising treating said secondary fiber with an effective amount for the purpose of a hydrophobically modified associative polymer.
38. The method as claimed in claim 37 wherein said hydrophobically modified associative polymer is a hydrophobically modified nonionic associative polymer.
39. The method as claimed in claim 37 wherein said hydrophobically modified associative polymer is a hydrophobically modified anionic associative polymer water-soluble anionic associative polymer which are derived from ethylenically unsaturated acids, ethylenically unsaturated monomers and unsaturated acid monomers in general.
40. The method as claimed in claim 38 wherein said hydrophobically modified nonionic associative polymer is a hydrophobically modified hydroxyethyl cellulose associative polymer.
41. The method as claimed in claim 38 wherein said hydrophobically modified nonionic associative polymer is a hydrophobically substituted acrylamide copolymer.
42. The method as claimed in claim 41 wherein said hydrophobically substituted acrylamide copolymer has the structure:
43. The method as claimed in claim 41 wherein said hydrophobically substituted acrylamide copolymer has the structure:
44. The method as claimed in claim 41 wherein said hydrophobically substituted acrylamide copolymer has the structure:
45. The method as claimed in claim 41 wherein said hydrophobically substituted acrylamide copolymer has the structure:
46. The method as claimed in claim 38 wherein said hydrophobically modified nonionic associative polymer is a hydrophobically substituted polyethylene oxide polymer.
47. The method as claimed in claim 46 wherein said hydrophobically substituted polyethylene oxide polymer has hydrophobic groups which are combined to said polyethylene oxide polymer by ester linkages.
48. The method as claimed in claim 47 wherein said hydrophobically substituted polyethylene oxide polymer is a polyethylene oxide dioleate ester.
49. The method as claimed in claim 46 wherein said hydrophobically substituted polyethylene oxide polymer is an associative water-soluble polyethylene oxide polymer with urethane linkages.
50. The method as claimed in claim 49 wherein said associative water-soluble polyethylene oxide polymer with urethane linkages is synthesized utilizing isocyanate compounds.
51. The method as claimed in claim 50 wherein said isocyanate compounds are selected from the group consisting of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and other dihydroxyl reactive materials.
52. The method as claimed in claim 49 wherein said associative water-soluble polyethylene oxide polymer is synthesized utilizing water-soluble diol compounds.
53. The method as claimed in claim 52 wherein said water-soluble diols are selected from the group consisting of polyethylene glycol compounds, and ethylene oxide/propylene oxide block copolymers.
54. The method as claimed in claim 53 wherein said polyethylene glycol compounds have the molecular weight from about 400 to about 1450.
55. The method as claimed in claim 53 wherein said associative water-soluble polyethylene oxide polymer further comprises synthesis utilizing a branching agent.
56. The method as claimed in claim 53 wherein said branching agent is selected from the group consisting of glycerol and pentaerythritol.
57. The method as claimed in claim 49 wherein said associative water-soluble polyethylene oxide polymer with urethane linkages has a molecular weight from about 10,000 to about 2,000,000.
58. The method as claimed in claim 37 wherein said hydrophobically modified associative polymer is delivered to said secondary fiber in a carrier solvent.
59. The method as claimed in claim 37 wherein said hydrophobically modified associative polymer is delivered to said pulp and secondary fiber as a powder or a slurry.
60. The method as claimed in claim 58 wherein said carrier solvent is water.
61. The method as claimed in claim 37 wherein said hydrophobically modified associative polymer is added to said pulp and papermaking system by spraying.
62. The method as claimed in claim 37 wherein said hydrophobically modified associative polymer is sprayed onto the paper machine wire, paper machine felt, paper machine press roll or other surfaces prone to deposition.
63. The method as claimed in claim 37 wherein said hydrophobically modified associative polymer is added to said secondary fiber with the furnish.
64. The method as claimed in claim 37 wherein said pitch deposition occurs on the metal surfaces of said repulping systems.
65. The method as claimed in claim 37 wherein said pitch deposition occurs on the metal surfaces of said repulping systems.
66. The method as claimed in claim 37 wherein said pitch deposition occurs on the plastic surfaces of said repulping systems.
67. The method as claimed in claim 1 wherein said pulp and papermaking system is experiencing the effects of dilution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87493992A | 1992-04-28 | 1992-04-28 | |
| US07/874,939 | 1992-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2091272A1 true CA2091272A1 (en) | 1993-10-29 |
Family
ID=25364903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002091272A Abandoned CA2091272A1 (en) | 1992-04-28 | 1993-03-09 | Methods for controlling the deposition of organic contaminants in pulp and papermaking processes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0568229A1 (en) |
| AU (1) | AU663170B2 (en) |
| CA (1) | CA2091272A1 (en) |
| FI (1) | FI931912A (en) |
| NO (1) | NO931206L (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2131143A1 (en) * | 1993-10-07 | 1995-04-08 | Betzdearborn Inc. | Method of inhibiting wet strength resin deposition in papermaking felts |
| AU754486B2 (en) * | 1998-03-16 | 2002-11-14 | Nalco Chemical Company | Contaminant dispersants useful in recycling of treated containers |
| US6113738A (en) * | 1998-03-16 | 2000-09-05 | Nalco Chemical Company | Use of additives to breakdown and stabilize wax during fiber recycle |
| US7166192B2 (en) | 2003-05-23 | 2007-01-23 | Hercules Incorporated | Method for controlling pitch and stickies deposition |
| US7534324B2 (en) * | 2005-06-24 | 2009-05-19 | Hercules Incorporated | Felt and equipment surface conditioner |
| WO2008013875A2 (en) | 2006-07-26 | 2008-01-31 | Hercules Incorporated | Hydrophobically modified poly(ethylene glycol) for use in pitch and stickies control in pulp and papermaking processes |
| BRPI0718537B1 (en) * | 2006-11-06 | 2017-07-18 | Solenis Technologies Cayman, L.P. | A method and composition for inhibiting the deposition of one or more organic contaminants in pulp production and paper production systems |
| AU2009226129B2 (en) | 2008-03-15 | 2013-10-17 | Solenis Technologies Cayman, L.P. | Clay slurries and use thereof in pulp and papermaking applications |
| US8048268B2 (en) | 2009-10-27 | 2011-11-01 | Enzymatic Deinking Technologies, Llc | Method of controlling organic contaminants in pulp and paper making processes |
| US9416490B2 (en) | 2010-03-10 | 2016-08-16 | Nalco Company | Cross-linked glycerol based polymers as digestion aids for improving wood pulping processes |
| US8728275B2 (en) * | 2012-07-27 | 2014-05-20 | Ecolab Usa Inc. | Glycerol-based polymers for reducing deposition of organic contaminants in papermaking processes |
| CN103422382A (en) | 2012-05-21 | 2013-12-04 | 埃科莱布美国股份有限公司 | A method and a composition for reducing viscosity of organic contaminants in pulp processes and papermaking processes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992249A (en) * | 1974-04-08 | 1976-11-16 | American Cyanamid Company | Control of pulp-paper mill pitch deposits |
| US4886575A (en) * | 1985-10-08 | 1989-12-12 | Betz Laboratories, Inc. | Detackification of adhesive materials contained in secondary fiber with polyvinyl alcohol |
| US4846933A (en) * | 1986-06-03 | 1989-07-11 | Betz Laboratories, Inc. | Process for controlling pitch deposition from pulp in papermaking systems |
| US4861429A (en) * | 1988-07-29 | 1989-08-29 | Betz Laboratories, Inc. | Process for inhibiting white pitch deposition in papermaking felts |
-
1993
- 1993-03-09 CA CA002091272A patent/CA2091272A1/en not_active Abandoned
- 1993-03-31 NO NO93931206A patent/NO931206L/en not_active Application Discontinuation
- 1993-04-06 AU AU36743/93A patent/AU663170B2/en not_active Ceased
- 1993-04-19 EP EP93303007A patent/EP0568229A1/en not_active Ceased
- 1993-04-28 FI FI931912A patent/FI931912A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO931206D0 (en) | 1993-03-31 |
| AU663170B2 (en) | 1995-09-28 |
| NO931206L (en) | 1993-10-29 |
| AU3674393A (en) | 1993-11-04 |
| FI931912A0 (en) | 1993-04-28 |
| EP0568229A1 (en) | 1993-11-03 |
| FI931912A (en) | 1993-10-29 |
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