FIELD OF THE INVENTION

The present invention relates to methods for inhibiting the deposi¬ tion of organic contaminants in pulp and papermaking systems

BACKGROUND OF THE INVENTION

The deposition of organic contaminants in the pulp and papermak¬ ing 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 processes The term "pitch" can be used to refer to deposits composed of organic con¬ stituents 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 com¬ ponents such as calcium carbonate, talc, clays, titanium and related materials

Stickles is a term that has been increasingly used to describe de¬ posits that occur in the systems using recycled fiber These deposits often contain the same materials found in "pitch" deposits in addition to adhesives, hot melts, waxes, and inks All of the aforementioned materi- als have many common characteristics including hydrophobicity, de- foamability, tackiness, low surface energy, and the potential to cause problems with deposition, quality, and efficiency in the process Diagram I shows the complex relationship between pitch and stickles discussed here DIAGRAM I

Pitch Stickles

Natural Resins (fatty and resin acids, fatty esters, X X insoluble salts, sterols, etc )

Defoamers (oil, EBS, silicate, silicone oils, X X ethoxylated compounds, etc )

Sizing Agents (Rosin size, ASA, AKD, hydrolysis X X products, insoluble salts, etc )

Coating Binders (PVAC, SBR) X X

Waxes X Inks X

Hot Melts (EVA, PVAC, etc ) X

Contact Adhesives (SBR, vinyl acrylates, X polyisoprene, etc.)

The deposition of organic contaminants can be detrimental to the efficiency of a pulp or paper mill causing both reduced quality and reduc¬ ed operating efficiency Organic contaminants can deposit on process equipment in papermaking systems 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 opera¬ tion 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.

Historically, the subsets of the organic deposit problems, "pitch" and "stickies" have manifested themselves separately, differently and have been treated distinctly and separately. From a physical standpoint, "pitch" deposits have usually formed from microscopic particles of adhesive mate- rial (natural or man-made) in the stock which accumulate on papermaking or pulping equipment. 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 difficulties related to these deposits included direct interference with 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.

From a physical standpoint, "stickies" have usually been particles of visible or nearly visible size in the stock which originate from the recy¬ cled fiber. These deposits tend to accumulate on many of the same sur¬ faces that "pitch" can be found on and causes many of the same difficul¬ ties 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 cleaning, but ceasing opera¬ tion for cleaning is undesirable because of the consequential loss of pro- ductivity, poor quality while partially contaminated and "dirt" which occurs when deposits break off and become incorporated in the sheet Prevent¬ ing 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-occurrence of stickies and pitch problems in a given mill It is desirable to find treatment chemicals and strategies which will be highly effective at eliminating both of these prob- lems without having to feed two or more separate chemicals The mate¬ rials of this invention have clearly shown their ability to achieve this goal

SUMMARY OF THE INVENTION

The present invention provides for methods for inhibiting the depo¬ sition of organic contaminants, such as pitch and stickies, from pulp in pulp and papermaking systems The methods comprise adding to the pulp or the surfaces of papermaking machinery an effective deposition inhibiting amount of a blood-related protein

DESCRIPTION OFTHE RELATEDART

"Pulp and Paper", by James Casey, Vol III, 3rd Ed , pp 1587-88, suggests gelatin as a remedy for pitch trouble Serial No 08/421 ,349 teaches that a composition of polyvinyl alcohol and high molecular weight gelatin in synergistic ratios will inhibit the deposition of organic contami- nants in pulp and papermaking systems

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to methods for inhibiting the deposi- tion of organic contaminants from pulp on the surfaces of papermaking machinery in pulp and papermaking systems comprising adding to the pulp or applying to the surfaces of the papermaking machinery an effec¬ tive deposition inhibiting amount of a blood-related protein

For purposes of the present invention, blood-related proteins are defined as proteins selected from the group consisting of albumins, globu¬ lins, blends of albumins and globulins and spray-dried animal blood cells

Organic contaminants include constituents which occur in the pulp (virgin, recycled or combinations thereof) having the potential to deposit and reduce paper machine performance or paper quality. These contami¬ nants include but are not limited to natural resins such as fatty acids, resin acids, their insoluble salts, fatty esters, sterols and other organic constituents such as ethylene bis-stearamide, waxes, sizing agents, ad¬ hesives, hot melts, inks, defoamers, and latexes which may deposit in papermaking systems

Blood is the transport system of the body, carrying nutrients and oxygen to all the cells and removing carbon dioxide and other wastes from them Blood consists of cells suspended in the liquid plasma The cells, which constitute 45% of the whole volume of blood, include the red cells (erythrocytes), the white cells (leukocytes) and the platelets (throm- bocytes). The plasma is a clear liquid constituting about 55% of the blood by volume. Because of a higher specific gravity, the cell elements can be separated from the plasma by ceπtπfugation (1.09 vs 1.03) Serum is the plasma without fibnnogen, a clotting protein

Cells

(A) Red cells

There are about 5,000,000 red blood cells per cubic milli¬ meter of the blood. Their main function is to carry oxygen from the lungs to the cells They also remove carbon diox- ide from the cells and carry to the lungs Hemoglobin is a protein that gives the color to the red cells and has a molecular weight of about 67,000

(B) White cells

There are about 6,000 white cells per cubic millimeter of blood Their function is to destroy harmful microorganisms.

(C) Platelets

There are about 250,000 platelets per cubit millimeter of blood They are concerned with the coagulation of blood

Plasma Serum albumins, serum globulins and fibrinogen are the most important protein components of the plasma The function of serum albumin is to maintain normal osmotic pressure and therefore the water balance of the body The serum globulins consist of alpha, beta, and gamma globulins. Gamma globulin contains antibodies and antitoxins the body uses to combat infection Fibrinogen is concerned with the clotting of blood In general, albumins are transport and storage proteins. Globulins are contractile proteins and protective proteins in vertebrate blood

In contrast, gelatins are derived by hydrolysis from collagen, and insoluble fibrous protein that occurs in vertebrates and is the main com¬ ponent of connective tissues, tendons and bones Gelatin is principally made today from cattle bones, cattle hides and pork skins, and has molecular weights in the range of 2,000 to 400,000.

As demonstrated in Diagram II, there are distinct differences in the composition of proteins such as gelatin, and serum albumin and spray- dried animal blood that can be seen in ammo acid content

DIAGRAM II

Amino acid composition of selected proteins

Spray-Dried Amino Acid Gelatin Serum Albumin Animal Blood Alanine 7 0.6 7.6

Arginine 8 4.9 4.0

Aspartic Acid 6 9.0 1 1 .0

Cystine 0.1 3.9 0.6

Glutamic Acid 10 15.6 8.7 Glycine 23 2.9 Al

Histidine 0.7 3.1 —

Hydroxylysine 1

Hydroxyproline 12 — — — — — —

Isoleucine 1 1 .8 0.6 Leucine 3 1 1.3 13.4

Lysine 3 1 1 .3 9.0

Methionine 0.8 1.2 0.8

Phenylalanine 2 6.4 7.1

Proline 15 6.0 — Serine 3 4.3 4.4

Threonine 2 5.3 3.6

Tyrosine 0.4 3.5 2.2

Valine 2 8.8 9.2

Tryptophan -- 0.2 1.2

The albumins, globulins, or blends of albumins/globulins useful in the present invention include but are not limited to serum globulin, serum albumin, blends of serum globulin/albumin, plasma globulin, plasma albu- min, and blends of plasma albumin/globulin. These albumins and globu¬ lins have molecular weights in the range of 12,000 to 1 ,000,000. The al¬ bumins and globulins useful in the present invention are readily commer¬ cially available. Preferred albumins and globulins include serum albumin and serum globulin. Proteins derived from blood cells (e.g., animal) are also useful in the present invention.

The compositions of the present invention are effective at inhibiting 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 inhibited The term "paper- making systems" is meant to include all pulp processes Generally, it is thought that these compositions can be utilized to inhibit deposition on all surfaces of the papermaking system from the pulp mill to the reel of the paper machine, having a pH of about 3 to about 12, and under a variety of system conditions More specifically, the blood-related proteins effectively decrease the deposition not only on metal surfaces but also on plastic and synthetic surfaces such as machine wires, felts, foils, Uhle boxes, rolls and headbox components

The blood-related proteins of the present invention may be used with other pulp and papermaking additives which include but are not limited to starches, titanium dioxide, defoamers, wet strength resins and sizing aids, dispersants and emulsifiers

The blood-related proteins of the present invention can be added to the papermaking system at any stage They may be added directly to the pulp furnish or indirectly to the furnish through the headbox The in¬ ventive compositions may also be sprayed onto surfaces that are suffer¬ ing from deposition, such as the wire, press felts, press rolls and other deposition-prone surfaces

The blood-related proteins of the present invention can 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 When

added by spraying techniques, the composition is preferably diluted with water to a satisfactory inhibitor concentration The compositions may be added specifically and only to a furnish identified as contaminated or may be added to blended pulps The compositions 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 Combi¬ nations of the above additive methods may also be employed by feeding the pulp millstock, feeding to the paper machine furnish, and spraying on the wire and the felt simultaneously

For purposes of the present invention, the term "an effective depo¬ sition inhibiting amount" is defined as that amount which is sufficient to inhibit deposition in pulp and papermaking systems The effective amount to be added to the papermaking system depends on a number of variables including the pH of the system, hardness of the water, temperature of the water, additional additives, and the organic contaminant type and content of the pulp Generally, from about 1 part to about 200 parts albumin and/or globulins per million parts of pulp are added to the papermaking system Preferably, from about 2 parts to about 100 parts of the inventive composition are added per million parts of pulp in the system

There are several advantages associated with the present inven¬ tion compared to prior processes These advantages include an ability to function without being greatly affected by the hardness content of the water in the system, an ability to function while not adversely affecting sizing and fines retention, an ability to function at low dosages, reduced environmental impact, an ability to allow the user to use a greater amount of recycled fiber in the furnish, and improved biodegradability

Further, the blood-related proteins have proven effective against both the pitch and stickies manifestation of organic deposition problems providing for an effective reduction of these problems in paper mills utilizing a variety of virgin and recycled fiber sources

The data set forth below were developed to demonstrate the unex¬ pected results occasioned by use of the present invention The following are included as being illustrations of the present invention and should not be construed as limiting the scope thereof

Examples

Standard Tape Detackification Test (STDT)

In order to establish the efficacy of the inventive compositions as deposition control agents on plastic surfaces and specifically for adhesive contaminants of the sort found in recycled pulp, a laboratory test was de¬ veloped utilizing adhesive-backed tapes as stickie coupons The stickle coupon can be fabricated from any type of adhesive tape that will not dis- integrate in water For this study, tapes made from a styrenebutadiene rubber and vinylic esters were used Both of these potential organic contaminants are known to cause stickies problems in secondary fiber utilization A second coupon was fabricated from polyester film such as MYLAR ', a product marketed by DuPont Chemical Company This material was chosen because paper machine forming fabrics are fre¬ quently made of polyester which is susceptible to considerable deposition problems caused by stickies and/or pitch

This test involved immersing a 2" x 4" adhesive tape and a 2" x 4" polyester Mylar coupon into a 600 gram solution being tested The solu¬ tion contained in a 600 mL beaker is placed in a water bath with agitation and heated to the desired temperature After 30 minutes of immersion, the tape and coupon are removed from the solution and pressed to 10,000 lb force for one minute A tensile test instrument (Instron) is then used to measure the force required to pull the two apart A reduction in the force required indicates that the "stickie" has been detackified The % control or detackification is calculated by the following equation

% detackification = (Untreated force - treated force) x 100

Untreated force

The results of this testing are presented in Table I

TABLE

Standard Tape Detackification Test

Concentration

Treatment (oom) PH Temp (°C) % Detackification

Serum Albumin 1 6 50 86 3

2 6 50 95 5

5 6 50 100

0 5 3 50 94 9

1 3 50 100

2 3 50 96

5 3 50 100

High molecular 1 6 50 69 0 weight gelatin 2 6 50 70 0

Alkyl substituted 2 6 50 48

Quaternized protein 10 6 50 72

Milk protein 2 6 50 6

High Molecular Weight 2 6 50 71 animal protein 10 6 50 88

TABl -E I (cont'd)

Standard Tape Detackification Test

Concentration

Treatment (oom) pH Temp. (°C) % Detackification

Albumin/globulin 0.2 6 50 79.8

Serum protein 0.5 6 50 93.0

1.0 6 50 97.0

2 6 50 100.0

Polyvinyl alcohol 1 6 25 51

2 6 25 67

5 6 25 92

0.5 6 50 76.2

1 6 50 93.4

2 6 50 99.4

As demonstrated in Table I, serum albumin proved more effective than the high molecular weight gelatin at detackifying stickies. Similarly, a combination of albumin and globulin at low dosage was more effective than the high molecular weight gelatin.

Further testing was performed to determine contact angle measure¬ ments using the Wilhelmy Plate Method. The advancing and receding contact angles of water on a polyester surface were measured after it had been coated with various of the inventive compositions. The purpose of this study is to evaluate the potential of the proteins to adsorb and/or desorb at a simulated organic contaminant's surface.

A clean piece of polyester (15 mm x 40 mm x 0.11 mm) was dipped in a protein solution of a given concentration for 30 seconds. The coated polyester surface was then dried at room temperature for two hours. Af¬ ter drying, the advancing and receding contact angles of water on the coated surface were measured for three cycles using a Dynamic Contact

Angle Analyzer (Cahn DCA-312). The DCA-312 could run multiple im¬ mersions on the same solid-liquid system. Polyester film was used be¬ cause its surface energy is close to that of the majority of organic con¬ taminants in papermaking systems, such as resin acids, rubber-based contact adhesives, ethylene vinyl acetate hot melts, fatty acids, etc. Additionally, the polyester surface is smooth and easy to clean and handle.

The results of this testing are presented in Table II.

TABLE II vater on polyester surface at 25°C

Concentration Receding Sample (pom) Contact Anαle

Water 54

Serum Albumin 5 13 10 12

High molecular weight gelatin 5 17 10 16

Albumin/globulin serum protein 5 17 10 16

Meat soluble protein 5 38 10 27

Tea-cocyl hydrolyzed collagen 5 52 10 48

Tea-cocyl hydrolyzed soy proteinn 5 48 10 45

Hydrolyzed wheat protein 5 49 10 48

TABLE II (cont'd)

DCA receding contact angle of water on polyester surface at 25°C

Concentration Receding

Sample (pprn) Contact Anαle

Hydrolyzed gelatin 5 42

10 34

Soybean protein 5 48 10 46

Polyvinyl alcohol 5 21 10 20

These results demonstrate that at comparable higher levels of treatment the albumin and albumin/globulin serum proteins are as effec- tive as the high molecular weight gelatin However, at these treatment levels for the tested compounds, all the compounds will work and a truer measure of the effectiveness of the inventive compositions is seen at lower dosages

Contact angle measurement provides information about the hydro¬ phobicity of a simulated stickies surface and the change in hydrophobicity as surface active materials are adsorbed and/or desorbed at the surface If the contact angle of the treated sample is lower than that of the untreat¬ ed sample, it indicates that the surface becomes more hydrophilic or less tacky with treatment

As seen in Table I, serum albumin and a blend of albumin/globulin serum protein proved more effective at reducing tackiness of the surface than the high molecular weight gelatin as well as other proteins

Further studies were performed using a goniometer to measure the contact angle The Mylar or tape adhesive surface is clamped on a film stage and placed inside a glass test cell The test solution is added to the cell by carefully pouring 15 mL of the solution into the cell The whole test cell is then placed inside the chamber of a goniometer available from Kruss as G1 Model The Mylar or tape surface was immersed in the solu¬ tion for 30 minutes to simulate the contact time in STDT An air bubble was positioned on the underside of the Mylar or tape surface using a microsyπnge with an inverted tip The contact angle of the air bubble was measured at various time intervals at room temperature or 50°C

The results of this testing of various proteins are presented in Tables III and IV

TABLE III

Goniometer Contact Angle Measurements at 25°C

Con icentration Contact Treatment pprn Surface Anαle

Water Mylar 58 Tape 91

Low molecular weight 5 Mylar 48 gelatin (MW * 1 ,500) 5 Tape 47 2 Tape 65

Low molecular weight 2 5 Mylar 49 gelatin (MW * 2,000)

Meat soluble protein 2 Tape 46

Animal protein 2 Mylar 46

5 Mylar 49 5 Tape 39

High molecular weight gelatin 2 Mylar 43 (MW * 50,000-100,000) 2 5 Mylar 37

TABLE III (cont'd)

Goniometer Contact Angle Measurements at 25°C

Concentration Contact

Treatment PPm Surface Anαle Polyvinyl alcohol 2.5 Tape 41

2.5 Mylar 45

2.5 Tape 65

5 Mylar 41

5 Tape 54

Globulin/albumin serum protein 2 Mylar 30 Bovine albumin 2 Mylar 12 Porcine albumin 2 Mylar 21 Spray-dried animal blood cells 2 Mylar 17 Nonylphenol ethoxylate ¹ 5 Mylar 59 10 Mylar 52

Ethyleneoxide-propyleneoxide 5 Mylar 60 Copolymer ² 10 Mylar 57

TABLE IV Goniometer Contact Angle Measurements at 50°C

Cc )ncentratior 1 Contact Treatment pprn Surface Anαle

Water Mylar 56

High molecular weight gelatin 2.5 Mylar 34

Nonylphenol ethoxylate ¹ 5 Mylar 48

Ethyleneoxide-propyleneoxide 5 Mylar 50 copolymer ²

Polyvinyl alcohol 2.5 Mylar 24 0.5 Mylar 50

Albumin/Globulin 2.5 Mylar 29 Serum protein 0.5 Mylar 29 0.25 Mylar 33

'Surfonic ^® N-95 available from Rohm & Haas Pluronic ^,s> F-108 available from BASF Wyandotte, Inc.

Table III demonstrates that at 25°C, the bovine albumin, porcine albumin, globulin/albumin serum protein and spray-dried animal blood cells show improvement over other known inhibitors by the significant reduction of the contact angle on both Mylar and adhesive tape surfaces

As evidenced in Table IV, at 50°C, the albumin/globulin serum protein exhibited much lower contact angle on the Mylar as compared to the gelatins tested, proving to be effective as a detackifier

While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modi¬ fications 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