USE OF STARCH WITH SYNTHETIC METAL SILICATES FOR IMPROVING A

PAPERMAKING PROCESS

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part to United States Patent Application Serial No.

11/231,662, which was filed on September 21, 2005, from which filing priority is hereby claimed and the disclosure of which is hereby incorporated by reference.

FIELD OF THE INVENTION

This disclosure relates to a method for increasing retention and dewatering during a papermaking process through the addition of a synthetic metal silicate to the papermaking process, as well as paper or paperboard produced from a synthetic metal silicate. This disclosure also relates to a method for increasing retention and dewatering during a papermaking process through the addition of a synthetic metal silicate and starch to the papermaking process.

BACKGROUND

Retention and dewatering systems for use in papermaking currently utilize any component or combination of components from the following list: flocculant, coagulant, and inorganic particulate. When one or more of these chemistries are added to an aqueous slurry containing cellulose fibers, fines, fillers, and other additives, and subsequently introduced onto a paper machine, sheet formation is facilitated with observed improvements in the retention and dewatering. Throughout the recent history of papermaking several different inorganic particulates have been used as part of the retention and dewatering system. The inorganic particulate has ranged from colloidal silica or silica sols, modified silica sols, and borosilicate sols, to naturally occurring smectite clays, used singly or in combination with each other. Even so, there is a need for a new synthetic inorganic particulate that provides even better retention and dewatering without sacrificing the properties of the paper or paperboard.

SUMMARY OF THE INVENTION

The present invention also provides for a method for increasing retention and dewatering during the papermaking process, comprising the step of: adding an effective amount of SMS to said papermaking process.

The present invention provides for a paper or paperboard produced from a slurry comprising cellulose fibers and an effective amount of SMS and starch.

The present invention also provides for a method for increasing retention and dewatering during the papermaking process, comprising the step of: adding an effective amount of SMS and starch to said papermaking process.

DETAILED DESCRIPTION OF THE INVENTION

"SMS" means a synthetic metal silicate of the following formula: (Mg ₃ . _* Vi _x ) Si ₄ Na _O j ₃ [Fy (OH) _2- J ₂ Oio _, wherein: x = 0 to 3.0; a.ndy = 0.01 to 2.0.

The SMS of the present invention can be made by combining simple silicates and lithium, magnesium, and fluoride salts in the presence of mineralizing agents and subjecting the resulting mixture to hydrothermal conditions. As an example, one might combine a silica sol gel with magnesium hydroxide and lithium fluoride in an aqueous solution and under reflux for two days to yield SMS. (See Industrial & Chemical Engineering Chemistry Research (1992), 31(7), 1654, which is herein incorporated by reference). One can also obtain the SMS directly from Nalco Company, Naperville, IL 60563. Currently SMS is available as Nalco Product No. DVP4J001.

"Papermaking process" means a method of making paper products from pulp comprising forming an aqueous cellulosic papermaking furnish, draining the furnish to form a sheet and drying the sheet. The steps of forming the papermaking furnish, draining and drying may be carried out in any conventional manner generally known to those skilled in the art. "COD" means chemical oxygen demand

"GCC" means ground calcium carbonate.

"HWK" means hardwood bleached kraft

"MCL" means mean chord length.

"SWK" means softwood bleached kraft. "TMP" means thermal mechanical pulp.

"PCC" means precipitated calcium carbonate.

"CTMP" means chemical thermal mechanical pulp.

"GWD" means groundwood pulp.

"DIP" means deinked pulp "kg" means Kilogram

"T" means ton

As stated above, the present invention provides for a method for increasing retention and dewatering during the papermaking process, comprising the step of adding an effective amount of SMS. SMS maybe added to said papermaking process as solid or as a dispersion. In one

embodiment, the SMS is added to a slurry located in said papermaking process. The slurry may comprise one or more cellulose fibers, fines and fillers dispersed in water.

In another embodiment, the effective amount of SMS added to said slurry is from 0.001 to 6 kg/T based upon the solids in the slurry or from 0.01 to 3 kg/T based on solids in the slurry. In another embodiment, a colloidal silica is added to the slurry of said papermaking process. In a further embodiment, the weight ratio of colloidal silica to SMS is 0.01:1 to 100:1.

In another embodiment, a colloidal borosilicate is added to said slurry of said papermaking process. In a further embodiment, the weight ratio of colloidal borosilicate to SMS is 0.01:1 to 100:1. In another embodiment, one or more polymers may be added to the slurry prior to, after, or in combination with the addition of said SMS. The polymers may be selected from the group consisting of the following types of polymers: cationic; anionic; non-ionic; zwiterionic; and amphoteric. In a further embodiment, the cationic polymers are selected from the group consisting of: naturally occurring carbohydrates; synthetic linear, branched, cross-linked flocculants; organic microparticulates; copolymers of acrylamide and diallydimethylammonium chloride; copolymers of dimethyl aminoethyl (meth)acrylate and acrylamide; copolymers of (meth)acrylic acid and acrylamide; copolymers of dimethyl aminoethyl (meth)acrylate and acrylamide; copolymers of dimethyl aminoethyl (meth)acrylate-methyl chloride quat and acrylamide; and terpolymers of dimethyl aminoethyl (meth)acrylate, acrylamide, and (meth)acrylic acid. An example of the organic microparticles referred to above is found in US Patent 5,274,055, Honig and Harris, which is herein incorporated by reference. In yet a further embodiment, the type of naturally occurring carbohydrates are selected from the group consisting of: guar gum and starch.

In a further embodiment, the anionic polymers are selected from the group consisting of: homo and copolymers of acrylic acid, and copolymers of methacrylamide 2-acrylamido-2- methlypropane sulfonate with acrylamide or methacrylamide.

In a further embodiment, the non-ionic polymers are selected from the group consisting of: polyethylene oxide, and polyacrylamide.

In another embodiment, one or more organic coagulants, inorganic coagulants, or combination thereof are added to said slurry. In yet a further embodiment, the organic coagulants are polyalkylenepolyamines prepared from epichlorohydrindimethylamine and ethyleneimines. In yet a further embodiment, the inorganic coagulants are selected from the group consisting of: alum; polyaluminum chloride and polyaluminum silicate sulfate.

In another embodiment, the invention comprises a method for increasing retention and dewatering during a papermaking process comprising the steps of adding an effective amount of SMS, wherein said SMS is added to a slurry of said papermaking process; and providing a paper or paperboard machine and forming a dry paper or paperboard. In a further embodiment, the SMS is added to said slurry prior to dewatering and forming a dry paper or paperboard on said paper or paperboard machine.

As stated above, the present invention provides for a method for increasing retention and drainage in a papermaking process comprising the steps of: adding both an effective amount of starch and an effective amount of SMS to a slurry of said papermaking process, wherein said starch is selected from the group consisting of: tapioca starch; potato starch; corn starch; waxy maize starch; rice starch; and wheat starch. In a further embodiment, one or more polymers may be added to the slurry. In yet a further embodiment, the polymers are selected from the group consisting of: cationic polymers; anionic polymers; non-ionic polymers; zwitterionic polymers; and amphoteric polymers. In another embodiment, the starch is added to said slurry, prior to, after, or in combination with the addition of said SMS.

In another embodiment, an effective amount of starch is added to the slurry of said papermaking process in an amount from about 0.1 to about 25 kg/t, based upon the solids in the slurry. In another embodiment, an effective amount of starch is added to the slurry of said papermaking process in an amount from about 2.5 to about 12.5 kg/t, based upon the solids in the slurry.

As stated above, the present invention provides for a method for increasing retention and drainage in a papermaking process comprising the steps of: adding both an effective amount of modified starch and an effective amount of SMS to a slurry of said papermaking process. In a further embodiment, one or more polymers maybe added to the papermaking process. In yet a further embodiment, the polymers are selected from the group consisting of: cationic polymers; anionic polymers; non-ionic polymers; zwitterionic polymers; and amphoteric polymers.

In another embodiment, the modified starch is added to said slurry, prior to, after, or in combination with the addition of said SMS.

In another embodiment, the modified starch is selected from the group consisting of: tapioca starch; potato starch; corn starch; waxy maize starch; rice starch; and wheat starch.

In another embodiment, the modified starch is either cationic or amphoteric.

In another embodiment, the slurry is a thin stock or a thick stock.

In another embodiment an effective amount of modified starch is added to said slurry of said papermaking process in an amount from about 0.1 to about 25 kg/t, based upon the solids in the slurry.

In another embodiment an effective amount of modified starch is added to said slurry of said papermaking process in an amount from about 2.5 to about 12.5 kg/t, based upon the solids in the slurry.

The present invention will be further described in the following examples, which show various application methods, but are not intended to limit the invention prescribed by the appended claims. Example 1

A synthetic lightweight coated thin stock having a consistency of 0.7 wt% was prepared. The thin stock solids consist of 50 dry wt% hydrogen peroxide bleached mixed TMP, 25 dry wt% bleached softwood kraft, 14.5 wt% kaolin clay, and 10.5 wt% ultrafine GCC. The mixed TMP consists of 80 wt% hardwood and 20 wt% softwood fiber. The bleached softwood kraft is dry lap pulp purchased from Weldwood, Hinton Canada. The softwood kraft was a repulped in deionized water and beaten to a 360 rnL Canadian Standard Freeness. Kaolin clay was purchased from Imerys, 100 Mansell Court East, Suite 300, Roswell, G 30074, while the GCC was obtained from Omya North America, 100 North Point Center East, Suite 310, Alpharetta, GA 30022. The thin stock was produced from the corresponding thick stocks by using the bleached mixed TMP filtrate and deionized water containing 2.0 mM calcium, 0.23 mM magnesium, 4.9 mM sulfate and 21.8 mM sodium. An appropriate quantity of salt solution was used with the TMP filtrate to yield the thin stock at 0.7 wt% consistency with 950 mg/1 COD, a pH of 8.2, and a conductivity of 2500 microS/cm. The cationic starch used herein is Solvitose N and is available from Avebe, Prins

Hendrikplein 20, 9641 GK Veendam, The Netherlands. The Commercial Product used in this example is CP 1131, which is a non-fluoride synthetic hydrous sodium lithium metal silicate and can be obtained from Rockwood Specialties, Ltd, Widnes, Cheshire, United Kingdom. The Nalkat® 2020 and 61067 are commercial products, which can be obtained from Nalco Company, 1601 West Diehl Road, Naperville, IL. 60563.

Flocculation activity was measured by Focused Beam Reflectance Measurement (FBRM), also known as Scanning Laser Microscopy or SLM, using the Lasentec™ M500 (Lasentec, Redmond, Wash.). A description of the theory behind the operation of the FBRM can be found in Preikschat, F. K. and Preikschat, E., "Apparatus and method for particle analysis," U. S. Patent Office, 4,871,251, 1989, which is herein incorporated by reference. The following

references are incorporated by reference and describe in detail how this technique is used to measure performance and how it correlates to paper machine experience: Gerli, A., Keiser, B. A ₁ , and Surya, P. I., "The use of focused beam reflectance measurement in the development of a new nanosize particle," Appita J., 54(1), 36-40(2001); Clemencon, I. and Gerli, A., "The effect of flocculant/microparticles retention programs on floe properties," Nord. Pulp Pap. Res. J., 14(1), 23-29(1999); Gerli, A., Oosterhof, F., and Keiser, B. A., "An inorganic nanosize particle - part of a new retention/dewatering system," Pap. Technol. (Bury, U. K.), 40(8), 41-45(1999). The change in the number average chord length or MCL of the thin stock as a function of time is used to characterize a flocculation response. The change in MCL caused by addition of particulate correlates with the additive performance in the papermaking process with the greater the δMCL (change in mean chord length) indicating better performance. The peak change in MCL gives a representation of the speed and extent of flocculation under the shear conditions present.

A 300 niL of synthetic light weight coated furnish was poured into a 500 mL glass beaker and place it onto the Focused Beam Reflectance Measurement (FBRM) stand. Mixing was started at 710 rpm. Coagulant, starch, flocculant and particulate were added as outlined in table entitled "Addition Sequence."

Addition Sequence

Time Event

0 start mixing at 710 rpm

6 add 4 kg/ton Nalkat® 2020

21 add 5 kg/ton Solvitose-N starch

51 add 1.5 kg/ton 61067

96 add particulate

In this example, the performance of the SMS is compared to that of the Commercial Product. The change in mean chord is compared for the samples. The results are illustrated in the following table.

Note: The inorganic particulate is added on an actives basis.

As can be seen from this data, the SMS provides significantly larger flocculation response compared to the Commercial Product. This larger flocculation response of the SMS has been shown to correlate with greater fines particle retention during papermaking.

Example 2

A blended synthetic alkaline fine paper thin stock at 0.5 wt% consistency was prepared. The solids of the thin stock are composed of 32 wt% SWK, 48 wt% HWK, and 20 wt% ultrafine GCC. The SWK is prepared from dry lap obtained from a mill located in Alberta Canada, repulped in deionized water at 2-4 wt% consistency and beaten to a 360 mL Canadian Standard Freeness (CSF). The HWK was prepared separately from dry lap originating from a Northern US mill, repulped in deionized water at 2-3 wt% consistency, and beaten to 360 mL CSF. The GCC was Ultrafine obtained from Omyafil. The corresponding thick stocks and GCC were combined and diluted with deionized water containing 1.5 mM calcium, 0.74 niM magnesium, 2.2 niM sodium, 2.99 mM chloride, 0.75 mM sulfate and 2.2 mM bicarbonate. The thin stock was 0.5 wt% consistency, with a pH of 8.1 and a conductivity of 600 microS/cm .

The comparative particulate in this example is Laponite® RD available commercially from Rockwood Specialties, Ltd, Widnes, Cheshire, United Kingdom. The Laponite® RD is a synthetic hydrous sodium lithium magnesium silicate which is identified by CAS No. 533320- 86-8 and has a typical chemical composition based on weight percent of: SiO ₂ 59.5; MgO 27.5; Li ₂ O 0.8; and Na ₂ O 2.8.

A 300 mL of synthetic alkaline fine paper slurry was poured into a 500 mL glass beaker and place it onto the Focused Beam Reflectance Measurement (FBRM) stand. Start mixing at 710 rpm. Starch, flocculant and inorganic particulate were added in the following addition sequence:

Addition Sequence

Time Event

0 start mixing at 710 rpm

15 add 5 kg/ton Solvitose-N starch

30 add 2 kg/ton 61067

75 add particulate

120 stop

The FBRM application is described in the previous example. In this example, the SMS is compared to Laponite RD. The results are summarized in the following table.

Note: The inorganic particulate is added on an actives basis.

As can be seen from this data, the SMS provides a significantly larger flocculation response compared to the previously existing and commercially available synthetic hydrous sodium lithium magnesium silicate known as Laponite RD. This larger flocculation response generated by SMS indicates greater fines retention during papermaking compared to what is currently available.

Example 3

In this example, the dewatering performance of the SMS is compared to that of a commercially available material in a light weight coated stock obtained from a mill in the

Canada. The make-up of the stock fiber is outlined in the table below. The cationic starch used in this study was Cato 31, which is commercially available from National Starch, 742 Grayson Street Berkeley, CA 94710-2677. The PCC is produced at the mill and was obtained therefrom. Nalkat® 7655 and Nalco 7526 are commercial products available from Nalco Company, 1601 West Diehl Road, Naperville, IL 60563. The Commercial Product used in this example is CP 1131, which is a non-fluoride synthetic hydrous sodium lithium metal silicate and can be obtained from Rockwood Specialties, Ltd, Widnes, Cheshire, United Kingdom.

Table. Stock fiber composition (wt%) for Example 3

Fiber Source

Coated Broke 19%

Uncoated Broke 6%

Mixed Fiber 75%

CTMP Peroxide Bleached 47%

GWD Peroxide Bleached 4%

CTMP 15%

Softwood Bleached Kraft 34%

PCC 3%

The blended fiber and filler solids were diluted with white water to 0.7 wt% consistency.

Vacuum dewatering analysis of the products was carried out using the Vacuum Drainage Tester (Herein referred to as VDT).

The VDT is a pad-forming device, meaning a cellulose fiber containing slurry is drained under vacuum onto a filter paper or wire resulting in the formation of a pad. As such, it is similar in principle of operation and dewatering information provided, to other vacuum dewatering devices described in the literature (e.g. see Forsberg, S. and Bengtsson, M., "The Dynamic Drainage Analyzer, (DDA)," Proceedings Tappi 1990 Papermaker's Conference, pp. 239-45, Atlanta, GA, April 23-25, 1990, which is incorporated by reference). The VDT used herein, identified as VDT+, which is available from Nalco Company, 1601 West Diehl Road, Naperville, IL, 60563, was modified so that mixing of chemical additives with the slurry was done in an upper chamber of the instrument. Subsequently, the treated slurry is transferred by gravity from the upper mixing chamber to the vacuum dewatering chamber. The dewatering rate, in mL/sec was calculated by determining the time necessary to collect 400 mL of filtrate or white water. The operational conditions are summarized in the table below.

Table: VDT+ Test Conditions

The results of the dewatering comparison are shown in the table below. As can be seen a higher dewatering rate, i.e. 15.7 mL/sec, was obtained with the inorganic particulate of this invention, the SMS, as compared to Commercial Product.

Note: The inorganic particulate is added on an actives basis.

Example 4

In this example, the effect of various modified starches on the dewatering performance of SMS, is determined in a 100% peroxide-bleached TMP stock from a paper mill in Canada. The stock characteristics are given in Table I.

Table I Characteristics of peroxide-bleached TMP Stock

The cationic corn starch used in this study is Cato 31, commercially available from National Starch, 742 Grayson Street, Berkeley, CA 94710-2677. The cationic tapioca starches used in this study are Dynabond 132 and Dynabond 180, medium and high charge, respectively ₅ commercially available from International Additive Concepts, 380 Crompton Street, Charlotte, NC ₅ 28273-6214 The cationic potato starch used in this study is Topcat 771 , commercially available from Penford Products, 1001 First Street, P.O. Box 428, Cedar Rapids, IA, 52404-2175. They are described in Table II.

Table II Measured Charge Density of Various Starches

The flocculant used is 6Dl 6 that is commercially available from Nalco Company, 1601 West Diehl Road, Naperville, IL 60563. Gravity dewatering analysis of the programs was carried out using the Dynamic Filtration System (DFS-03) manufactured by Mutek (BTG, Herrching, Germany). During dewatering measurement, 1 L of the stock is filled into the stirring compartment and subjected to a shear of 800 rpm during the addition of the chemical additives as described in Table III. The stock is drained through a 25 mesh screen for 60 seconds and the filtrate amount is determined gravimetrically over the drainage period.

Table HI Dynamic Filtration System (DFS-03) Test Conditions

The results of the dewatering comparison for SMS with the various modified starches previously described in Table II are given in Table IV as the drainage mass collected after 60 seconds. The peroxide-bleached TMP stock used is described in Table I. As can be seen, a significantly higher dewatering performance was observed for the 6D16/SMS program in the presence of the potato and tapioca starches compared to corn starch.

Table IV

Dewatering performance of 6D16/SMS program with different modified starches 6Dl 6 dosed @ 0.6 kg/ton, SMS dosed @ 2 kg/ton

Example 5

This example demonstrates the effect of various modified starches described in Table II on the dewatering performance of SMS, using a stock described in Table V from a paper mill in Canada.

Table V Characteristics of GWD/peroxide bleached GWD/DIP/CTMP stock

The cationic corn starch used in this study is Cato 31, commercially available from National Starch, 742 Grayson Street, Berkeley, CA 94710-2677. The cationic tapioca starches used in this study are Dynabond 132 and Dynabond 180, medium and high charge, respectively,commercially available from International Additive Concepts, 380 Crompton Street, Charlotte, NC, 28273-6214 The cationic potato starch used in this study is Topcat 771, commercially available from Penford Products, 1001 First Street, P.O. Box 428, Cedar Rapids, IA, 52404-2175. They are described in Table II. Gravity dewatering test was carried out using the Dynamic Filtration System (DFS-03) manufactured by Mutek (BTG, Herrching, Germany). During dewatering measurement, 1 L of the stock is filled into the stirring compartment and subjected to a shear of 800 rpm during the addition of the chemical additives as described in Table III. The stock is drained through a 25 mesh screen for 60 seconds and the filtrate amount is determined gravimetrically over the drainage period. The flocculant used for some of the tests is 61067 that is commercially available from Nalco Company, 1601 West Diehl Road, Naperville, IL 60563.

The dewatering results for SMS dosed at 1.0 kg/t with cationic corn, potato and tapioca starches and flocculant dosed at 1.0 kg/t are shown in Table VI as the drainage mass collected after 60 seconds. Higher drainage masses were obtained in the presence of medium charge tapioca and potato starches compared to medium charge corn starch, indicating superior drainage performance for these programs compared to the program with medium charge corn starch. Similarly, higher drainage performance was observed for medium charge tapioca starch compared to medium charge corn starch for tests carried out without flocculant as part of the program as shown in Table VII.

Table VI

Dewatering performance of 61067/SMS program with different modified starches 61067 dosed @ 1.0 kg/t, SMS dosed @ 1.0 kg/t

Table VII.

Dewatering performance of SMS program with different modified starches

SMS dosed @ 2.0 kg/t