USOO67841.46B1 (12) United States Patent (10) Patent No.: US 6,784,146 B1 Luo et al. (45) Date of Patent: Aug. 31, 2004

(54) DEINKING METHOD AND COMPOSITION 5,225,046 A 7/1993 Borchardt FOR WASTEPAPER 5,281,348 A 1/1994 Letscher 5,387,355 A 2/1995 Letscher

(75) Inventors: Jing Luo, Acworth, GA (US); DavidAA D. S.E.2 : - - 2 A : 189. allen8LO . . . . .et . . . al...... 162/5 ES"E. SS Mill 5,651861. A * 7/1997 Larson et al...... 162/5 y, Marietta, 5,665,204 A * 9/1997 Rodriguez et al...... 162/5 5,807464 A * 9/1998 Jobbins et al...... 162/5 (73) ASSignee: syn Chemicals, Inc., Marietta, GA 6,103,056. A 8/2000 Irinatsu et al...... 162/4 FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this FR 1453.204 8/1966 patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. GB 1347971 2/1974 OTHER PUBLICATIONS (21) Appl. No.: 09/699,303 U.S. Environmental Protection Agency; Premanufacture (22) Filed: Oct. 27, 2000 Notice for New Chemical Substances. Case No. TS-OOO122 7 (incomplete article). (51) Int. Cl.' ...... C11D 1/72 U.S. Environmental Protection Agency; Premanufacture (52) U.S. Cl...... 510/174; 510/356; 510/421; Notice for New Chemical Substances, Document Control 1624; 1625 No. 51980000062; EPA Case No. P98.62–65; TS-000122; (58) Field of Search ...... Sio S.R." pp. 000001-000163; Aug. 18, 1998. s s * cited by examiner (56) References Cited Primary Examiner-Charles Boyer U.S. PATENT DOCUMENTS (74) Attorney, Agent, or Firm-Clark G. Sullivan; King & 3,098,784. A 7/1963 Gorman, Jr. et al. Spalding LLP 3,354,028 A 11/1967 Illingworth (57) ABSTRACT 3,392,083 A 7/1968 Illingworth 3,446,696 A 5/1969 Illingworth The present invention is a deinking method and composition 3,501,373 A 3/1970 Illingworth that uses at least 50% by weight based on the total weight of 3,766,001 A 10/1973 Gleason et al. 3,767,524 A 10/1973 Gleason Surfactants of non-ionic, C16 to C25 aliphatic, monohydric 3,808.089 A 4/1974 Von Koeppen et al. alcohol alkoxylates having 14 to 40 moles of ethylene oxide 3,932.206 A 1/1976 Illingworth et al. per mole of alcohol and 0 to 10 moles of propylene oxide per 4,162,186 A 7/1979 Wood et al. mole of alcohol. Using deinking compositions to deink 4,311,552 A 1/1982 Brucato et al. wastepaper pulp wherein the Surfactants primarily include 4,360,439 A 11/1982 Calmanti et al...... 252/61 the C16 to C18 aliphatic alcohol alkoxylates of the invention 4.483,741 A 11/1984 Maloney et al. produces paper having excellent brightness and low effec 4,518,459 A 5/1985 Freis et al...... 162/5 tive residual ink concentrations. In addition, a low amount of 4,618,400 A 10/1986 Wood et al. sizing agents is used to produce paper having acceptable 4,666.558 A * 5/1987 Wood et al...... 162/5 4,935,096 A 6/1990 Gallagher et al. levels of water repellency. 4.959,123 A 9/1990 Lehmann et al...... 162/5 5,094,716 A 3/1992 Letscher 12 Claims, No Drawings US 6,784,146 B1 1 2 DENKING METHOD AND COMPOSITION impacts the coefficient of friction, which can cause problems FOR WASTEPAPER in the paper Such as crepe wrinkles, bursts and telescoping. Therefore, there is a need in the art to produce a deinking composition that reduces the amount of sizing agents needed FIELD OF THE INVENTION to produce paper having high water repellency. The present invention relates to deinking methods and compositions for waste paper and particularly to Washing SUMMARY OF THE INVENTION ink removal methods and compositions for recycle mills that The present invention is a deinking method and compo use leSS Sizing agents to produce paper having increased Sition that overcomes the problems associated with conven brightness and reduced effective residual ink concentration tional deinking compositions. The deinking method and (ERIC). composition uses at least 50% by weight based on the total weight of Surfactants of non-ionic, C16 to C25 aliphatic, BACKGROUND OF THE INVENTION monohydric alcohol alkoxylates having 14 to 40 moles of The paper industry has been practicing wastepaper recy ethylene oxide per mole of alcohol and 0 to 10 moles of cling to regenerate usable cellulosic fiber for paper making 15 propylene oxide per mole of alcohol. It has been discovered for many decades. In these processes, ink is removed from that using deinking compositions to deink wastepaper pulp the wastepaper pulp using a Suitable deinking composition. wherein the surfactants primarily include the C16 to C25 By controlling the deinking process, a recycling mill can aliphatic alcohol alkoxylates of the invention unexpectedly affect the properties of the paper Such as the brightneSS and produces paper having increased brightness and Signifi can improve the usability of the cellulosic fiber for paper cantly decreased effective residual ink concentration manufacturing. (ERIC). Furthermore, it has also been discovered that using There are two major types of deinking methods or these C16 to C25 aliphatic alcohol alkoxylates to deink practices, namely flotation/washing combination deinking wastepaper pulp unexpectedly produces paper that requires and wash deinking. Flotation/washing combination deinking a Substantially lower amount of sizing agents to produce refers to a deinking process wherein the ink released by the 25 paper having acceptable levels of water repellency. deinking composition is Separated from the cellulosic fibers Therefore, the deinking composition of the invention can be primarily through the flotation devices or flotation cells of used in industries Such as the newsprint industry with the recycling process prior to passing the pulp through reduced sizing aent deposition on the machinery and thus washing stages (e.g. throuh washers). Wash deinking, on the increased paper machine runability. Furthermore, the deink other hand, refers to a deinking process wherein the ink ing composition of the invention produces low levels of released by the deinking composition is separated from the foaming as is desired in wastewater deinking processes. cellulosic fibers primarily in the Washing Stages. The present invention comprises a deinking composition Many deinking compositions have been developed spe comprising one or more Surfactants, the Surfactants includ cifically for wash deinking processes. In particular, various 35 ing at least 50% by weight, preferably at least about 70% by types of Surfactants have been described as effective deink weight, and more preferably at least about 80% by weight ing agents. These Surfactants include alkyl phenol based on the total weight of Surfactants of non-ionic, C16 to alkoxylates, alpha olefin Sulfonates, and aliphatic alcohol C25 aliphatic, monohydric alcohol alkoxylates having 14 to alkoxylates, as well as many other nonionic and anionic 40 moles of ethylene oxide per mole of alcohol and 0 to 10 Surfactants and mixtures of Surfactants and other chemical 40 moles of propylene oxide per mole of alcohol. In one agents. Generally, all of these compositions are required to preferred embodiment of the invention, the surfactants in the have fluidity at room temperature for ease of feeding. composition consist essentially of non-ionic, C16 to C25 Conventional deinking compositions for wash deinking aliphatic, monohydric alcohol alkoxylates having 14 to 40 processes have been directed to improving deinking perfor moles of ethylene oxide per mole of alcohol and 0 to 10 mance only, and particularly directed to removing ink from 45 moles of propylene oxide per mole of alcohol. Preferably, pulp to produce pulp with acceptable brightness for paper the aliphatic alcohol alkoxylates of the invention are C16 to making. There is a need to further improve the brightness of C18 aliphatic alcohol alkoxylates. For the C16-C25 ali the paper pulp produced by wash deinking processes. phatic alcohol alkoxylates of the invention, the average Furthermore, conventional deinking compositions signifi number of ethylene oxide groups per alkoxylate molecule is cantly increase the water absorbency of paper and thus do 50 preferably from about 16 to about 30 and the average not provide the amount of water repellency desired for number of propylene oxide groups per alkoxylate molecule certain types of paper Such as recycled newSprint. AS a is preferably from 0 to about 6. The C16-C25 aliphatic result, paper made from wash deinking processes that use alcohol alkoxylates of the invention can be Saturated or conventional deinking compositions has poor press room unsaturated. Preferably, the C16 to C25 aliphatic alcohol performance in the printing facility due to the extreme water 55 alkoxylates are Saturated and have the formula: absorbency of the paper. To improve the press room runability, paper manufacturers have had to use large amounts of a sizing agent, Such as alkyl ketene dimer wherein R is a straight chain or branched chain C16-C25 (AKD), in the manufacture of the paper to improve the water alkyl group, n is from 14 to 40 and m is from 0 to 10. More resistance (size) of the paper. Unfortunately, however, using 60 preferably, the C16-C25 aliphatic alcohol alkoxylates of the large amounts of sizing agents results in the deposition of invention are straight chained. The C16-C25 aliphatic alco sizing agents on paper machinery, which is a significant hol alkoxylates of the invention are preferably based on problem in the recycled newSprint industry. In particular, primary or Secondary alcohols, and are more preferably because of the deposition of sizing agents on paper based on primary alcohols. The deinking composition of the machinery, the paper machinery must be cleaned on a 65 invention can further include from 0 to about 30% by weight frequent basis thereby affecting the runability of the paper of one or more fatty acids based on the total weight of machinery. Moreover, the excessive use of sizing agents also surfactants. Preferably, the fatty acids are C8 to C20 fatty US 6,784,146 B1 3 4 acids and can be Selected from the group consisting of lauric average number of ethylene oxide groups per molecule in acid, oleic acid, Stearic acid, tall oil fatty acid, tallow fatty the C16 to C25 aliphatic alcohol alkoxylates of the invention acid, coconut fatty acid, and mixtures thereof. is from about 14 to about 40 moles, and preferably from The present invention further includes a process for about 16 to about 30. The average number of propylene deinking wastepaper comprising the Steps of contacting oxide groups per molecule in the C16 to C25 aliphatic wastepaper pulp with the deinking composition discussed alcohol alkoxylates of the invention is from 0 to about 10, above. The surfactants (including the C16 to C25 aliphatic preferably from 0 to about 6. When the C 16 to C25 aliphatic alcohol alkoxylates of the invention) are preferably present alcohol alkoxylates of the invention include both ethylene in the deinking composition in an amount from about 0.3% oxide and propylene oxide groups, these alkoxylate groups to about 0.7% by weight based on the oven-dry weight of the can occur randomly in the molecule or can occur in blockS. wastepaper pulp. In addition, the wastepaper pulp is pref The C16 to C25 aliphatic alcohol alkoxylates used in the erably contacted with the deinking composition at a pH of deinking compositions of the invention include one or more from greater than 7 to about 10. The resulting wastepaper aliphatic alcohol alkoxylates within the C16-C25 range and pulp can be used to make paper having increased brightness are typically blends of two or more of these alkoxylates. and low effective residual ink concentrations. In addition, in 15 The C16 to C25 aliphatic alcohol alkoxylates used in industries that use Sizing agents to produce paper Such as the accordance with the invention can be prepared by any recycled newsprint industry, the wastepaper pulp can be methods known in the art. For example, it is known in the used to make paper having good water repellency without art to produce aliphatic alcohol alkoxylates by adding to an using large amounts of Sizing agents. alcohol or mixture of alcohols to be ethoxylated or These and other features and advantages of the present propoxylated, a calculated amount, e.g., from about 0.1 invention will become more readily apparent to those skilled percent by weight to about 0.6 percent by weight, preferably in the art upon consideration of the following detailed from about 0.1 percent by weight to about 0.4 percent by description, which describes both the preferred and alterna weight, based on total alcohol, of a Strong base, typically an tive embodiments of the present invention. alkali metal or alkaline earth metal hydroxide Such as 25 Sodium hydroxide or potassium hydroxide, which Serves as DETAILED DESCRIPTION OF THE a catalyst for the ethoxylation or propoxylation. The result INVENTION ing mixture can be dried, as by vapor phase removal of any In the following detailed description, preferred embodi water present, and the amount of ethylene oxide or propy ments are described in detail to enable practice of the lene oxide needed to provide the desired amount of ethoxy invention. Although the invention is described with refer lation or propoxylation is added. The resulting mixture is ence to these specific preferred embodiments, it will be allowed to react until the ethylene oxide or propylene oxide understood that the invention is not limited to these pre is consumed, the course of the reaction being followed by ferred embodiments. But to the contrary, the invention the decrease in reaction pressure. Where the alcohols are to includes numerous alternatives, modifications and equiva be randomly ethoxylated and propoxylated, the desired lents as will become apparent from consideration of the 35 amounts of ethylene oxide and propylene oxide can be following detailed description. added together to the alcohol mixture. Alternatively, where The present invention is a deinking method and compo the alcohols are to include block ethoxylation and Sition for wastepaper recycling that produces paper having propoxylation, the desired amount of one of ethylene oxide excellent brightness, low ERIC values, and good water and propylene oxide is added first to the alcohol mixture and repellency properties without the need to use large amounts 40 reacted with the alcohol and then the other alkylene oxide is of sizing agents. The deinking compositions of the invention added. The C16 to C25 aliphatic alcohol alkoxylates used in typically include water, one or more Surfactants as described the invention are commercially available, e.g., from EthoX below, and optionally fatty acids. Corporation or ICI Surfactants/Uniqema. The Surfactants in the deinking compositions of the inven It has been discovered that the C16 to C25 aliphatic tion primarily include non-ionic, C16 to C25 aliphatic, 45 alcohol alkoxylates of the invention directly and positively monohydric alcohol alkoxylates having 14 to 40 moles of affect the brightness, ERIC values, and water repellency of ethylene oxide per mole of alcohol and 0 to 10 moles of the paper produced using the deinking compositions of the propylene oxide per mole of alcohol. More preferably, the invention. Therefore, the Surfactants of the invention include number of moles of ethylene oxide per mole of alcohol is at least 50% by weight, preferably at least about 70% by from 16 to 30, and even more preferably 18 to 25. In 50 weight, and more preferably at least about 80% by weight addition, the number of moles of propylene oxide per mole based on the total weight of Surfactants of these C16 to C25 of alcohol is more preferably from 0 to 6. The C16 to C25 aliphatic alcohol alkoxylates. To maximize the benefits of aliphatic alcohol alkoxylates of the invention are water the C16 to C25 aliphatic alcohol alkoxylates of the Soluble and can be Saturated or unsaturated, Straight chained invention, the Surfactants in the composition can consist or branched. In addition, the C16 to C25 aliphatic alcohol 55 essentially of non-ionic, C16 to C25 aliphatic, monohydric alkoxylates of the invention can be derived from primary or alcohol alkoxylates having 14 to 40 moles of ethylene oxide secondary alcohols. Preferably, the C16-C25 aliphatic alco per mole of alcohol and 0 to 10 moles of propylene oxide per hol alkoxylates are C16-C18 aliphatic alcohol alkoxylates. mole of alcohol. Nevertheless, the deinking composition can The C16 to C25 aliphatic alcohol alkoxylates of the inven include other Surfactants to provide other desired properties tion are preferably Saturated and Straight chained, and pref 60 to the deinking composition or to the resulting paper. For erably derived from primary alcohols. The preferred C16 to example, nonionic and anionic Surfactants Such as C16-C25 C25 aliphatic alcohol alkoxylates of the invention can be alkoxylated aliphatic polyols, C6-C15 alkoxylated aliphatic represented by the following formula: alcohols, alkoxylated fatty or other alkoxylated aliphatic carboxylic acids, alkoxylated aliphatic thiols, alkoxylated 65 aliphatic amines, alkoxylated aliphatic Sulfonates, and wherein R is a straight chain or branched chain C16-C25 alkoxylated C16-C25 aliphatic monohydric alcohols having alkyl group, n is from 14 to 40 and m is from 0 to 10. The low alkoxylation levels (e.g. less than 10 total alkoxylate US 6,784,146 B1 S 6 units per alcohol molecule). The deinking compositions of In industries that use sizing agents to produce paper the invention typically include no more than 50%, prefer having a desired level of water repellency Such as the ably no more than 30%, and more preferably no more than recycled newsprint industry, large amounts of sizing agents about 20% of these additional surfactants by weight based must be used with conventional deinking Surfactants on the total weight of Surfactants in the composition. In because the conventional deinking Surfactants significantly addition, the compositions of the invention are preferably increase the water absorbency of the paper. It has been “NPE-free,” i.e., are free of nonylphenol ethoxylates, which unexpectedly discovered that the C16 to C25 aliphatic are Sometimes considered not to be environmental friendly. alcohol alkoxylates of the invention have significantly leSS The deinking composition of the invention can further of an effect on increasing the water absorbency of the paper. include from 0 to about 30% by weight of one or more fatty Therefore, leSS Sizing agent is needed to produce paper acids based on the total weight of surfactants. Preferably, the having the same level of water repellency. This unexpected fatty acids are present in an amount from 0 to about 18% by benefit also benefits the runability of the paper making weight based on the total weight of Surfactants. The fatty machinery because leSS deposition of the sizing agents acids are preferably C8 to C20 fatty acids and can be occurs on the paper machinery. Therefore, the paper machin Selected from the group consisting of lauric acid, oleic acid, 15 ery can be operated without the need to frequently shut down Stearic acid, tall oil fatty acid, tallow fatty acid, coconut fatty the machinery to remove the sizing agent deposits or to even acid, and mixtures thereof. replace the paper machinery. The deinking compositions of the invention differ from The present invention will now be further described by conventional deinking compositions in that the deinking the following non-limiting examples, which demonstrate the compositions of the invention tend to be Solid or waxy at room temperature (i.e. 20 C.). Solid deinking compositions unexpected results produced by the C16 to C25 aliphatic have generally been avoided in conventional processes, alcohol alkoxylates of the invention. which have instead used liquid compositions. However, the deinking compositions can easily be made and kept fluid by EXAMPLE 1. maintaining the temperature of the deinking composition at 25 To demonstrate the improvement in deinking efficiency elevate temperatures, e.g. at greater than about 105 F. for produced by the deinking compositions of the invention, a the C16-C18 aliphatic alcohol alkoxylates of the invention. parallel comparison between conventional wash deinking Therefore, the deinking compositions of the invention can Surfactants or compositions and the deinking compositions be delivered to the pulping System using existing mill of the present invention was conducted as illustrated below. equipment. In each case, 0.45% of the deinking Surfactant(s) based on The deinking process of the invention is generally con the oven-dry weight of wastepaper were applied to the ducted by pulping printed wastepaper materials in the pres pulper at a pH of about 7.8. The pulp slurry was then ence of the deinking composition in a vessel that is com Subjected to a washing treatment by diluting the pulp slurry monly known in the art as a “pulper' or “repulper.” Pulping to 1% and thickening it to 8%. The deinked pulp was then is normally conducted under a specific Set of conditions 35 formed into a paper sheets or pads which were evaluated for including temperature, pH, water hardness, and the like. brightness and ERIC. ERIC is the abbreviation for Effective Preferably, the deinking temperature ranges from about Residual Ink Concentration and is measured with a TECH room temperature to about 150 F., the pH ranges from NIBRITE(RTB-1C instrument manufactured by Technidyne greater than 7 to about 10, and the water hardneSS ranges Corporation. The ERIC value is a measure of the effect of from about 30 to about 300 PPM CaCO. The deinking 40 the remaining ink, or the Overall darkening effect of the composition is added to the pulper in an amount Such that residual ink. The lower the ERIC value the lower the amount the amount of the surfactants (including the C16 to C25 of residual ink on the fiber. The ERIC value is convention aliphatic alcohol alkoxylates) present in the pulper are from ally used by mills, as well as research facilities and product about 0.3 to about 0.7% by weight based on the oven-dry development facilities to determine ink retention in paper weight of the waste paper. In addition to the deinking 45 sheet. Percentages are on a per weight basis. The results are composition of the invention, additional chemicals can be tabulated below. added to the pulper Such as Sodium hydroxide to control the pH of the composition in the pulper, and alkali metal phosphates and Silicates to modify the properties of the composition in the pulper. 50 Surfactants or Brightness, ERIC, After the pulping Step, the pulped slurry is Subjected to compositions % PPM cleaning, Screening, and washing Stages where ink and other Prior ar Commercial Wash Deinking SO.4 357 contaminants are separated from the cellulosic fiber Stream. Agent 1" Then, the deinked pulp is thickened and then bleached to the Prior ar Commercial Wash Deinking 50.6 344 target brightness and Sent to the paper machine where it is 55 Agent 2' Prior ar C linear alcohol (EO), 49.8 396 made into paper. Various paper machine additives, Such as Prior ar Dodecylphenol (EO)ss 46.8 662 Strength aids, drainage aids, and paper Sizing agents are Prior ar Secondary C-C alcohol 48.6 429 typically added to the paper machine. The paper is generally EOPO (cloud point at 41° C.) made to meet certain specifications Such as brightness, Prior ar Secondary C-Cls alcohol 49.1 340 EOPO (cloud point at 38° C.) count, strength, Size (water repellency) or water absorbency 60 Prior ar Nonylphenol (EO) 48.4 445 level, and the like. The pulping, cleaning, Screening, Prior ar Linear C alcohol 49.3 431 Washing, thickening and bleaching StepS used to make paper (EO)12/CCEO) according to the invention are generally known in the art and Prior ar Tridecyl alcohol (EO), 49.4 4.38 Prior ar Tridecyl alcohol (EO), 50.3 325 are described, for example, in R. G. Macdonald and J. N. Prior ar Tridecyl alcohol (EO)s 49.5 372 Franklin, Pulp and Paper Manufacture, 2" ed., Vol. 3; 65 Prior ar Tridecyl alcohol 49.9 367 Papermaking and Paperboard Making, McGraw-Hill Book (EO)ffatty acid at 85%/15% Co., New York, 1970. US 6,784,146 B1 7 8 EXAMPLE 2 -continued To demonstrate the versatility of the deinking composi Surfactants or Brightness, ERIC, tions of the invention, an exemplary deinking composition compositions % PPM of the invention and a conventional deinking composition Prior art Linear C14 is alcohol were tested at different processing conditions. The Superi (EO)/fatty acid at 85%/15% 50.3 336 ority of the deinking composition of the present invention at Prior art Linear C alcohol (EO)12 49.8 334 various pHs is demonstrated below. Prior art Linear C is Alcohol (EO), SO.1 359 Prior art Decyl alcohol (EO), 49.3 358 Invention Linear Cs alcohol (EO)2 52. t 219 Invention Linear Calcohol 52.3 237 (EO)/fatty acid at 85%/15% 85% Linear Invention Mixed C1s is alcohol (EO)2o 51.8 232 C14-15 Invention Mixed C1s is alcohol primary 85% Linear (EO)offatty acid at 85%/15% 51.5 243 alcohol C.1s alcohol Comparative Mixed C is alcohol 15 (EO)/15% (EO)./15% (EO)offatty acid at 70%/30% fatty acid fatty acid Invention Mixed C1s is alcohol (EO)1s 51.5 240 Invention Mixed C is alcohol (EO) 51.9 221 Solid Content, wt % 5 5 Invention Mixed C1s is alcohol (EO)2s 51.6 242 Temperature, F. 125 125 Invention Linear Cs alcohol (EO) as 52.2 225 Surfactant, wt % O.45 O.45 Invention Linear Calcohol 51.9 243 based on solid (EO)/(PO). Random Water Hardness, PPM 1OO 1OO Invention Linear Calcohol 51.5 256 Pulping time, min. 7 7 (EO)s (PO) Random Washing (1% to 8%) Yes Yes Invention Linear Calcohol 51.6 266 Brightness, 7% Brightness, 7% (EO) (PO). Blocked pH after pulping = 6.5 40.3 40.9 Invention Mixed C1s is alcohol 51.7 232 pH after pulping = 8.0 41.4 42.9 (EO)/SLF18 at 25 pH after pulping = 9.5 40.O 41.O 80/20 Invention Mixed C is alcohol 51.3 265 Washing was conducted by diluting the pulp slurry to 1% with water and (EO)/TDA8.5 at thickening the slurry to 8% on a mesh screen. 80/20 'Commercial Wash Deinking Agent 1 is believed to be a blend of EXAMPLE 3 C14-C15 alcohols with (EO) and fatty acids. °Commercial Wash Deinking Agent 2 is believed to include C14-C15 The Superiority of the deinking of composition the inven alcohols with (EO) as the main component. The fatty acid used in this example and the following examples primarily tion under various processing temperatures is demonstrated includes oleic acid. in the table below. SLF18 is an ethoxylated/propoxylated secondary C14 alcohol with a cloud point at 18 C. available from BASF Corporation. 35 TDA8.5 is an ethoxylated tridecyl alcohol with 8.5 moles of ethylene Oxide per molecule of alcohol. 85% Linear C14-15 primary 85% Linear The Surfactants tested in this example included deinking alcohol Cs alcohol Surfactants disclosed in prior art patents and commercially 40 (EO)/15% (EO)./15% available Surfactants, as well as the Surfactants of the present fatty acid fatty acid invention. Repeatedly, it was demonstrated that the Surfac Solid Content, 5 5 tants used in the deinking compositions of the invention wt % pH after pulping 8 8 were more effective in deinking waste paper. 45 Surfactant, wt % O.45 O.45 based on solid In particular, as shown above, the use of the C16 to C18 Water Hardness, 1OO 1OO aliphatic alcohol alkoxylates of the invention in deinking PPM Pulping time, 7 7 compositions repeatedly produced unexpected increases in min. brightness and decreases in ERIC values over conventional 50 Washing (1% to 8%) Yes Yes Surfactants. The benefits of the invention were even realized Brightness, Brightness, % % when up to about 20% of conventional surfactants were used Pulping 40.6 41.5 in the deinking composition and it is believed that greater Temperature = 115°E amounts of conventional surfactants (up to about 30% or Pulping 41.4 42.9 even up to about 50%) could be used with the surfactants of 55 Temperature = 105E the invention to produce increased results over the use of Pulping 41.2 42.4 conventional Surfactants alone. In addition, the benefits of Temperature = the Surfactants of the invention were realized even when 95°E fatty acids were used in an amount of about 18% by weight 60 Washing was conducted by diluting the pulp slurry to 1% with water and of the total surfactants used and it is believed that up to 30% thickening the slurry to 8% on a mesh screen. could be used without sacrificing the benefits of the inven tion. It is also believed that the benefits of the invention would be realized if aliphatic alcohol alkoxylates having EXAMPLE 4 larger carbon chains were used (i.e. C19 to C25) especially 65 The Superiority of the deinking composition of the inven since the C18 aliphatic alcohol alkoxylates of the invention tion at various water hardness values (calculated as CaCO produced Such beneficial results. in PPM) is demonstrated in the following table. US 6,784,146 B1 10 to reach the desired size level or water repellency required by the printing process. Reducing the usage of sizing agents leads to reduced machine deposition and improved machine 85% Linear 85% Linear C1 is primary C1s runability. The size level, the water repellency, or the resis alcohol alcohol tance to water absorbency is normally monitored by either (EO)/15% (EO)./15% measuring the weight gain using a Cobb test or the water fatty acid fatty acid drop using a water drop test. Solid Content, wt % 5 5 Example 6 demonstrates the impact of the deinking pH after pulping 8 8 Surfactant, wt % O.45 O.45 Surfactants or compositions of the invention and conven based on solid tional deinking Surfactants or compositions on the rosin/ Pulping Temperature, F. 115 115 alum sizing of paper. The effect of roSin/alum size is Pulping time, minutes 7 7 determined in this example by measuring the water gain (in Washing (1% to 8%) Yes Yes Brightness, Brightness, grams) using a Cobb test. Handsheets were made at 5 g dry % % 15 fiber/sheet and each sheet was treated with 12#/ton alum and Water Hardness = 100 41.4 42.9 4#/ton rosin size. The sheets (other than the blanks) were PPM Water Hardness = 200 40.O 41.9 treated with 2#/ton of the surfactants listed. The pulp was PPM adjusted to a pH of 5.7-5.8 before formation of the hand Water Hardness = 400 39.4 40.7 sheets and was left to sit overnight. The Cobb test involved PPM Soaking the handsheet Specimens in distilled water for 3 minutes and measuring the gain in weight from the absorp Washing was conducted by diluting the pulp slurry to 1% with water and tion of water by the paper sheet. Well-sized paper will thickening the slurry to 8% on a mesh screen. absorb less water, and therefore will have leSS weight gain. EXAMPLE 5 The composition in the present invention has leSS impact on 25 rosin/alum sizing than conventional deinking Surfactants as The deinking compositions of the present invention are shown below. also more effective in deinking aged wastepaper than con ventional deinking compositions. It is known in the art that wastepaper when aged becomes more difficult to be deinked. This is normally known as the “summer effect.” tills have Description Water Gain, g focused a significant amount of effort to increasing the Surfactant of Surfactant (Cobb Test)* deinking chemical usage at the pulper and/or the bleaching Blank No surfactant O6 chemical usage after deinking to boost the final brightness of Present Cs(EO)20 18 Invention recycled paper based on aged wastepaper. The deinking Present Mixed C1s 1s 2.4 Surfactants in the invention allow the mill to deinkaged 35 Invention (EO)offatty acid wastepaper more effectively. A Series of deinking tests were (85%/15%) conducted with wastepaper aged for different periods of time Present Mixed C1s 1s 3.0 Invention (EO)o using the exemplary deinking composition of the invention BIO-TERGE (RAS-40 Alpha olefin 0.4 described in Examples 2-4 and the conventional deinking sulfonates composition described in Examples 2-4 and the brightness (anionic increase between the deinking composition of the present 40 surfactant) RHODAMOX (R) LO2 Lauryl 0.5 invention and the conventional deinking composition after dimethylamine deinking was measured. Results are provided below. Oxide (cationic surfactant) IGEPAL (R) CO-730 Nonyl phenol (EO)" 3.5 45 SURFONIC (R) L24-9 Linear C2 14 5.8 Age of Brightness alcohol (EO) Wastepaper, Improvement NEODOL (R) 45-13 Linear C14 1s 6.3 months (ISO Brightness)" alcohol (EO) Linear 6.6 2 O.2 C11-C1s 9 O.9 50 alcohol 12 1.1 (EO)offatty acid 18 1.5 (85%/15%) PLURONIC (R) L-10 Blocked 6.7 "Absolute brightness improvement on the washed pulp. EOPOEO polymer AS shown above, a Significant increase in brightness was 55 NEODOL (R) 45-13 Linear C14 is 7.0 blend alcohol observed particularly with increased wastepaper age. This (EO)/Fatty acid demonstrates a further advantage of the invention in that it (85%/15%) can be used effectively with aged wastepaper. IGEPAL (R) RC-52O Nonyl phenol 7.4 (EO)ss EXAMPLE 6 IGEPAL (R) CO-630 Nonyl phenol 7.5 60 (EO), It has been demonstrated repeatedly that the deinking RHODASURF (R) L-77 Linear 7.8 compositions of the present invention are capable of improv alcohol (EO), ing ink removal efficiency under various processing condi RHODASURF (R) LA-12 Linear 8.2 alcohol (EO), tions as shown in the previous examples. In addition to these RHODASURF (R) TDA Tridecyl 8.5 benefits, it has been unexpectedly discovered that pulp 65 8.5 alcohol (EO)ss treated or deinked with the deinking compositions of the POLYTERGENT (R) Secondary 9.1 invention requires leSS Size application at the paper machine US 6,784,146 B1 11 12 completely absorbed by the sheet. A longer water drop time -continued indicates better sizing effect or less water absorbency. The following table demonstrates that pulp deinked with the Description Water Gain, g composition of the present invention provides higher sizing Surfactant of Surfactant (Cobb Test)* levels (measured by longer water drop times) compared to SLF-18 C14. 1s alcohol the levels of the conventional deinking compositions at alkoxylates various levels of Surfactant usage rates. (cloud Point at 18° C.) IGEPAL (R) RC-630 Alkyl phenol 19.9 (EO) Water Drop, seconds "BIO-TERGE (R) products are available from Stefan Company. *RHODAMOX(R) products are available from Rhodia, Inc. 85% Linear IGEPAL (R) products are available from Rhodia, Inc. 85% Linear C141s primary SURFONIC (R) L24-9 is available from Huntsman Corporation. Surfactant C.1s alcohol alcohol NEODAL (E) 45-13 is available from Shell. 15 Concentration, (EO)/15% (EO)/15% PLURONIC (R) products are available from BASF Corporation. #ft fatty acid fatty acid RHODASURF (R) products are available from Rhodia, Inc. POLYTERGENT (R) SLF-18 is available from BASF Corporation. O 310 310 1. 270 160 2 225 90 AS shown above, the water gain for the examples that use 4 18O 35 the deinking compositions of the invention is between about 8 12O 8 1.8 g and 3.0 g, whereas the examples that use conventional 12 65 3 non-ionic Surfactants have a water gain in the range from 13.5 to 19.9 g. Clearly, the paper sheet made using the deinking compositions of the invention has significantly leSS AS shown in this example, introducing deinking Surfac water gain than the paper sheet made using conventional 25 tants lowered the sizing effect of the paper sheet, as indicated non-ionic deinking Surfactants. In other words, Significantly by the shorter water drop time in Seconds. However, using leSS alum size is required to reach the desired size effect the deinking composition of the invention reduces the water when pulp is prepared using the deinking composition of the drop time at a much slower rate than conventional deinking invention compared to pulp prepared using conventional compositions. In another words, less sizing agent is required non-ionic deinking compositions. It is noted that anionic and for the final paper product to have certain “Size' or water cationic Surfactants produced good water gain values. absorbency when paper is produced with pulp deinked with Nevertheless, these Surfactants are known in the art to have the compositions of the present invention compared to poor deinking properties. conventional deinking compositions. Again, as with the effects on brightness and ERIC value, EXAMPLE 8 it would be expected that in addition to the C16 to C18 35 The impact of the deinking Surfactants of the invention on aliphatic alcohol alkoxylates used in the examples, that AKD sizing was also evaluated in an actual deinking and C19-C25 aliphatic alcohol alkoxylates could also be used to sheet forming Sequence at a given Surfactant concentration. provide Significant and unexpected increases in water In this example, a deinking composition according to the repellency, especially considering the results from using invention and a conventional deinking composition were C18 linear alcohols. Furthermore, it is believed that the 40 added to the pulper at 9+/ton of oven-dry fiber. The waste benefits of the invention would be realized when up to about paper was pulped in each case under identical temperatures, 20% of conventional surfactants were used in the deinking pHs, water hardnesses, and other chemical usage rates, etc. composition and it is believed that greater amounts of and the wash was deinked on the mesh Screen in an identical conventional surfactants (up to about 30% or even up to manner. The deinked pulp was diluted to 1% consistency about 50%) could be used with the surfactants of the 45 and AKD sizing agent was applied to the pulp at various invention to produce increased results over the use of usage rates. The water drop was measured to determine the conventional Surfactants alone. In addition, the benefits of effect of the Surfactants on the water absorbency or sizing the Surfactants on water repellency of the invention were effect of paper formed using the pulp from these examples. realized even when fatty acids were used in an amount of about 18% by weight of the total surfactants used and it is 50 believed that up to 30% could be used without sacrificing the benefits of the invention. Water Drop, seconds EXAMPLE 7 85% Linear 85% Linear C141s primary Another group of Sizing agents includes alkyl ketene 55 AKD C.1s alcohol alcohol dimer (AKD) and alkenyl succinic anhydride (ASA) and size dosage, (EO)/15% (EO)/15% they function Similarly to one another. In this example, the LB per ton fatty acid fatty acid impact of an exemplary deinking composition of the inven O 0.72 O6 tion on AKD sizing is evaluated against a conventional 1O 5 4 deinking composition using a water drop test. For this 60 2O 62 33 example, the pulp slurry was connected with the two deink 3O 336 151 ing compositions at the provided Surfactant concentrations 45 850 38O and 20+/ton of AKD size was applied to the pulp prior to sheet formation. The water drop was determined by applying AS shown above, the deinking composition of the inven a pre-determined quantity of destilled water (normally either 65 tion provides improved paper Size to the deinked pulp, 5 or 10 um) onto the Surface of the paper sheet and particularly at the rates typically used by mills, i.e., an AKD measuring the time in Seconds for the water droplet to be usage rate of 20 and above. This provides additional evi US 6,784,146 B1 13 14 dence to the evidence from Example 7 that the deinking flotation (the “accept”) and brightness and ERIC values compositions of the invention offer a significant reduction in were determined as shown below. the AKD size usage rate as well as improved deinking performance. Moreover, the reduction of size usage on the paper machine also reduces the deposition potential associ ated with AKD and its derivatives and allows mills to have Flotation Ink Removal improved machine runability. 85% Linear 85% Linear C141s primary EXAMPLE 9 C.1s alcohol alcohol (EO)/15% (EO)1/15% The impact of the deinking composition on machine fatty acid fatty acid deposition was evaluated using a specialized laboratory test. Floated Pulp 46.3 43.9 In this test, the deinked pulps prepared in Example 8 were Brightness, 7% separately added to a KitchenAid(R) mixer under controlled Floated Pulp 1109 1471 conditions to Simulate the shear force experienced on the ERIC, PPM paper machine wires and felts. Equal amounts of the sizing 15 agent, in this case 20 pounds perton of AKD was added. The pulps were each mixed at typical machine temperatures and The improved brightness and the lower ERIC value of the pH's (125 F. and pH 6) for an hour and the blades of the pulp treated with the deinking compositions of the invention mixer were visually examined for deposition potential. The indicates that ink was more easily removed when the deink pulp deinked with the conventional deinking composition ing composition of the invention was used as opposed to the and the pulp deinked with the deinking composition of the conventional deinking compositions. invention were tested and the results indicated that the pulp EXAMPLE 12 deinked with the Surfactants of the invention had consider ably less deposition potential. A mill trial of a deinking composition of the invention was 25 conducted. The mill processed 100% old newsprint with EXAMPLE 10 three stages of wash deinking and used 100% of the deinked The deinking composition of the invention has a signifi pulp to manufacture various grades of newsprint. This cantly reduced foaming potential compared to conventional allowed the benefits of the deinking compositions of the deinking Surfactants. High foam potential is generally asso invention to be monitored in both deinking plant and the ciated with low efficiency at wash Stages, water clarification paper machine. The data measured include deinking Surfac Stages, etc. A deinking Surfactant of the present invention tant usage rate, washed pulp brightness, ERIC, water absor was tested against a conventional deinking Surfactant under bency measured using a water drop test, and defoamer usage on the paper machine. The results are Summarized in the the conditions currently used in Several wash deinking mills. table below. Foam potential tests were conducted by introducing air at a 35 given rate into pulp slurry and measuring the weight of the foam removed from the vessel. The pulp slurry was tested at 1% consistency, defined as the weight percentage of fibrous Pre trial material in the pulp slurry. The results are presented below. data (85% Trial data 40 Linear C14 1s (85% Linear primary alcohol C.1s alcohol (EO)/15% (EO)./15% Foam Potentional fatty acid) fatty acid) Weight in grams Surfactant Usage 8.5-9.0 7.5 Rate, LB/Ton 85% Linear 45 Average Washed 44-46 46-49 85% Linear C14 is primary Pulp Brightness, 76 Drinking Mill C.1s alcohol alcohol Average Washed 450-600 350-460 Processing (EO)./15% (EO)1/15% Pulp ERIC, PPM Conditions fatty acid fatty acid Water Drop of Paper 50-70 80-130 A Mill Conditions 550 799 Sheet, seconds 50 B Mill Conditions 355 52O Defoamer Usage 8O 1O C Mill Conditions 321 500 Rate, ml/minutes Clarified Water 20-40 20-30 D Mill Conditions 293 370 Turbidity, NTU

In all cases, the deinking composition of the invention 55 Based on the laboratory data Suggesting the Significant produced reduced foaming potential. improvement of deinking efficiency using the deinking compositions of the invention, the mill elected to conduct EXAMPLE 11 the trial at a lower usage rate of 7.5 #/ton instead of the The deinking compositions of the invention were also normal 8.5–9.0 #/ton used for conventional deinking com tested in flotation processes and improved ink removal was 60 positions. The washed pulp brightness improved by 1-3 also observed in these processes. In this example, the points on average and the ERIC value decreased by about wastepaper was pulped in the usual manner with deinking 100-150 PPM using the deinking composition of the inven Surfactant or composition added in the pulper. The pulp was tion. Thus, even at a reduced usage, the deinking composi then diluted to 1% consistency and subjected to air flotation tion of the invention was able to deliver improved wash for 90 seconds in a laboratory float device (float cell). Foam 65 deinking efficiency, thereby allowing the mill to lower the that contained ink was removed or rejected from the cell. bleach chemical usage rate for Several grades of paper. The Pads were made from the pulp left in the vessel after deinking composition of the invention was also compatible US 6,784,146 B1 15 16 with the water clarification chemistry. The dissolved air 3. The proceSS according to claim 1, wherein R is a flotation (DAF) units operated well and turbidity was main Straight chained, C16-C18 alkyl group. tained at or slightly below the pre-trial levels. The defoamer 4. The process according to claim 1, wherein the alkoxy usage rate was also reduced from 80 ml/min to about 10 lates are based on primary or Secondary alcohols. ml/min. One important observation was the increase in 5. The process according to claim 1, wherein the recycled water drop on the final paper sheets. The mill went from the newSprint pulp stream further comprising from 0 to about pre-trial water drop average of 50-70 to 80-130 during the 25% by weight of one or more fatty acids based on the total period while the same AKD size usage rate was maintained weight of Surfactants. on the paper machine. The initial mill trial demonstrates the 6. The process according to claim 5, wherein Said one or improved wash deinking efficiency, reduced foaming more fatty acids are Selected from the group consisting of potential, and Size benefit associated with the deinking lauric acid, oleic acid, Stearic acid, tall oil fatty acid, tallow compositions of the invention. fatty acid coconut fatty acid, and mixtures thereof. AS shown above, the nature of the Surfactants in the 7. The process according to claim 1, wherein the alkoxy deinking compositions of the invention is very important. In lates are present in an amount from about 0.3% to about particular, the Surfactants used in the deinking compositions 15 0.7% by weight based on the oven-dry weight of the of the invention have a positive impact on deinking effi newSprint. ciency by positively affecting the ability of the Surfactants to 8. The process according to claim 1, wherein the recycled effectively release the printed ink from the cellulosic fiber, newsprint pulp stream is at a pH of from about 7 about 10. by effectively Stabilizing the released inks in the aqueous 9. In a non-flotation proceSS for making recycled paper phase to prevent them from depositing back onto the fiber, from recycled newsprint pulp that uses leSS Sizing agents to and by allowing the stabilized ink to be separated from the produce paper with the same level of water repellency, the fiber during the Washing operation. Therefore, the Surfac improvement comprising: adding a deinking composition tants used in the deinking compositions of the invention that is Solid at room temperature to a recycled newsprint have a positive effect on the resulting paper as demonstrated pulp stream in a Washing Stage and Separating ink released by the unexpected increase in paper brightness and decrease 25 by the recycled newsprint, the composition comprising in ERIC values over conventional deinking compositions active ingredients consisting of non-ionic, aliphatic, mono that use conventional deinking Surfactants. Furthermore, for hydric alcohol Surfactant alkoxylates of the following Struc industries Such as the recycled newsprint industry that use ture: sizing agents to produce paper having a desired level of water repellency, the Surfactants used in the deinking com positions of the invention have a significant positive effect on the paper machine runability because less sizing agent is wherein R is a straight chain or branched chain alkyl of from needed to produce paper having the desired water repel about 16 to about 18 carbons and n is from about 18 to about lency. The deinking compositions of the invention are also 25, wherein the proceSS produces paper using leSS Sizing able to deink aged wastepaper better than conventional 35 agents. deinking compositions. In addition, the deinking composi 10. A non-flotation process for deinking wastepaper com tions of the invention can produce better ink Separation at prising adding a deinking composition that is Solid at room different pHs, water hardneSS levels, temperatures, and temperature to a recycled newsprint pulp Stream in a wash Washing consistencies than conventional deinking compo ing Stage and Separating ink by released by the recycled Sitions. The deinking compositions of the invention accom 40 newSprint, the composition comprising active ingredients plish these benefits while still producing the low levels of consisting of non-ionic, aliphatic, monohydric alcohol Sur foaming desired in the art for wastewater deinking pro factant alkoxylates of the following Structure: CCSSCS. It is understood that upon reading the above description of the present invention, one skilled in the art could make 45 changes and variations therefrom. These changes and varia wherein R is a Straight chain or branched chain alkyl group tions are included in the Spirit and Scope of the following of from about 16 to about 18 carbons and n is from about 18 appended claims. to about 25. What is claimed is: 11. A non-flotation proceSS for deinking recycled news 1. A non-flotation process for deinking recycled newsprint 50 print comprising adding a deinking composition that is Solid comprising adding a deinking composition that is Solid at at room temperature to a recycled newsprint pulp stream in room temperature to a recycled newsprint pulp stream in a a washing Stage and Separating ink released by the recycled Washing Stage and Separating ink released by the recycled newSprint, the composition comprising active ingredients newSprint, the composition comprising active ingredients consisting of non-ionic, aliphatic, monohydric alcohol Sur consisting of alkoxylates of the following Structure: 55 factant alkoxylates of the following Structure: wherein R is a Straight chain or branched chain alkyl group wherein R is a straight chain or branched chain C18 alkyl of from about 16 to about 18 carbons and n is from about 18 60 group, and n is 21. to about 25. 12. The process of claim 11, wherein R is a Straight chain. 2. The process according to claim 1, wherein the alkoxy lates are Saturated.