Solvent for removal of hydrolyzed alkenyl succinic anhydride sizing agent deposits
Patent Information
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- DOW GLOBAL TECHNOLOGIES LLC
- Filing Date
- 2023-08-24
- Publication Date
- 2026-07-01
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Figure PCTCN2023114568-FTAPPB-I100001 
Figure PCTCN2023114568-FTAPPB-I100002 
Figure PCTCN2023114568-FTAPPB-I100003
Abstract
Description
SOLVENT FOR REMOVAL OF HYDROLYZED ALKENYL SUCCINIC ANHYDRIDE SIZING AGENT DEPOSITS
[0001] Field of Disclosure
[0002] Embodiments of the present disclosure are directed to a solvent for removal of hydrolyzed alkenyl succinic anhydride sizing agent deposits.Background
[0003] Alkenyl succinic anhydride (ASA) is a chemical compound used in various industrial applications, particularly in the production of paper and paperboard. It is an anhydride derivative of alkenyl succinic acid and is primarily used as a sizing agent in sizing paper. Sizing paper helps to reduce the paper′sabsorbency and increase its resistance to water, making it suitable for various printing and writing applications. The sizing process involves treating either the paper pulp or the paper itself with ASA, where it forms a thin hydrophobic film. This film prevents the paper from absorbing water-based inks or other liquids, ensuring better print quality and reduced ink feathering.
[0004] ASA is commonly used as an aqueous emulsion in an internal sizing process in paper making because of its reactivity, good efficiency, and ability to precipitate calcium carbonate. When added internally to the paper, the ASA emulsion is added to the aqueous fiber suspension prior to forming the paper, where the ASA reacts with the paper fibers at the dry stage. Once dry, the ASA confers hydrophobic characteristics to the hydrophilic surface of paper, imparting resistance against the penetration of water.
[0005] Due to the high reactivity of ASA with water and the coalescence phenomenon, however, the ASA sizing agent will hydrolyze in the paper making process, causing deposits of particulate matter on the paper making machinery. These deposits can lead to mechanical breakdowns of the paper making machinery and even paper breakage. To reduce the negative impact of these deposit, the hydrolyzed ASA sizing agents formed during the paper making process needs to be removed. As such, there is a need in the art for a method of removing the hydrolyzed ASA sizing agents from the paper making process.Summary
[0006] The present disclosure provides various embodiments, including addressing the above shortcomings by providing a method of removing deposits derived from a hydrolyzed alkenyl succinic anhydride (ASA) sizing agent from paper production equipment. The method includes providing an aqueous solution that includes a glycol ether of Formula I:
[0007] R1-O- (AO) n-H (I)
[0008] where R1 is selected from the group consisting of a C1 to C8 alkyl, phenyl or a phenyl substituted by one or more R2, where R2 is a (C1-C4) hydrocarbyl; n is an integer from 1 to 6 and AO is selected from the group consisting of an ethylene oxide unit, a propylene oxide unit and combinations thereof; and adding the aqueous solution to the paper production equipment that includes the hydrolyzed ASA sizing agent deposits; soaking the hydrolyzed ASA sizing agent deposits in the aqueous solution for a predetermined time and at a predetermined temperature to form dissolved hydrolyzed ASA sizing agent deposits; and removing the aqueous solution with the dissolved hydrolyzed ASA sizing agent deposits from the paper production equipment.
[0009] Embodiments of the present disclosure also include a system that includes paper production equipment and deposits derived from a hydrolyzed ASA sizing agent, where the system includes the paper production equipment having the deposits derived from the hydrolyzed ASA sizing agent; and the aqueous solution, where at least a portion of the hydrolyzed ASA sizing agent deposits in the paper production equipment soak in the aqueous solution to dissolve the hydrolyzed ASA sizing agent deposits.Detailed Description
[0010] During paper manufacturing, a sizing agent is typically added to the paper pulp after the pulping and refining stages but before the formation of the paper web. Briefly, after the raw materials (e.g., softwood, hardwood, recycled paper, agricultural residues, or specialty fibers like cotton or flax) are turned into pulp (through mechanical or chemical pulping) , the pulp is mixed with water to create a pulp slurry or pulp stock. This slurry contains the individual fibers that will eventually form the paper sheet. At this point, the sizing agent along with other chemical additives are introduced into the pulp stock. The pulp stock with the sizing agent is then introduced onto a moving mesh screen or wire to form the wet paper web. The paper web then passes through a series of pressing, drying and calendaring steps to remove the water and begin the paper finishing process.
[0011] Deposits derived from hydrolyzed alkenyl succinic anhydride (ASA) sizing agent in paper production equipment are the unwanted accumulation of precipitates resulting from the breakdown or transformation (e.g., the hydrolysis) of the ASA sizing agent during the above described papermaking process. As discussed above, sizing agents are chemicals used in the paper industry to control the absorption and penetration of liquids into paper fibers. ASA sizing agents are commonly used for this purpose. These agents are added to the paper pulp or to the paper surface during the manufacturing process to enhance the paper′swater resistance, printability, and other properties. During the manufacturing process, the ASA sizing agent can undergo hydrolysis due to exposure to moisture, heat, and / or alkaline conditions, which can lead to deposits that foul and disrupt the paper production equipment. For example, the deposits can accumulate on any number of parts of the paper production equipment, including rollers, screens, wires, and other machinery parts, which can have negative impacts on the paper production process and the quality of the final product. For example, deposits can build up on equipment surfaces, leading to reduced efficiency and increased downtime for maintenance and cleaning; deposits can negatively impact paper quality, causing surface defects, reduced printability, and uneven sizing distribution; and regular cleaning and maintenance to remove deposits can increase operational costs for paper manufacturers.
[0012] Embodiments of the present disclosure provide for a method and system for removing deposits derived from a hydrolyzed ASA sizing agent from paper production equipment. For the various embodiments, the method of removing deposits derived from a hydrolyzed ASA sizing agent from paper production equipment include providing an aqueous solution that includes a glycol ether of Formula I: R1-O- (AO) n-H (I)
[0013] where R1 is selected from the group consisting of a C1 to C8 alkyl, phenyl or a phenyl substituted by one or more R2, where R2 is a (C1-C4) hydrocarbyl; n is an integer from 1 to 6 and AO is selected from the group consisting of an ethylene oxide unit, a propylene oxide unit and combinations thereof. For the various embodiments, the AO can consist of a random copolymer of the propylene oxide unit and the ethylene oxide unit. In an alternative embodiment, the AO can consist of a block copolymer of the propylene oxide unit and the ethylene oxide unit. In an additional embodiment, the AO can consist of just the propylene oxide unit. For example, the propylene oxide unit can be selected from the group consisting of a 1, 2-propylene oxide unit, a 2, 3-propylene oxide unit and combinations thereof. Alternatively, the AO consists of the ethylene oxide unit. For the various embodiments, the R1 is preferably a linear C3 to C8 alkyl. Preferred examples of the glycol ether of Formula I according to the present disclosure are selected from the group consisting of 2-phenoxyethanol, polyethylene glycol monophenyl ether, tripropylene glycol methyl ether, dipropylene glycol n-butylether, tripropylene glycol monobutyl ether, diethylene glycol hexyl ether, polypropylene glycol n-propyl ether and a combination thereof.
[0014] For the various embodiments, the phenyl substituted by one or more R2, where R2 is a (C1-C4) hydrocarbyl can include the following. The (C1-C4) hydrocarbyl can be selected from a (C1-C4) alkyl, such as methyl, ethyl, propyl or butyl (e.g., n-butyl, sec-butyl, iso-butyl and tert-butyl) . Examples of other (C1-C4) hydrocarbyl groups include alkenyl and alkynyl groups of (C3-C4) . Examples of the substituted phenyl include, but are not limited to, methyl-phenyl (in either the ortho, meta or para position) and ethyl-phenyl (in either the ortho, meta or para position) , as are known in the art.
[0015] The glycol ether of Formula I can be formed from known techniques or acquired commercially. For example, an etherification reaction involving an alcohol (e.g., R-OH) and an alkylene oxide (e.g., ethylene oxide or propylene oxide) and a catalyst, as are known in the art, can be used in forming the glycol ether of Formula I. The reaction proceeds by mixing the alcohol (R-OH) and the alkylene oxide (EO or PO) in a desired molar ratio for the desired length of the polymer chain (n) . The catalyst used can include, depending on the alkylene oxide, potassium hydroxide (KOH) or sulfuric acid (H2SO4) . Reaction temperatures can range from 100 ℃ to 180 ℃, depending on the alkylene oxide, while reaction pressures can be from 101 to 1013 kPa, again depending upon the alkylene oxide used in the reaction. The glycol ether of Formula I can also be acquired commercially from sources such as DOW Inc., BASF, Eastman Chemical Company, Shell Chemicals, and LyondellBasell, among others.
[0016] For the various embodiments, the aqueous solution includes 0.25 weight percent (wt. %) to 1 wt. %of the glycol ether of Formula I based on a total weight of the aqueous solution. Preferably, the aqueous solution includes 0.5 wt. %to 1 wt. %of the glycol ether of Formula I based on a total weight of the aqueous solution. For the various embodiments, the aqueous solution can include one or more of the glycol ether of Formula I. For example, the aqueous solution can include a mixture of two or more of the glycol ether of Formula I. For example, the aqueous solution can include 2-phenoxyethanol and one of dipropylene glycol n-butylether, tripropylene glycol monobutyl ether; diethylene glycol hexyl ether or polypropylene glycol n-propyl ether. Combinations of three of the glycol ethers of Formula I are also possible. Ratios of the combinations of the glycol ethers of Formula I can be from 0.25∶1 to 1∶0.25, where the total wt. %of the combinations of the glycol ethers of Formula I is 0.25 wt. %to 1 wt. %based on a total weight of the aqueous solution. Other ratios are possible. So, for example and as seen in Inventive Example 12 below, a 1∶1 ratio of a mixture of 2-phenoxyethanol and dipropylene glycol n-butylether can have 0.5 wt. %of the 2-phenoxyethanol and 0.5 wt. %dipropylene glycol n-butylether so that the aqueous solution has 1 wt. %of the glycol ethers of Formula I.
[0017] For the various embodiments, the aqueous solution can be alkaline. As provided herein, being alkaline includes having a pH of greater than 7. For example, the aqueous solution of the present disclosure can have a pH of greater than 7 to 13. Preferably, the aqueous solution of the present disclosure can have a pH of 9 to 13. More preferably, the aqueous solution of the present disclosure can have a pH of 11 to 13. Most preferably, the aqueous solution of the present disclosure can have a pH of 12 to 13. The pH of the aqueous solution can be adjusted to the desired alkaline pH through the use of a substance that increases the concentration of hydroxide ions (OH-) in the aqueous solution. For example, a strong base such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) could be added to the aqueous solution to raise the pH to the devised value. Basic salts such as sodium carbonate (Na2CO3) or calcium hydroxide (Ca (OH) 2) might also be used to raise the pH to the devised value.
[0018] The method of the present disclosure further includes adding the aqueous solution, as provided herein, to the paper production equipment that includes the hydrolyzed ASA sizing agent deposits. For the various embodiments, the aqueous solution of the present disclosure that is added to the paper production equipment that includes the hydrolyzed ASA sizing agent deposits can be a neat solution of water with the glycol ether (s) of Formula I at the wt. %values along with the compound used to adjust the pH, both as provided herein. For this process, the aqueous solution can be added to the paper production equipment in place of the paper pulp solution. So, for example, the paper pulp solution can be removed from the paper production equipment after which the aqueous solution of the present disclosure is added to the paper production equipment to form dissolved hydrolyzed ASA sizing agent deposits. In other words, the aqueous solution of the present disclosure replaces the paper pulp solution to dissolve the deposits derived from the hydrolyzed ASA sizing agent in the paper production equipment.
[0019] Alternatively, the aqueous solution added to the paper production equipment having the hydrolyzed ASA sizing agent deposits can be derived, formed or made from the paper pulp solution (or portions of the paper pulp solution) used in the paper making process itself. For example, the glycol ether (s) of Formula I could be added directly to the paper pulp solution to provide the wt. %values of glycol ether (s) of Formula I provided herein, along with making any desired pH adjustments as provided herein. As used herein, the paper pulp solution can include the components used in making a paper product, where such components can include, but are not limited to, water, fibers (as discussed herein) , and various additives to facilitate the papermaking process and enhance the final paper′sproperties. Additives can include, but are not limited to, fillers such as calcium carbonate or kaolin, retention aids, sizing agents, dyes and pigments, strength additives, optical brighteners, and chemicals for the initial pulping process, such as sulfates, sulfites, or other agents depending on the type of pulp being produced.
[0020] The embodiments of the present disclosure further include soaking the hydrolyzed ASA sizing agent deposits in the aqueous solution added to the paper production equipment for a predetermined time and at a predetermined temperature to form dissolved hydrolyzed alkenyl succinic anhydride sizing agent deposits. For the various embodiments, the predetermined time can be from 0.5 to 3 hours. Longer or shorter times may also be possible as dictated by the nature of the hydrolyzed ASA sizing agent deposits in the paper production equipment. For the various embodiments, the predetermined temperature can be from 15 ℃ to 85 ℃. Again, higher or lower temperatures may also be possible as dictated by the nature of the hydrolyzed ASA sizing agent deposits in the paper production equipment. For the various embodiments, the use of mechanical agitation (e.g., mechanical stirring or jet agitation) to distribute the aqueous solution through the paper production equipment is possible.
[0021] The embodiments of the present disclosure further include removing the aqueous solution with the dissolved hydrolyzed alkenyl succinic anhydride sizing agent deposits from the paper production equipment. As discussed and illustrated herein, the dissolved hydrolyzed ASA sizing agent deposits are transformed from what are initially particles that are visible with the naked eye (e.g., particles larger enough to be seen and to cause mechanical and performance problems in the paper making equipment) to microscopic particles, among other things, which can then be rinsed or washed away from the paper production equipment.
[0022] For the various embodiments, the method and system of removing deposits derived from the hydrolyzed ASA sizing agent can be done with one or more of the components of the paper production equipment in place (e.g., in situ) . Alternatively, the method and system of removing deposits derived from the hydrolyzed ASA sizing agent can be accomplished by removing one or more of the components of the paper production equipment to undergo the method as discussed herein.
[0023] Embodiments of the present disclosure further include a system that includes paper production equipment and deposits derived from the hydrolyzed ASA sizing agent, where the system includes the paper production equipment, as described herein, having the deposits derived from the hydrolyzed ASA sizing agent, and the aqueous solution as provided herein, where at least a portion of the hydrolyzed ASA sizing agent deposits in the paper production equipment soak in the aqueous solution to dissolve the hydrolyzed ASA sizing agent deposits. For the various embodiments, the hydrolyzed ASA sizing agent deposits in the paper production equipment soak in the aqueous solution at the predetermined time (e.g., 0.5 to 3 hours) and at the predetermined temperature of 15 ℃ to 85 ℃ to dissolve the hydrolyzed ASA deposits.
[0024] EXAMPLES
[0025] The Inventive Examples (IE) and Comparative Examples (CE) were derived using the following materials and methods. A BYKO-spectra mini lamp house with a standard light source was used to observe the IE and CE. All IE and CE images provided herein were taken inside the light lamp house to ensure consistent light source. A 2100P TURBIDIMETER (HACH) was used to test the turbidity of the IE and CE. Table 1 provides the glycol ethers used in the IE and CE. All compounds in Table 1 were acquired from DOW Inc.
[0026] TABLE 1
[0027] Experimental Procedures
[0028] IE and CE were prepared as follows. Aqueous solutions of the glycol ether for IE and CE were prepared at the weight percent (wt. %) as provided in Tables 2 and 3. To the aqueous solution add a 10 wt. %sodium hydroxide aqueous solution dropwise to adjust the pH to 12.8. 0.05 grams of deposits derived from a hydrolyzed alkenyl succinic anhydride sizing agent from paper production equipment (ASA deposits) were weighted and placed into a 60 mL plastic (PP) bottle (bottle) having a magnetic stir bar. For each IE and CE, 40 grams of the aqueous solution was added to the bottle. The contents of the bottle was then heat to 60 ℃ with stirring at a rate of 200 rpm for 2 hours. The turbidity of each of the IE and CE was observed at zero (0) , one (1) and two (2) hours during the 2-hour heating and stirring process. The results are provided in Tables 2 and 3 below.
[0029] Table 2 -Turbidity of ASA deposits for IE and CE after stiring at 60 ℃ for 1 hour and 2 hours.
[0030] Table 3 -Turbidity of ASA deposits for IE before and after stiring at 60 ℃ for 1 hour and 2 hours.
[0031] Results
[0032] Table 2 show the ASA deposits before (0 hour) and after stirring IE (1 wt. %) and CE (1 wt. %) for 1 and 2 hours. Before the experiments, the ASA deposits were large blue pieces. After stirring at 60 ℃ for 1 hour, the blue deposit in water (CE-A) and 2EH-5PO (CE-B) still remain large pieces, and the solution remain colorless and slightly cloudy. In the HeCb 1 wt. %water solution sample (IE-1) , the blue ASA deposits turned into much smaller particles after stirring for 1 hour. After stirring for 2 hours, those blue particles could no longer be observed and the HeCb sample (IE-1) solution showed a blue cloudy appearance. The Poly PnP (IE-2) and TPM (IE-3) sample also showed good dissolution capability on ASA deposits.
[0033] The turbidity of water, IE and CE were tested to better understand the dissolve process (Tables 2-3) . The turbidity of water (CE-A) remained at about 19 NTU after 2 hours stirring. The turbidity of 2EH-5PO (CE-B) was 116 NTU (1 hour) and 128 NTU (2 hours) . 2EH-5PO was insoluble in water and after stirring, 2EH-5PO was partly dispersed in water, causing an increase in turbidity. HeCb (IE-1) showed great capability in dissolution of ASA deposits with the turbidity quickly increased to over 1000 NTU.
[0034] Tables 2-3 show the performance of EPh, DPnB and TPnB and EPh6 at different concentrations. After stirring, the largest pieces were dissolved, giving it a blue cloudy appearance. In the 1 wt. %DPnB (IE-5) solution, the blue particles could no longer be observed after 2 hours stirring, indicating excellent dissolve capability.
[0035] Blending EPh (0.5 wt. %) + DPnB (0.5 wt. %) (IE-12) ; EPh (0.5%) + TPnB (0.5%) (IE-13) ; EPh (0.25 wt. %) + DPnB (0.25 wt. %) (IE-14) ; and EPh (0.25%) + TPnB (0.25%) (IE-15) were evaluated. As seen in Table 3, the IE showed good performance as most of the blue particles were dissolved / dispersed. The cloudiness was measured to better understand if the ASA deposits had dispersed in solvent solution. The higher the cloudiness indicates more dissolved / dispersed ASA deposits. In Table 3, the turbidity of 0.5%EPh + 0.5%TPnB (IE-13) significantly increased from 1.12 NTU to 489 NTU after 2 hours stirring, showing that significant amount of ASA deposit had been dissolved.
Claims
1.A method of removing deposits derived from a hydrolyzed alkenyl succinic anhydride sizing agent from paper production equipment, comprising:providing an aqueous solution that includes a glycol ether of Formula I:R1-O- (AO) n-H (I)wherein R1 is selected from the group consisting of a C1 to C8 alkyl, phenyl or a phenyl substituted by one or more R2, where R2 is a (C1-C4) hydrocarbyl; n is an integer from 1 to 6 and AO is selected from the group consisting of an ethylene oxide unit, a propylene oxide unit and combinations thereof; andadding the aqueous solution to the paper production equipment that includes the hydrolyzed alkenyl succinic anhydride sizing agent deposits;soaking the hydrolyzed alkenyl succinic anhydride sizing agent deposits in the aqueous solution for a predetermined time and at a predetermined temperature to form dissolved hydrolyzed alkenyl succinic anhydride sizing agent deposits; andremoving the aqueous solution with the dissolved hydrolyzed alkenyl succinic anhydride sizing agent deposits from the paper production equipment.2.The method of claim 1, wherein the AO consists of the propylene oxide unit.3.The method of any one of claims 1-2 wherein the propylene oxide unit is selected from the group consisting of a 1, 2-propylene oxide unit, a 2, 3-propylene oxide unit and combinations thereof.4.The method of claim 1, wherein the AO consists of the ethylene oxide unit.5.The method of any one of claims 1-4, wherein the R1 is selected from a linear C3 to C8 alkyl.6.The method of claim 1, wherein the glycol ether of formula I is selected from the group consisting of 2-phenoxyethanol, polyethylene glycol monophenyl ether, tripropylene glycol methyl ether, dipropylene glycol n-butylether, tripropylene glycol monobutyl ether, diethylene glycol hexyl ether, polypropylene glycol n-propyl ether and a combination thereof.7.The method of any one of claims 1-6, wherein the aqueous solution includes two or more of the glycol ether of Formula I.8.The method of any one of claims 1-7, wherein the aqueous solution includes 0.25 weight percent (wt. %) to 1 wt. %of the glycol ether of Formula I based on a total weight of the aqueous solution.9.The method of any one of claims 1-7, wherein the aqueous solution includes 0.5 wt. %to 1 wt. %of the glycol ether of Formula I based on a total weight of the aqueous solution.10.The method of any one of claims 1-9, wherein the aqueous solution is alkaline.11.The method of any one of claims 1-10, wherein the aqueous solution has a pH of 12 to 13.12.The method of any one of claims 1-11, wherein the predetermined time is 0.5 to 3 hours.13.The method of any one of claims 1-12, wherein the predetermined temperature is 15 ℃ to 85 ℃.14.A system that includes paper production equipment and deposits derived from a hydrolyzed alkenyl succinic anhydride sizing agent, the system comprising:the paper production equipment having the deposits derived from the hydrolyzed alkenyl succinic anhydride sizing agent; andthe aqueous solution of any one of claims 1-13, wherein at least a portion of the hydrolyzed alkenyl succinic anhydride sizing agent deposits in the paper production equipment soak in the aqueous solution to dissolve the hydrolyzed alkenyl succinic anhydride sizing agent deposits.15.The system of claim 14, wherein the hydrolyzed alkenyl succinic anhydride sizing agent deposits in the paper production equipment soak in the aqueous solution at a predetermined time of 0.5 to 3 hours and at a predetermined temperature of 15 ℃ to 85 ℃ to dissolve the hydrolyzed alkenyl succinic anhydride sizing agent deposits.