Modified alkyl sulfonic acids and uses thereof

Abstract

A method for delignification of plant material, the method comprising providing the plant material containing cellulose fibers and lignin, and exposing the plant material to a composition comprising an alkyl sulfonic acid and a peroxide, wherein the alkyl sulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1, and the exposure time is sufficient to remove substantially all of the lignin present on the plant material. Also disclosed are compositions capable of achieving delignification.

Description

[Technical field]

[0001] TECHNICAL FIELD TO WHICH THEINVENTION BELONGS The present invention relates in broad terms to methods and compositions useful for decomposing organic matter, such as biomass, by oxidation, such as delignification of wood material, and more specifically to methods and compositions for doing so under conditions milder than those under which the Kraft process is carried out. [Background technology]

[0002] 2. Background of the Invention The largest energy consumer in paper production is the production of pulp. Wood and other plants from which pulp is made contain three main components: cellulose fibers, lignin, and hemicellulose, as well as water. The primary objective of pulping is to separate the fibers and lignin. Lignin is a three-dimensional polymer that acts as a kind of mortar that holds all the fibers together in the plant. Lignin is undesirable in pulp and does not add anything to the final product. Wood pulping involves breaking down the bulk structure of fibrous raw materials, such as chips, stems, and other plant parts, into their constituent fibers. Cellulose fibers are the most important component in the papermaking process. Hemicellulose is a shorter branched carbohydrate polymer made up of various sugar monomers randomly arranged in an amorphous polymeric structure. The presence of hemicellulose in the finished pulp is not as important for the stiffness of the paper as cellulose. This is also true for biomass conversion. The challenges are similar; the desired results are different. In biomass conversion, further degradation to monovalent carbohydrates is the desired outcome, but in pulp and paper processes this is usually stopped soon after lignin dissolution.

[0003] There are two main approaches to the preparation of wood pulp or woody biomass: mechanical and chemical processing. Mechanical processing or pulping generally aims to physically tear the wood chips, thus splitting the cellulose fibers and separating them from each other. The disadvantages of this method are that the cellulose fibers are cut or damaged, resulting in shorter fibers, and that lignin is mixed or left in the cellulose fibers, resulting in impurities in the final product. The process is also energy-intensive and capital-intensive, since it requires high pressure, caustic chemicals, and heat. There are several approaches and processes for chemical pulping. These generally focus on breaking down the lignin and hemicellulose into water-soluble molecules. These broken down components are separated from the cellulose fibers by washing, without damaging the cellulose fibers. This chemical process is energy-intensive, since it requires a large amount of heat, and also often requires stirring and mechanical intervention, which increases the inefficiency and cost of the process.

[0004] Pulping methods exist that combine the chemical and mechanical aspects of pulping to varying degrees. Examples include thermomechanical pulping (commonly referred to as TMP) and chemi-thermo-mechanical pulping (CTMP). Through the selection of advantages offered by each common pulping method, the process is designed to reduce the amount of energy required for the mechanical aspects of the pulping process. This can also have a direct impact on the strength loss of fibers subjected to these combined pulping approaches. Generally, these approaches shorten the chemical treatment (compared to conventional chemical pulping) and then perform a mechanical treatment to separate the fibers.

[0005] The most common method for producing pulp for papermaking is the Kraft process. In the Kraft process, wood chips are converted into wood pulp, which is an almost pure cellulose fiber. The multi-step Kraft process begins with the impregnation of the wood chips with a chemical solution. This is done by wetting the wood chips and preheating them with steam. During this process, the wood chips expand, expelling the air contained within them and replacing it with liquid. The chips are then saturated with black and white liquors. Black liquor is generated during the Kraft process. It contains water, lignin residues, hemicellulose, and inorganic chemicals. White liquor is a highly alkaline aqueous solution containing sodium hydroxide and sodium sulfide. The wood chips are soaked in each solution and then cooked. To delignify the wood chips, they are boiled for several hours at temperatures up to 176°C. At this temperature, the lignin breaks down and water-soluble fragments are produced. After cooking, the remaining cellulose fibers are collected and washed.

[0006] Caro's acid, also known as peroxymonosulfuric acid (H2SO5), is one of the strongest oxidizing agents known. Several reactions are known for the preparation of Caro's acid, but one of the simplest involves the reaction of sulfuric acid (H2SO4) with hydrogen peroxide (H2O2). Once prepared in this manner, Caro's acid can be further reacted to produce potassium monopersulfate (PMPS), a valuable bleaching and oxidizing agent. Caro's acid has several known useful applications, most notably in wood delignification.

[0007] U.S. Patent No. 5,080,756 teaches an improved kraft pulping process, characterized in that a spent concentrated sulfuric acid composition containing organic matter is added to a kraft recovery system to provide a mixture enriched in its total sulfur content which is subjected to dehydration, pyrolysis and reduction in a recovery furnace. The organic matter of the sulfuric acid composition is particularly useful as a source of thermal energy that can easily maintain high heat levels to promote the oxidation and reduction reactions that occur in the furnace, resulting in the formation of sulfides which are used to prepare a cooking liquor suitable for pulping.

[0008] Rackemann et al. in “The effect of pretreatment on methanesulfonic acid-catalyzed hydrolysis of bagasse to levulinic acid, formic acid and furfural” (2018) disclose the use of methanesulfonic acid on bagasse pretreated with an alkaline solution.

[0009] US Patent Application No. 2016 / 0074549 discloses an activated hydrogen peroxide disinfectant composition for low foaming applications. A concentrated solution for dilution by the end user is provided, comprising a hydrogen peroxide source, a non-surface active organic sulfonic acid or salt thereof, a non-ionic surfactant, and an optional organic acid. Also provided is a ready-to-use hydrogen peroxide disinfectant solution, comprising hydrogen peroxide, a non-surface active organic sulfonic acid or salt thereof, a non-ionic surfactant, water as a solvent, and a biocidal amount of an optional organic acid. An end user can disinfect a surface of microorganisms by contacting the surface with the disinfectant composition for a time effective to kill a majority of the microorganisms present on the surface.

[0010] Biofuel production is also a potential application of the Kraft process. A current drawback of biofuel production is the need to use food-grade plant parts (such as seeds) to convert carbohydrates into fuel in a reasonably efficient process. Carbohydrates can also be obtained from cellulosic fibers by using non-food-grade biomass in the Kraft process, but the Kraft process is energy-intensive for delignification, making it a less commercially viable option. To build a plant-based chemical resource cycle, there is a great need for energy-efficient processes that can utilize plant-based feedstocks that do not compete with human food production.

[0011] The kraft pulping process is the most widely used chemical pulping process in the world, but it is very energy demanding and also has drawbacks, such as, for example, unpleasant odors emanating from the pulping plant surroundings and general exhaust gases that are currently strongly regulated in many pulp and paper manufacturing jurisdictions. In view of current environmental and economic issues, climate change, and the introduction of emission fees, it is highly desirable to optimize current pulping processes in order to provide at least linear quality fiber without currently causing substantial harm to the environment during its production. Thus, there remains a need for compositions that are capable of delignifying wood material at lower temperatures and pressures than those currently used, and without the need for additional capital investments.

[0012] In view of current environmental problems and climate changes due to anthropogenic pollution, it is desirable to be able to carry out organic matter decomposition by mild oxidation, which would allow the pulping technology to be updated and provide good quality fiber without substantial harm to the environment during its production.Therefore, there remains a need for compositions capable of carrying out delignification of wood material under moderate temperatures and pressures. Summary of the Invention

[0013] Summary of the Invention According to one aspect of the present invention, there is provided an aqueous acidic composition comprising: Alkyl sulfonic acids; and Peroxides, An aqueous composition comprising: wherein the alkylsulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1.

[0014] The inventors have discovered that delignification of organic materials, such as wood materials (such as, but not limited to, chips or sawdust), can occur at temperatures substantially lower than those used during conventional kraft pulping. Indeed, experiments conducted at room temperature with the preferred compositions according to the present invention have shown that they degrade the lignin present in wood chips to obtain high quality cellulose fibers. According to a preferred embodiment of the method according to the present invention, wood samples were treated at 30° C. during exposure to the compositions according to the preferred embodiments of the present invention. According to a preferred embodiment of the present invention, the energy costs involved in pulp delignification can be substantially reduced by applying a method including the preferred compositions of the present invention.

[0015] These teachings would reduce the energy requirements and therefore capital costs in the pulping process, making it less polluting by burning less fossil fuels or organic matter to generate the heat required in conventional pulping processes. Also, many of the valuable components of biomass that are normally decomposed or destroyed in the kraft process, such as aromatic monomers, could be retained. The technology disclosed herein represents a substantial advancement not only environmentally, but also as a method for producing chemical compounds that are used as building blocks or starting materials in many industrial chemical processes.

[0016] According to one aspect of the present invention, there is provided an aqueous acidic composition comprising: Alkyl sulfonic acids; and Peroxides, An aqueous acidic composition comprising: wherein the acid is present in an amount ranging from 20 to 65 wt % of the total weight of the composition, and the peroxide is present in an amount ranging from 1 to 30 wt % of the total weight of the composition.

[0017] According to another aspect of the present invention, there is provided an aqueous acidic composition comprising: Alkyl sulfonic acids; and Peroxides, An aqueous acidic composition comprising: wherein said alkylsulfonic acid and said peroxide are present in a molar ratio of 1:1 or greater.

[0018] Preferably, the composition further comprises a compound that includes an amine moiety.

[0019] Preferably, the alkyl sulfonic acid is selected from the group consisting of: alkyl sulfonic acids, where the alkyl group ranges from C1 to C6, linear or branched; and combinations thereof. Preferably, the alkyl sulfonic acid is selected from the group consisting of methane sulfonic acid; ethane sulfonic acid; propane sulfonic acid; 2-propane sulfonic acid; isobutyl sulfonic acid; t-butyl sulfonic acid; butane sulfonic acid; iso-pentyl sulfonic acid; t-pentyl sulfonic acid; pentane sulfonic acid; t-butyl hexane sulfonic acid; and combinations thereof. More preferably, the alkyl sulfonic acid is methane sulfonic acid.

[0020] According to yet another aspect of the present invention there is provided an aqueous composition comprising: Alkyl sulfonic acids; and Peroxides, 1. An aqueous composition for use in biomass / wood delignification comprising: wherein the alkylsulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1.

[0021] Preferably, the peroxide is hydrogen peroxide.

[0022] According to another aspect of the present invention, there is provided a method comprising: 1. A method for delignification of biomass / plant material comprising the steps of: - providing said plant material comprising cellulose fibers and lignin; - said plant material in need, Alkanesulfonic acids; and Exposure to a composition containing peroxide; Including, wherein the alkanesulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1 and the time of exposure is sufficient to remove substantially all of the lignin present on the plant material. Preferably, the composition further comprises a compound comprising an amine moiety. Preferably, the compound comprising an amine moiety has a molecular weight of less than 300 g / mol. Also, preferably, the compound comprising an amine moiety is a primary amine. More preferably, the compound comprising an amine moiety is an alkanolamine. Also, preferably, the compound comprising an amine moiety is a tertiary amine.

[0023] According to a preferred embodiment of the present invention, the alkanolamine is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, and combinations thereof. Preferably, the alkanolamine is triethanolamine.

[0024] The inventors have discovered that delignification of wood materials (e.g., but not limited to, wood chips or other common biomass) can occur at temperatures substantially lower than those used during conventional kraft pulping. Indeed, several experiments have been performed at average room temperatures ranging from 18-21°C with the preferred composition, which have shown that the present invention decomposes the lignin present on wood chips to liberate cellulose fibers very efficiently. According to another preferred embodiment of the method according to the present invention, wood samples were dissolved at 30°C upon exposure to the composition according to the preferred embodiment of the present invention. According to a preferred embodiment of the present invention, the energy costs, capital costs involved, and associated emissions currently discharged in pulp delignification can be significantly reduced by applying a method including the preferred composition of the present invention.

[0025] In accordance with a preferred embodiment of the present invention, a multi-step process is provided that relies on time, temperature and molar ratios of the preferred compositions of the present invention, where separate steps of dissolution achieve the following: 1. Delignification; 2. Dissolution of hemicellulose; and 3. Dissolution of crystalline cellulose. [Brief description of the drawings]

[0026] Brief description of the drawings The present invention may be more fully understood in consideration of the following description of various embodiments of the invention in conjunction with the accompanying drawings, in which: FIG. [Figure 1-4] Figure 1 is a photograph of wood chips in a composition according to a preferred embodiment of the present invention at t=1 minute; Figure 2 is a photograph of wood chips in a composition according to a preferred embodiment of the present invention at t=60 minutes; Figure 3 is a photograph of wood chips in a composition according to a preferred embodiment of the present invention at t=1 day; and Figure 4 is a photograph of wood chips in a composition according to a preferred embodiment of the present invention at t=8 days. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS It will be appreciated that numerous specific details have been provided to provide a thorough understanding of the exemplary embodiments described herein. However, those skilled in the art will appreciate that the embodiments described herein may be practiced without these specific details. In other instances, well-known methods, procedures, and components have not been described in detail so as not to obscure the embodiments described herein. Furthermore, this description should not be considered as in any way limiting the scope of the embodiments described herein, but rather as merely illustrating implementations of various embodiments described herein.

[0028] According to a preferred embodiment of the present invention, an acidic composition is provided that includes an alkylsulfonic acid component and a peroxide component. When the composition is contacted with a biomass such as wood chips, the wood chips are delignified, leaving the cellulose and hemicellulose intact. Such a process is advantageous in preparing pulp from organic matter. Separating the lignin from the cellulosic and hemicellulose systems facilitates the recovery of lignin monomers and the like. Lignin monomers are chemicals that constitute the lignin structure before it is hydrolyzed by acid.

[0029] According to a preferred embodiment of the present invention there is provided a method for treating organic material to obtain pulp and / or cellulosic material, said method comprising the steps of: - Providing organic material containing cellulose and lignin; - providing an acidic composition comprising an alkylsulfonic acid component and a peroxide component; - contacting the organic material with the composition for a time sufficient to remove substantially all of the lignin from the organic material; and Optionally, separating the lignin from the cellulose.

[0030] According to a preferred embodiment of the present invention, the remaining cellulose material can be further treated to finally obtain glucose monomers. Preferably, this treatment step is carried out with sulfuric acid or a modified acid containing a sulfuric acid component.

[0031] Preferably, the processing of the delignified organic matter includes an intermediate step in which hemicellulose is separated from the cellulose and then removed from the remaining cellulose. The separated hemicellulose can then be further processed to obtain various chemical compounds for future use. The remaining cellulose can be further decomposed by acid hydrolysis to obtain glucose monomers. The resulting glucose can be used as a starting block for various industrial chemical processes.

[0032] According to a preferred embodiment of the method according to the invention, the recovered lignin does not require substantial processing to further separate it from hemicellulose and / or cellulose, since the method is quite selective. Preferably, the implementation of the method under its proper control greatly facilitates further processing of the lignin prior to application in other fields. Lignin has many applications in many fields, as an additive for drilling oil and gas wells, agrochemicals, specialty polymers, and most commonly as a fuel source. Lignin and its derivatives are a multi-billion dollar market in various industries, and it would be highly advantageous to improve the supply chain and reduce the amount of processing required for future use.

[0033] Experiments carried out with aqueous acidic compositions according to preferred embodiments of the present invention have shown that under controlled reaction conditions it is possible to delignify wood chips and eliminate or at least substantially minimize the degradation of cellulose, whereby degradation is understood to mean the blackening or charring of cellulose (conversion to carbon black), which is emblematic of uncontrolled acid attack on cellulose and its staining.

[0034] Experiment 1 A preferred embodiment of the composition according to the present invention was tested to determine its ability to delignify wood chips.

[0035] Experiments were completed using approximately 0.2g of wood and approximately 20g of solution. The mixture was stirred at 200 rpm for 1 hour at a temperature of 30°C (Figures 1 and 2). Figures 3 and 4 show the wood chips in the solution over time. The solution tested was a mixture of methanesulfonic acid and hydrogen peroxide in a ratio of 5.6 to 1, and the resulting composition was titrated with permanganic acid with the results shown in Table 1 below.

[0036] [Table 1]

[0037] The pH value recorded was −0.45 at ambient conditions (pH<0). The molar ratio of MSA to peroxide was 5.6:1.

[0038] According to a preferred embodiment of the present invention, methanesulfonic acid is the major component in terms of volume and weight percentage of the composition of the present invention. According to a preferred embodiment of the present invention, the pH of the composition is less than 1, and according to another preferred embodiment of the present invention, the pH of the composition is less than 0.5.

[0039] Figures 3 and 4 show the delignification of wood chips in the presence of an alkylsulfonic acid (methanesulfonic acid) and hydrogen peroxide at a temperature of about 22°C for up to 8 days. It is noteworthy that there is no trace of carbon black at the end of the experiment (day 8), indicating that the cellulosic material has not been broken down into its most basic components.

[0040] The above experiments clearly demonstrate that compositions according to the present invention not only provide adequate dissolving acid for delignification of plant material, but are also valuable in limiting the degradation of cellulosic materials into carbon black residues, resulting in higher yields and profitability for plant operators while reducing emissions and risks to employees, contractors and the public.

[0041] A method for obtaining glucose from wood pulp would represent an important advance over current processes where such conversion is chemically, energy-, and emission-intensive, costly, and hazardous while not producing highly efficient results, especially in large-scale operations. Wood can be delignified, but to improve efficiency and yield, increase safety, and reduce overall costs, it would be desirable to employ compositions that the operator has some control over in order to preserve the cellulose rather than decomposing it into carbon black.

[0042] Preferably, the alkyl sulfonic acid compound and hydrogen peroxide are present in an amount ranging from a molar ratio of 1:1 to 15:1. Preferably, the resulting pH of the composition is less than 1, more preferably, the resulting pH of the composition is less than 0.5.

[0043] According to a preferred embodiment of the present invention, the compound containing a sulfonic acid moiety is selected from the group consisting of alkylsulfonic acids, where the alkyl group ranges from C1 to C6 and is linear or branched; and combinations thereof. Preferably, the compound containing a sulfonic acid moiety is selected from the group consisting of methanesulfonic acid; ethanesulfonic acid; propanesulfonic acid; 2-propanesulfonic acid; isobutylsulfonic acid; t-butylsulfonic acid; butanesulfonic acid; iso-pentylsulfonic acid; t-pentylsulfonic acid; pentanesulfonic acid; t-butylhexanesulfonic acid; and combinations thereof. More preferably, the compound containing a sulfonic acid moiety is methanesulfonic acid.

[0044] As would be understood by one of ordinary skill in the art, alkylsulfonic acid is understood to include alkylsulfonic acid compounds where the alkyl is saturated or unsaturated, cyclic, straight chain or branched, and / or substituted or unsubstituted.

[0045] In accordance with a preferred embodiment of the present invention, the combination of high concentrations of alkylsulfonic acid and peroxide can result in a modified acid composition that can provide controlled delignification of organic materials and leave cellulosic fibers relatively unaffected.

[0046] When wood delignification is carried out using compositions according to preferred embodiments of the present invention, the process can be carried out at temperatures and pressures significantly lower than those currently used in conventional kraft pulping processes. The advantages are considerable, some of which are listed here: Whereas kraft pulping processes require temperatures around 176-180°C to carry out the delignification step, preferred embodiments of the process according to the present invention can delignify wood at temperatures as low as 25°C. According to preferred embodiments of the present invention, wood delignification can be carried out at temperatures as low as 10°C. According to preferred embodiments of the present invention, wood delignification can be carried out at temperatures as low as 0°C. According to preferred embodiments of the present invention, wood delignification can be carried out at temperatures as low as 20°C. According to preferred embodiments of the present invention, wood delignification can be carried out at temperatures as low as 30°C. According to another preferred embodiment of the present invention, wood delignification can be carried out at temperatures as low as 40°C. According to yet another preferred embodiment of the present invention, wood delignification can be carried out at temperatures as low as 50°C. According to yet another preferred embodiment of the invention, wood delignification can be carried out at temperatures as low as 60°C. According to yet another preferred embodiment of the invention, wood delignification can be carried out at temperatures as low as 80°C. According to yet another preferred embodiment of the invention, wood delignification can be carried out at temperatures as low as 90°C. According to yet another preferred embodiment of the invention, wood delignification can be carried out at temperatures as low as 100°C. According to yet another preferred embodiment of the invention, wood delignification can be carried out at temperatures as low as 120°C. According to yet another preferred embodiment of the invention, wood delignification can be carried out at temperatures as low as 130°C.

[0047] In each one of the above preferred embodiments, the temperature at which the process is carried out is substantially lower than current energy intensive and relatively inefficient kraft processes.

[0048] Furthermore, the Kraft process requires high pressures to perform wood delignification. In accordance with preferred embodiments of the present invention, wood delignification can be performed at atmospheric pressure. This in turn avoids the need for highly specialized and expensive industrial equipment. It also allows for the implementation of delignification units in many parts of the world where the implementation of paper pulp facilities was previously infeasible for a variety of reasons.

[0049] Some of the advantages of the process according to the preferred embodiment of the present invention over the conventional kraft process are substantial, since the heat input in the latter is not only a major polluting source but is also a large part of the reason why the resulting pulp is so expensive. The energy savings alone from the implementation of the process according to the preferred embodiment of the present invention will be reflected in lower cost pulp and environmental benefits, both of which will have an immediate impact and will provide commercial and environmental benefits for generations to come.

[0050] Further cost savings from the practice of processes according to preferred embodiments of the present invention can be found in the absence or minimization of restrictive regulations regarding the operation of high temperature, high pressure pulp cookers.

[0051] A method to obtain glucose from wood pulp would represent an important advance over current processes in which such conversion is chemically intensive, costly, and does not produce noteworthy results, especially in large-scale operations. It would be desirable to employ a composition that delignifies the biomass, but also allows the operator some control to preserve the cellulose rather than decomposing it into carbon black, providing an additional source of income for the operators of such facilities.

[0052] In accordance with a preferred embodiment of the method of the present invention, the separation of lignin is effectively performed and the resulting cellulose fibers can be further processed to obtain glucose monomers.Glucose chemistry has numerous applications including, but not limited to, as a precursor in the preparation of widely used chemicals such as diacetonides, dithioacetals, ethanol, glucosides, glucals, and hydroxyglucals.

[0053] Another advantage of using the preferred compositions of the present invention compared to current kraft pulping is the lack of harmful gases or vapors. The source of vapors in the kraft pulping process is believed to be primarily the release of SO2. Delignification with the preferred compositions of the present invention has thus far, and to the extent of available detection capabilities, not resulted in the production of SO2.

[0054] Methanesulfonic acid (MSA), triethanolamine (TEOA) and hydrogen peroxide were formulated with varying concentrations of MSA, TEOA and hydrogen peroxide and reacted with biomass (wood chips) overnight at room temperature and pressure to evaluate the effect of varying the molar ratio. Control studies were conducted for each formulation in which only kraft lignin or cellulose was added to the biomass. Commercial lignin (Sigma-Aldrich; Lignin, kraft; Prod# 471003) was used as a control in the study. Commercial cellulose (Sigma-Aldrich; Cellulose, fibers (medium); Prod# C6288) was also used as a control in the study.

[0055] The solid phase of each blend was filtered after 20 hours reaction time, washed with water, and then dried in an oven at 45 °C to constant dry weight. All data are the average of three consecutive runs. An effective blend is one that dissolves all the lignin and leaves the cellulose as intact and undamaged as possible. The experimental results are reported in Table 2 below.

[0056] [Table 2]

[0057] MSA:H 2 O 2 A batch process in which the above were blended in a 1:1 molar ratio. A larger batch process was carried out to evaluate and validate the composition and process previously performed on a smaller scale. To prepare for the larger batch process, 548 g of methanesulfonic acid (MSA) (70%) and 453 g of hydrogen peroxide (29%) were mixed in a large beaker at room temperature (no cooling was required due to the low exothermicity of the reaction). The molar mix ratio was 1:1. 50 g of unsized wood chips (sawdust) were added and the mixture was stirred at ambient conditions. After 20 h, the reaction mixture was transferred to a filter system equipped with a 20 μm Teflon filter sheet and the remaining solids were dried at 45 °C for 12 h. The solids yield compared to the added biomass was 54.2%.

[0058] The resulting cellulose had a hydrocarbon content of 93.0%, which was determined to be close to the Sigma-Aldrich cellulose Lot# WXBC9745V-95.7% standard used for comparison. The moisture content was 3.38%, which was determined to be equivalent to the Sigma-Aldrich cellulose Lot# WXBC9745V-3% standard used for comparison. Kappa# = 11, meaning that delignification was not complete but sufficient for cardboard and practical paper. X-ray diffraction showed an apparent crystallinity of 58.2%, which was consistent with previously tested values. Also, Aldrich commercial cellulose was measured at 61.3%. Samples were examined under a scanning electron microscope and showed a very high fiber content.

[0059] According to another preferred embodiment of the present invention, the composition can be used for the decomposition of organic matter by oxidation, as used in water treatment, water purification and / or desalination. An example of this is the removal (i.e., destruction) of algae on filtration membranes. Such membranes are expensive, so it is economically important to use them as long as possible. However, it is difficult to remove organic matter that accumulates over time, and new approaches are needed that are efficient and cause as little damage to the membrane as possible. Mineral acids are too strong, so they can remove organic matter, but they will damage the filtration membrane. The preferred composition of the present invention improves this problem, as it is less aggressive than mineral acids, and as a result, organic pollutants can be removed with a much gentler approach, thus minimizing damage to the membrane.

[0060] Although the foregoing invention has been described in some detail for purposes of clarity and understanding, it will be understood by those skilled in the relevant art, once familiar with this disclosure, that various changes in form and detail may be made therein without departing from the true scope of the invention as set forth in the appended claims. In relation to the present invention, the following is further disclosed: [1] Alkyl sulfonic acids; and Peroxides, An aqueous acidic composition comprising: wherein the acid is present in an amount ranging from 20 to 65 wt % of the total weight of the composition, and the peroxide is present in an amount ranging from 1 to 30 wt % of the total weight of the composition. [2] Alkyl sulfonic acids; and Peroxides, An aqueous acidic composition comprising: wherein said alkylsulfonic acid and said peroxide are present in a molar ratio of 1:1 or greater. [3] The composition according to any one of [1] to [2], further comprising a compound containing an amine moiety. [4] The composition according to any one of [1] to [3], wherein the alkylsulfonic acid is selected from the group consisting of alkylsulfonic acids in which the alkyl group is in the range of C1-C6 and is linear or branched; and combinations thereof. [5] The composition according to any one of [1] to [3], wherein the alkyl sulfonic acid is selected from the group consisting of methanesulfonic acid; ethanesulfonic acid; propanesulfonic acid; 2-propanesulfonic acid; isobutylsulfonic acid; t-butylsulfonic acid; butanesulfonic acid; isopentylsulfonic acid; t-pentylsulfonic acid; pentanesulfonic acid; t-butylhexanesulfonic acid; and combinations thereof. [6] The composition according to any one of [1] to [5], wherein the compound containing a sulfonic acid moiety is methanesulfonic acid. [7] Alkyl sulfonic acids; and Peroxides, 1. An aqueous composition for use in biomass / wood delignification comprising: wherein the alkylsulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1. [8] The composition according to any one of [1] to [7], wherein the peroxide is hydrogen peroxide. [9] 1. A method for delignification of biomass / plant material comprising the steps of: - providing said plant material comprising cellulose fibers and lignin; - said plant material in need, Alkyl sulfonic acids; and Exposure to a composition containing peroxide; Including, wherein the alkyl sulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1, and the time of exposure is sufficient to remove substantially all of the lignin present on the plant material.

[10] The method of [9], wherein the composition further comprises a compound comprising an amine moiety.

[11] The method of claim 10, wherein the compound comprising an amine moiety has a molecular weight of less than 300 g / mol.

[12] The method of claim 9, wherein the compound containing an amine moiety is a primary amine.

[13] The method according to [9], wherein the compound containing an amine moiety is an alkanolamine.

[14] The method according to [9], wherein the compound containing an amine moiety is a tertiary amine.

[15] The method of claim 13, wherein the alkanolamine is selected from the group consisting of monoethanolamine; diethanolamine; triethanolamine; and combinations thereof.

[16] The method according to

[12] , wherein the alkanolamine is triethanolamine.

[17] 1. An aqueous composition for use in delignification of plant biomass, comprising: Alkyl sulfonic acids; and Peroxides, The composition comprising:

[18] 1. An aqueous composition for use in the decomposition of cellulose from a plant biomass source, comprising: Alkyl sulfonic acids; and Peroxides, The composition comprising:

[19] 1. An aqueous composition for use in the degradation of hemicellulose from plant biomass sources, comprising: Alkyl sulfonic acids; and Peroxides, Including, The composition, wherein the alkyl sulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1, and the time of exposure is sufficient to remove substantially all of the lignin present on the plant material.

[20] The composition according to any one of

[15] to

[18] , wherein the peroxide is hydrogen peroxide.

[21] 1. A method for delignification of plant biomass or biomass material, comprising the steps of: - providing said biomass material comprising cellulose fibers and lignin; - the biomass material required, Alkyl sulfonic acids; and Exposure to a composition containing peroxide; Including, wherein the alkyl sulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1, and the time of exposure is sufficient to remove substantially all of the lignin present on the plant material.

Claims

1. Alkyl sulfonic acids; A compound containing an amine moiety selected from the group consisting of alkanolamines; and Peroxides, An aqueous acidic composition comprising: wherein said acid is present in an amount ranging from 20 to 65 wt % of the total weight of the composition, and said peroxide is present in an amount ranging from 1 to 30 wt % of the total weight of the composition; wherein said alkylsulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:

1.

2. Alkyl sulfonic acids; A compound containing an amine moiety selected from the group consisting of alkanolamines; and Peroxides, An aqueous acidic composition comprising: wherein said alkylsulfonic acid and said peroxide are present in a molar ratio ranging from 1:1 to 15:

1.

3. 3. The composition of any one of claims 1 to 2, wherein the alkyl sulfonic acid is selected from the group consisting of alkyl sulfonic acids, where the alkyl group ranges from C1 to C6, and is linear or branched; and combinations thereof.

4. The alkylsulfonic acid is methanesulfonic acid; ethanesulfonic acid; Propanesulfonic acid; 2-propanesulfonic acid; isobutylsulfonic acid; t-butylsulfonic acid; butanesulfonic acid; 4. The composition of any one of claims 1 to 3, wherein the sulfonic acid is selected from the group consisting of isopentyl sulfonic acid; t-pentyl sulfonic acid; pentane sulfonic acid; t-butyl hexane sulfonic acid; and combinations thereof.

5. The composition described in any one of claims 1 to 4, wherein the alkylsulfonic acid is methanesulfonic acid.

6. The composition according to any one of claims 1 to 5, wherein the peroxide is hydrogen peroxide.

7. The composition of claim 1, wherein the compound containing an amine moiety has a molecular weight of less than 300 g / mol.

8. The composition of claim 1, wherein the alkanolamine is selected from the group consisting of monoethanolamine; diethanolamine; triethanolamine; and combinations thereof.

9. The composition of claim 8, wherein the alkanolamine is triethanolamine.

10. Alkyl sulfonic acids; A compound containing an amine moiety selected from the group consisting of alkanolamines; and Peroxides, 1. An aqueous composition for use in biomass / wood delignification comprising: wherein said alkylsulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:

1.

11. A method for delignification of plant material comprising the steps of: - providing said plant material comprising cellulose fibres and lignin; - said plant material in need, Alkyl Sulfonic Acid A compound containing an amine moiety selected from the group consisting of alkanolamines; and exposing the composition to a peroxide; Including, wherein the alkyl sulfonic acid and peroxide are present in a molar ratio ranging from 1:1 to 15:1, and the time of exposure is sufficient to remove substantially all of the lignin present on the plant material.

12. 12. The method of claim 11, wherein the compound comprising an amine moiety has a molecular weight of less than 300 g / mol.

13. The method of claim 11, wherein the compound containing an amine moiety is selected from the group consisting of monoethanolamine; diethanolamine; triethanolamine; and combinations thereof.

14. The method of claim 11, wherein the compound containing an amine moiety is triethanolamine.

15. The method according to any one of claims 11 to 14, wherein the peroxide is hydrogen peroxide.

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