MODIFIED SULFURIC ACID AND USES THEREOF

Abstract

An aqueous composition comprising: sulfuric acid; a modifying agent comprising a carbonyl-containing nitrogenous base compound; and a peroxide. Said composition being capable of delignifying biomass under milder conditions than conditions under which kraft pulping takes place.

Claims

1. An aqueous acidic composition comprising: sulfuric acid; a modifying agent comprising a carbonyl-containing nitrogenous base compound; and a peroxide.

2. The composition according to claim 1, wherein sulfuric acid, said carbonyl-containing nitrogenous base compound are present in a molar ratio ranging from 28:1 to 2:1.

4. The composition according to claim 1, wherein sulfuric acid and carbonyl-containing nitrogenous base compound are present in a molar ratio ranging from 20:1: to 5:1.

5. The composition according to claim 1, wherein sulfuric acid and said carbonyl-containing nitrogenous base compound are present in a molar ratio of approximately 10:1.

6. The composition according to claim 1, where said carbonyl-containing nitrogenous base compound is selected from the group consisting of: caffeine; lysine; creatine; glutamine; creatinine; 4-aminobenzoic acid; glycine; NMP (N-methyl-2-pyrrolidinone); histidine; DMA (N,N-dimethylacetamide); arginine; 2,3-pyridinedicarboxylic acid; hydantoin; and combinations thereof.

7. An aqueous composition for use in the processing and depolymerisation of cellulose from a plant source, wherein said composition comprises: sulfuric acid present in an amount ranging from 20 to 80 wt % of the total weight of the composition; a modifying agent comprising a carbonyl-containing nitrogenous base compound; and a peroxide; wherein the sulfuric acid and the carbonyl-containing nitrogenous base compound are present in a mole ratio ranging from 2:1 to 28:1.

8. The composition according to claim 7, wherein sulfuric acid and carbonyl-containing nitrogenous base compound are present in a molar ratio ranging from 20:1: to 5:1.

9. The composition according to claim 8, wherein sulfuric acid and said carbonyl-containing nitrogenous base compound are present in a molar ratio of approximately 10:1.

10. The composition according to claim 8, where said carbonyl-containing nitrogenous base compound has a molecular weight below 300 g/mol.

11. The composition according to claim 8, where the peroxide is hydrogen peroxide.

12. A one-pot process to separate lignin from a lignocellulosic feedstock, said process comprising the steps of: providing a vessel; providing said lignocellulosic feedstock; providing a composition comprising; an acid; a modifying agent comprising a carbonyl-containing nitrogenous base compound; and a peroxide; exposing said lignocellulosic feedstock to said composition in said vessel for a period of time sufficient to remove at least 80% of the lignin present said lignocellulosic feedstock; optionally, removing a liquid phase comprising dissolved lignin fragments from a solid phase comprising cellulose fibres.

13. The process according to claim 12, wherein said acid is sulfuric acid.

14. The process according to claim 12, wherein said peroxide is hydrogen peroxide.

15. The process according to any claim 12, wherein the period of time is sufficient to remove at least 90% of the lignin present on said plant material.

16. The process according to claim 12, wherein the temperature of the composition prior to the step of exposing it to the lignocellulosic feedstock is below 50° C.

17. The process according to claim 12, wherein said carbonyl-containing nitrogenous base compound is selected from the group consisting of: caffeine; lysine; creatine; glutamine; creatinine; 4-aminobenzoic acid; glycine; NMP (N-methyl-2-pyrrolidinone); histidine; DMA (N,N-dimethylacetamide); arginine; 2,3-pyridinedicarboxylic acid; hydantoin; and combinations thereof.

18. The process according to claim 12, wherein said carbonyl-containing nitrogenous base compound is selected from the group consisting of: caffeine; creatine; glutamine; creatinine; 4-aminobenzoic acid; glycine; NMP (N-methyl-2-pyrrolidinone); histidine; DMA (N,N-dimethylacetamide); 2,3-pyridinedicarboxylic acid; hydantoin; and combinations thereof

19. The process according to claim 12, wherein sulfuric acid and said carbonyl-containing nitrogenous base compound are present in a molar ratio ranging from 28:1: to 2:1.

20. The method according to claim 12, wherein sulfuric acid and carbonyl-containing nitrogenous base compound are present in a molar ratio ranging from 20:1: to 5:1.

21. The method according to claim 12, wherein sulfuric acid and said carbonyl-containing nitrogenous base compound are present in a molar ratio of approximately 10:1.

Description

DESCRIPTION OF THE INVENTION

[0058] The experiments carried out using an aqueous acidic composition according to a preferred embodiment of the present invention as shown that wood chips can undergo delignification under controlled reaction conditions and eliminate or at least minimize the degradation of the cellulose. Degradation is understood to mean a darkening of cellulose, which is symbolic of an uncontrolled acid attack on the cellulose and staining thereof.

[0059] The carbonyl-containing nitrogenous base compound together in the presence of sulfuric acid and the peroxide component, seems to generate a coordination of the compounds which acts as a modified sulfuric acid. In that respect, it is believed that the presence of the carbonyl-containing nitrogenous base compound forms an adduct with the sulfuric acid to generate a modified sulfuric acid, and therefore acts as a modifying agent. The strength of the modified acid is dictated by the moles of sulfuric acid to the moles of the carbonyl-containing nitrogenous base compound. Hence, a composition comprising a molar ratio of 6:1 of sulfuric acid: the carbonyl-containing nitrogenous base compound would be much less reactive than a composition of the same components in a 28:1 molar ratio.

[0060] When performing delignification of wood using a composition according to a preferred embodiment of the present invention, the process can be carried out at substantially lower temperatures than temperatures used in the conventional kraft pulping process. The advantages are substantial, here are a few: the kraft pulping process requires temperatures in the vicinity of 176-180° C. in order to perform the delignification process, a preferred embodiment of the process according to the present invention can delignify wood at far lower temperatures, even as low as 20° C. According to a preferred embodiment of the present invention, the delignification of wood can be performed at temperatures as low as 0° C. According to a preferred embodiment of the present invention, the delignification of wood can be performed at temperatures as low as 10° C. According to a preferred embodiment of the present invention, the delignification of wood can be performed at temperatures as low as 30° C. According to another preferred embodiment of the present invention, the delignification of wood can be performed at temperatures as low as 40° C. According to yet another preferred embodiment of the present invention, the delignification of wood can be performed at temperatures as low as 50° C. According to yet another preferred embodiment of the present invention, the delignification of wood can be performed at temperatures as low as 60° C. Other advantages include: a lower input of energy; reduction of emissions and reduced capital expenditures; reduced maintenance; lower shut down/turn around costs; also there are health, safety and environment (“HSE”) advantages compared to conventional kraft pulping compositions.

[0061] In each one of the above preferred embodiments, the temperature at which the processes are carried out are substantially lower than the current energy-intensive kraft process.

[0062] Moreover, the kraft process uses high pressures to perform the delignification of wood which is initially capital intensive, dangerous, expensive to maintain and has high associated turn-around costs. According to a preferred embodiment of the present invention, the delignification of wood can be performed at atmospheric pressure. This, in turn, circumvents the need for highly specialized and expensive industrial equipment such as pressure vessels/digestors. It also allows the implementation of delignification units in many of parts of the world where the implementation of a kraft plant would previously be impracticable due to a variety of reasons.

[0063] Some of the advantages of a process according to a preferred embodiment of the present invention, over a conventional kraft process are substantial as the heat/energy requirement for the latter is not only a great source of pollution but is in large part the reason the resulting pulp product is so expensive and has high initial capital requirements. The energy savings in the implementation of a process according to a preferred embodiment of the present invention would be reflected in a lower priced pulp and environmental benefits which would have both an immediate impact and a long-lasting multi-generational benefit for all.

[0064] Further cost savings in the full or partial implementation of a process according to a preferred embodiment of the present invention, can be found in the absence or minimization of restrictive regulations for the operation of a high temperature and high-pressure pulp digestors.

Experiment #1

Preparation of a Composition According to a Preferred Embodiment of the Present Invention

[0065] For the H.sub.2SO.sub.4:H.sub.2O.sub.2:caffeine blend with a 20:20:1 molar ratio, 54.4 g of concentrated sulfuric acid (93%) was mixed with 5.0 g caffeine (present as a modifying agent). Then, 60.5 g of a hydrogen peroxide solution in water (29%) was slowly added to the acid. As the mixing releases a large amount of heat, the beaker was placed in an ice bath. Addition of the hydrogen peroxide solution at this scale takes about 20 minutes. The pH of the resulting composition was less than 1.

Delignification Experiments

[0066] After mixing, the resulting composition is split into 4 equal parts. One part was exposed to 1.5 g of wood shavings, another part was exposed to commercially available lignin and another part was exposed to commercially available cellulose respectively and stirred at ambient conditions for 3 hours. The fourth part of the blend is kept as a blend reference sample.

[0067] Control tests were run for the respective mixtures with just kraft lignin or just cellulose added instead of biomass. Commercially available lignin (Sigma-Aldrich; Lignin, kraft; Prod #471003) was used as a control in the testing. Commercially available cellulose (Sigma-Aldrich; Cellulose, fibers (medium); Prod #C6288) was also used as a control in the testing.

[0068] The solid phase of each blend was filtered off after 3 h of reaction time, rinsed with water and dried in an oven at 45° C. to constant weight. An effective blend should dissolve all lignin and leave the cellulose as intact as possible. The results of the experiments conducted with several compositions are reported in Table 1 below.

TABLE-US-00001 TABLE 1 Recovery of solids (% of initial mass) after 3 h reaction time Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:Creatinine 42.2% 3.1%   94% 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:Caffeine 49.49% 6.46% 92.54% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:Caffeine 47.68% 0.00% 94.96% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:Caffeine 45.58% 1.94% 94.00% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:Creatine 45.64% 6.32% 98.84% monohydrate

[0069] A blend with a ratio of 10:10:1 of sulfuric acid (93% conc. used) to hydrogen peroxide (as 29% solution) to creatinine results in a mass recovery of over 49% from wood and over 90% for the cellulose control. However, the remaining lignin in the lignin control sample is an indication that the composition is not optimized for complete lignin removal. The pulp produced with such a composition can still have commercial applications.

[0070] A blend with a ratio of 10:10:1 of sulfuric acid (93% conc. used) to hydrogen peroxide (as 29% solution) to caffeine results in a mass recovery of over 45% from wood and close to 95% for the cellulose control. The lignin control sample showed is an indication that the composition is performing very well for lignin removal and produces a pulp which has a wide array of potential commercial applications.

[0071] A blend with a ratio of 10:10:1 of sulfuric acid (93% conc. used) to hydrogen peroxide (as 29% solution) to creatine monohydrate results in a mass recovery of over 45% from wood and close to 99% for the cellulose control. The remaining lignin in the lignin control sample is an indication that the composition is not optimized for lignin removal, but with only 6.32% of lignin control left, the composition is still deemed quite effective.

[0072] The above experiments provide clear indications that a preferred composition according to the present invention not only provides an adequate dissolving acid to delignify plant material but is also valuable in controlling the delignification to prevent the ultimate degradation of cellulosic material into carbon black residue resulting in higher yields potentially for the operators thus increasing profitability while reducing emissions and the risk to the employees, contractors and public.

[0073] Additional testing was carried out to confirm the above initial results and to explore the feasibility of using other compounds with similar features as modifying agent. The results of the experiments are set out below in Tables 2 to 14.

TABLE-US-00002 TABLE 2 Recovery of solids (% of initial mass) after 3 h reaction time using creatinine asmodifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:creatinine 57.8% 0% 95.1% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:creatinine 42.2% 3.1%.sup.  .sup. 94% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:creatinine 54.3% 0% 96.50% 

TABLE-US-00003 TABLE 3 Recovery of solids (% of initial mass) after 3 h reaction time using caffeine as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:caffeine 49.5% 6.5%.sup.  92.5% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:caffeine 47.7% 0% .sup. 95% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:caffeine .sup. 46% 2% 98.50% 

TABLE-US-00004 TABLE 4 Recovery of solids (% of initial mass) after 3 h reaction time using creatine as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:creatine 60.1% 26.6% 92.8% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:creatine 45.6%  6.3% 98.8% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:creatine 62.3%   0% 98.50%

TABLE-US-00005 TABLE 5 Recovery of solids (% of initial mass) after 3 h reaction time using glycine as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:glycine 46.6% 5.9% 95.1% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:glycine 42.9% 2.0% 94.0% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:Glycine 39.6% 2.3% 86.3%

TABLE-US-00006 TABLE 6 Recovery of solids (% of initial mass) after 3 h reaction time using histidine as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:histidine 49.1% 27.5% 91.96% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:histidine 46.0% 5.8% 95.8% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:histidine 35.2% 0.8% 94.7%

TABLE-US-00007 TABLE 7 Recovery of solids (% of initial mass) after 3 h reaction time using arginine as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:arginine 51.6% 28.3% 95.00% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:arginine 46.7% 12.2% 95.6% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:arginine 45.3% 3.7% 93.4%

TABLE-US-00008 TABLE 8 Recovery of solids (% of initial mass) after 3 h reaction time using lysine as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:lysine 71.3% 55.6% 95.0% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:lysine 46.4% 19.9%  100% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:lysine 58.2% 25.1% 92.8%

TABLE-US-00009 TABLE 9 Recovery of solids (% of initial mass) after 3 h reaction time using glutamine as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:glutamine 50.11% 0% .sup. 100% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:glutamine 49.5% 0% 99.98% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:glutamine 45.11% 0% 62.55%

TABLE-US-00010 TABLE 10 Recovery of solids (% of initial mass) after 3 h reaction time using 4-aminobenzoic acid (4-AMBZ) as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:4AMBZ n/a n/a n/a 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:4AMBZ 44.1% 0% 97.1% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:4AMBZ 49.8% 0% 98.7%

TABLE-US-00011 TABLE 11 Recovery of solids (% of initial mass) after 3 h reaction time using NMP as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:NMP 45.0% 2.2%.sup.  94.4% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:NMP 39.1% 0% 95.7% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:NMP 42.3% 0% 92.3%

TABLE-US-00012 TABLE 12 Recovery of solids (% of initial mass) after 3 h reaction time using DMA as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 5:5:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:DMA 46.0% 4.6% 99.1% 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:DMA 40.0% 2.7% 94.1% 20:20:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:DMA 43.3% 1.6% 91.4%

TABLE-US-00013 TABLE 13 Recovery of solids (% of initial mass) after 3 h reaction time using 2,3-pyridinedicarbocylic acid (23PDC) as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:23PDC 45.4% 0% 96.1%

TABLE-US-00014 TABLE 14 Recovery of solids (% of initial mass) after 3 h reaction time using hydantoin as modifying agent Wood Lignin Cellulose Molar Yield Yield Yield Ratio Chemical (%) (%) (%) 10:10:1 H.sub.2SO.sub.4:H.sub.2O.sub.2:hydantoin 53.6% 0% 92.4%

[0074] A method to yield glucose from wood pulp would represent a significant advancement to the current process where the conversion of such is chemical and energy intensive, costly, emissions intensive and dangerous all while not resulting in highly efficient results, especially in large-scale operations. It is desirable to employ a composition which may delignify wood but also allows the operator some control in order to preserve the cellulose rather than degrading it to carbon black resulting in higher efficiencies and yields along with increased safety and reduced overall costs.

[0075] According to a preferred embodiment of the method of the present invention, the carbonyl-containing nitrogenous base compound is selected from the group consisting of: caffeine; lysine; creatine; glutamine; creatinine; 4-aminobenzoic acid; glycine; NMP (N-methyl-2-pyrrolidinone); histidine; DMA (N,N-dimethylacetamide); arginine; 2,3-pyridinedicarboxylic acid; hydantoin; and combinations thereof. Preferably, the carbonyl-containing nitrogenous base compound is selected from the group consisting of: caffeine; creatine; glutamine; creatinine; 4-aminobenzoic acid; glycine; NMP (N-methyl-2-pyrrolidinone); histidine; DMA (N,N-dimethylacetamide); 2,3-pyridinedicarboxylic acid; hydantoin; and combinations thereof.

[0076] According to a preferred embodiment of the method of the present invention, the separation of lignin can be effected and the resulting cellulose fibers can be further processed to yield glucose monomers. Glucose chemistry has a multitude of uses including as a starting block in the preparation of widely used chemicals including but not limited to diacetonide, dithioacetal, glucoside, glucal and hydroxyglucal to name but a few.

[0077] According to another preferred embodiment of the present invention, the composition can be used to decompose organic material by oxidation such as those used in water treatment, water purification and/or water desalination. An example of this is the removal (i.e. destruction) of algae on filtration membranes. As such membranes can be quite expensive, it is imperative that they be used for as long as possible. However, given the difficulty to remove organic matter which accumulates on it over time, new approaches are necessary to do so efficiently and with as little damage to the membrane as possible. Mineral acids are too strong and, while they will remove the organic matter, will damage the filtration membranes. A preferred composition of the present invention remedies this issue as it is less aggressive than the mineral acids and, as such, will remove the organic contaminants in a much milder approach, therefore sparing the membrane.

[0078] While the foregoing invention has been described in some detail for purposes of clarity and understanding, it will be appreciated by those skilled in the relevant arts, once they have been made familiar with this disclosure that various changes in form and detail can be made without departing from the true scope of the invention in the appended claims.