Process for the production of oxidized wood products

Abstract

The present invention relates to a process for the production of oxidized wood products, comprising step a) reacting chips of one or more wood products in a basic solution at a pH between 8 and 14 under an oxygen atmosphere at a pressure of at least 0.1 MPa, or at least 0.9 MPa. A copper catalyst may be used in the process.

Claims

1. A process for the production of vanillin, vanillic acid, acetovanilone, syringaldehyde, and veratraldehyde from softwood, hardwood, lignin, or a mixture thereof, comprising the step a) reacting chips of the one or more wood products in a basic solution, wherein the basic solution is an aqueous solution with bases selected from the group comprising NaOH, KOH, Ca(OH).sub.2 and Mg(OH).sub.2, at a pH between 8 and 14, wherein the basic solution has a molarity of 3 to 5 M, under an oxygen atmosphere using substantially pure oxygen, at a pressure between 0.5 and 10 MPa and wherein the temperature is below 160° C., under stirring for between 6 and 36 hours, wherein a use of a metal catalyst is disclaimed, and wherein the reaction results in one or more of vanillin, vanillic acid, acetovanilone, syringaldehyde, and veratraldehyde.

2. The process according to claim 1, wherein the pressure is between 0.5 and 1.5 MPa.

3. The process according to claim 1, wherein the temperature is between 50 and 160° C.

4. The process according to claim 1, wherein the temperature is between 70 and 140° C.

5. The process according to claim 1, wherein the pH is between 10 and 14.

6. The process according to claim 1, wherein the chips of the one or more wood products are unprepared and non-hydrolysed chips.

7. The process according to claim 1, wherein the one or more wood products are one or more short-rotation energy crops selected from softwoods and hardwoods.

8. The process according to claim 1, wherein the one or more wood products are one or more softwoods selected from the group comprising pine, spruce and cedar.

9. The process according to claim 1, wherein the one or more wood products are one or more hardwoods selected from the group comprising aspen, birch, cotton woods, beech, poplar, willow and eucalyptus.

10. The process according to claim 1, wherein the one or more wood products are lignin.

11. The process according to claim 1, wherein the process comprises a further step b) comprising neutralizing the oxidized product of step a) extracting the product with an organic phase and filtering the oxidized product.

12. The process according to claim 11, wherein the oxidized product obtained after filtering is reused in the process.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention will now be explained more closely by the description of different embodiments of the invention and with reference to the appended figures.

(2) FIG. 1 shows chromatography data of copper catalyzed oxidation of lignin (Example 9)

(3) FIGS. 2A, 2B, 2C shows a GC-MS (EI) analysis (Example 9)

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

(4) As used herein “short-rotation energy crops” means fast growing softwoods, such as pine, spruce, birch and cedar or hardwoods, such as aspen, cotton woods, poplar, willow and eucalyptus.

(5) Wt % as used herein are percentages of the total weight of the solution or of the final material.

(6) The invention relates to a process for the production of oxidized wood products, comprising or consisting of step a) reacting chips of one or more wood products in a basic solution at a pH between 8 and 14 and under an oxygen atmosphere at a pressure of at least 0.1 MPa. The process of the invention may be used for the production of vanillin, vanillic acid, acetovanillone, syringaldehyde, veratraldehyde and biofuels from wood products, such as soft and hardwoods, lignin. The process is especially useful for the production of compounds that can be used in pharmaceutical or cosmetic products or in food products.

(7) The chips of the wood product used in the process do not need to be prepared prior to use in the process. Thus, no hydrolysis or washing of the chips is needed. The wood product may be mechanically prepared by cutting the wood product into chips. The chips may have an average diameter of about 0.2 cm, or between, 0.1 and 10 cm.

(8) The process may be performed at a pressure of at least 0.7 or 0.9 MPa. By increasing the pressure to between 0.8 and 2 MPa, the wood product oxidises quicker. The pressure may be between 0.5 and 10 MPa, or between 0.5 and 2 MPa, or between 0.5 and 1.5 MPa, or between 0.9 and 1.1 MPa or about 1.0 MPa.

(9) The basic solution is an aqueous solution with bases selected from the group comprising or consisting of NaOH, KOH, Ca(OH).sub.2 and Mg(OH).sub.2. The base may be NaOH.

(10) The basic solution has a molarity of 5 M or less. The basic solution may have a molarity 4.5 M or less, or 4 M or less, or 3.5 M or less. The basic solution may be a 3 to 5 M, or 4 M NaOH aqueous solution.

(11) Both air and oxygen may be used in the process of the invention. Advantageously, substantially pure or pure oxygen is used. The oxygen may have a purity of 95%, or 98% or 99%, or 99.9%.

(12) The invention relates to a process for the production of oxidized wood products, comprising or consisting of step a) reacting chips of one or more wood products in an aqueous solution with NaOH as a base having a molarity of 5 M or less and a pH between 12 and 14 under an oxygen atmosphere at a pressure between 0.9 and 1.1 MPa. Substantially pure or pure oxygen may be used.

(13) The temperature used in step a) is below 160° C., or 50 and 160° C., or between 60 and 150° C., or between 70 and 140° C., or between 71 and 139° C. or between 71 and 109° C. The reaction time for step a) depends on the temperature. An optimum reaction time can be achieved when the process is performed at a temperature between 71 and 139° C.

(14) The wood products are one or more short-rotation energy crops. A mixture of two or more species of short-rotation energy crops may be used in the process of the invention, Commonly, one species of short-rotation energy crop is used. The one or more wood products may be one or more softwoods. The one or more softwoods may be selected from the group comprising or consisting of pine, spruce, birch and cedar, or mixtures thereof. The wood product may be one or more hardwoods. The one or more hardwoods may be selected from the group comprising or consisting of aspen, cotton woods, poplar, beech, willow and eucalyptus, or mixtures thereof.

(15) The wood product may be lignin or oligomers of lignin or derivatives thereof. The process of the invention may also be used for oxidation of substantial pure primary, secondary and/or tertiary alcohols, in which case the wood product may be selected from the group comprising C.sub.1-6alcohol, such as ethanol, hexanol or benzyl-C.sub.1-6alcohol, or mixtures thereof. The invention relates to a process for the production of oxidized wood products, comprising or consisting of step a) reacting chips of one or more softwood in an aqueous solution with NaOH as a base NaOH having a molarity of 3 to 5 M and a pH between 12 and 14 under an oxygen atmosphere at a pressure between 0.9 and 1.1 MPa at a temperature between 60 and 150° C. The softwood may be lignin. Substantially pure or pure oxygen may be used.

(16) The process may be performed at atmospheric pressure of about 0.1 MPa. The process for the production of oxidized wood products may then comprise or consist of a step a) reacting the one or more wood product with oxygen gas or air in a water-based solvent comprising a liquid base at a pH between 8 and 14, whereby the process is performed under atmospheric pressure from 100500 to 102500 kPa, (i.e. about 0.1 MPa).

(17) The base may be selected from NaOH, KOH, Ca(OH).sub.2 and Mg(OH).sub.2. The molarity of the basic aqueous solution may be between 2 and 6 M, or between 3 and 5 M.

(18) The wood product may be as defined anywhere herein. In the process performed at atmospheric pressure of about 0.1 MPa, suitable the wood product may be selected from the groups comprising or consisting of C.sub.7-40alcohol, softwood, hardwood, polymers of lignin or derivatives thereof, paper, grass, plants, starches, grass, straw, herbaceous crops, saw dust, corn stover, other cellulose waste products and any combination thereof.

(19) The temperature of the process performed at atmospheric pressure of about 0.1 MPa may be between 60 and 150° C. or between 71 and 110° C.

(20) In one aspect, a Cu(0) catalyst in the form of pure copper may be used in step a) when the pressure is below 0.9 or 0.7, or 0.4, or 0.2 MPa or at atmospheric pressure (0.1 MPa). Copper may be used as pure copper in the form of pieces of a wire or a plate. The weight ratio of wood product to Cu(0) catalyst is from 50:1 to 1:1. The ratio may be 20:1 to 1:1 or 20:1 to 2:1. The ratio may be 50:1 to 5:1.

(21) In another aspect, the Cu(0) catalyst is reused.

(22) A (co-)catalyst may be added in step a). Examples of a non-metal (co-)catalyst may be 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) or derivatives thereof, or 2-azaadamantane-N-oxyl.

(23) Any kind of short-rotation energy crop as defined herein may be used in this process. In the process performed at atmospheric pressure of about 0.1 MPa, and using a none metal catalyst, suitable wood products may be selected from the groups comprising softwood, hardwood, lignin, paper, grass, plants, starches, grass, straw, herbaceous crops, saw dust, corn stover, other cellulose waste products and any combination thereof.

(24) Oxygen or air may be used in the process using the non-metal catalyst, or substantially pure oxygen may be used. The amount of non-metal (co-)catalyst used may be from 1 to 10 mol %, or from 2 to 7 mol %, or about 5 mol %.

(25) In one aspect, step a) is performed under stirring for 6 to 36 hours.

(26) The process may also comprise or consist of

(27) step a1) of reacting the wood product with a Cu(0) catalyst and oxygen gas or air in a non-aqueous and solvent-free environment (i.e. water or organic solvent) under atmospheric pressure and optionally adding a co-catalyst, and

(28) step a2) adding a liquid base at a pH between 8 and 14 in a water-based solvent, under atmospheric pressure (about 0.1 MPa).

(29) The Cu(0) catalyst may be a copper wire or plate, or pieces thereof, or copper powder. The reaction mixture may be heated to a temperature from 50 to 150° C., or from 75 to 105° C. The reaction is preferably performed under stirring for between 4 and 48 hours, or between 12 and 36 hours or between 6 and 36 hours.

(30) The base may be selected from NaOH, KOH, Ca(OH).sub.2 and Mg(OH).sub.2. One base may be NaOH. The base may be used at a concentration of 1 to 5 M, or about 2 M.

(31) Examples of a co-catalyst are 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) or derivatives thereof, or 2-azaadamantane-N-oxyl.

(32) The amount of co-catalyst used may be from 1 to 10 mol %, or from 2 to 7 mol %, or about 5 mol %.

(33) The ratio of catalyst to co-catalyst may be from 20:1 to 1:1, or from 1:2 to 1:1.

(34) The ratio of co-catalyst to wood product may be from 1:100 to 1:20, or from 1:14 to 1:20.

(35) The ratio of wood-product to catalyst to co-catalyst may be from 50:1:1 to 50:1:2 to 20:20:1, or from 20:1:1 to 20:1:2 to 20:20:1.

(36) The process may comprise a further step b) comprising neutralizing the oxidized product of step a), extracting the product with an organic phase and filtering the oxidized product. Prior to performing step b), the temperature of the reaction mixture may be reduced to room temperature.

(37) Preferably, the reaction mixture obtained after step a) is cooled down to room temperature prior to performing step b). Neutralization may be done by adding an acid to the reaction mixture, such a hydrochloride (HCl) or sulfuric acid, and the like. The pH of the neutralized solution may be below 7, such as between 1 and 5, or about 2.

(38) The aqueous phase obtained after filtering and neutralization may be extracted with an organic solvent. Examples of organic solvents may be ethyl acetate (EtOAc), diethyl ether (Et.sub.2O) and dichloromethane (CH.sub.2Cl.sub.2). The extracted organic phase can be evaporated, and the crude mixture filtered through e.g. a short silica gel column.

(39) Process step b) is performed at atmospheric pressure from 100500 to 102500 kPa, or 101325 kPa (about 0.1 MPa).

(40) The solid material obtained after filtering may be reused in the process. The solid material may be filtered off and washed with water and then reused in the next cycle of the process.

(41) The Cu(0) catalyst may also be reused or recycled. After filtering, the Cu(0) catalyst can be cleaned by washing the catalyst with an acid, e.g. 2M HCl. A black layer formed on the catalyst may be scraped off, after which the catalyst can be washed with water before reusing the catalyst in the next process.

(42) The invention thus relates to a process for oxidation of alcohols, which process may be performed as outlined below.

(43) I-a) The process may comprise or consist of step a) reacting chips of one or more wood products in a basic solution at a pH between 10 and 14 under an oxygen atmosphere at a pressure of at least 0.9 MPa, and step b) of neutralizing the oxidized product of step a), extracting the product with an organic phase and filtering the oxidized product.

(44) I-b) The process may comprise or consist of step a) of reacting the wood products with oxygen gas or air in a water-based solvent comprising a liquid base at a pH between 8 and 14, whereby the process is performed under atmospheric pressure from 100500 to 102500 kPa (about 0.1 MPa), and step b) of neutralizing the oxidized product of step a), extracting the product with an organic phase and filtering the oxidized product.

(45) I-c) The process may comprise or consist of step a) reacting chips of one or more wood products in a basic solution at a pH between 10 and 14 under an oxygen atmosphere at a pressure of at 0.7 MPa or less, in the presence of a Cu(0) catalyst, and step b) of neutralizing the oxidized product of step a), extracting the product with an organic phase and filtering the oxidized product.

(46) I-d) The process may comprise or consist of step a) reacting chips of one or more wood products in a basic solution at a pH between 10 and 14 under an oxygen atmosphere at a pressure of at 0.7 MPa or less, in the presence of a non-metal catalyst, such as TEMPO, and step b) of neutralizing the oxidized product of step a), extracting the product with an organic phase and filtering the oxidized product.

(47) The one or more wood products in processes I-a to I-d may be selected from the groups comprising or consisting of C.sub.7-40alcohol, softwood, hardwood, polymers of lignin or derivatives thereof, paper, grass, plants, starches, grass, straw, herbaceous crops, saw dust, corn stover, other cellulose waste products and any combination thereof.

(48) The one or more wood products may be one or more softwoods. The one or more softwoods may be selected from the group comprising or consisting of pine, spruce, birch and cedar, or mixtures thereof. The wood product may be one or more hardwoods. The one or more hardwoods may be selected from the group comprising or consisting of aspen, cotton woods, poplar, beech, willow and eucalyptus, or mixtures thereof.

(49) The wood product may be lignin or oligomers of lignin or derivatives thereof. The process of the invention may also be used for oxidation of substantial pure primary, secondary and/or tertiary alcohols, in which case the wood product may be selected from the group comprising C.sub.1-6alcohol, such as ethanol, hexanol or benzyl-C.sub.1-6alcohol, or mixtures thereof.

(50) II-a1) The process may comprise or consist of step a1) of reacting the wood product with a Cu(0) catalyst and oxygen gas or air in a non-aqueous and solvent-free environment (i.e. water or organic solvent) at atmospheric pressure (about 0.1 MPa), and step b) of neutralizing the oxidized product of step a1), extracting the product with an organic phase and filtering the oxidized product.

(51) II-b) The process may comprise or consist of step a1) of reacting the wood product with a Cu(0) catalyst and oxygen gas or air in a non-aqueous and solvent-free environment (i.e. water or organic solvent), and a co-catalyst, such as TEMPO, and step b) of neutralizing the oxidized product of step a1), extracting the product with an organic phase and filtering the oxidized product, whereby the process is performed under atmospheric pressure from 100500 to 102500 kPa (about 0.1 MPa).

(52) The wood product in processes II-a or II-b may be selected from the groups comprising or consisting of C.sub.1-6alcohol, such as ethanol, hexanol or benzyl-C.sub.1-6alcohol or oligomers of lignin or derivatives thereof. The process may be performed on straight or branched C.sub.1-6-alcohols, such as primary and/or secondary alcohols. Examples of such alcohols may be methanol, ethyl alcohol, such as ethanol, propyl alcohol, such as isopropanol, butyl alcohol, such a 1-butanol, pentyl alcohol, such as 1-pentanol or hexyl alcohol, such as 1-hexanol. The alcohol may be ethyl alcohol or hexanol. The alcohol may be benzyl-alcohol, such as phenyl methanol. The one or more wood products may be one or more softwoods. The one or more softwoods may be selected from the group comprising or consisting of pine, spruce, birch and cedar, or mixtures thereof. The wood product may be one or more hardwoods. The one or more hardwoods may be selected from the group comprising or consisting of aspen, cotton woods, poplar, beech, willow and eucalyptus, or mixtures thereof.

(53) The wood product may be lignin or oligomers of lignin or derivatives thereof. The process of the invention may also be used for oxidation of substantial pure primary, secondary and/or tertiary alcohols, in which case the wood product may be selected from the group comprising C.sub.1-6alcohol, such as ethanol, hexanol or benzyl-C.sub.1-6alcohol, or mixtures thereof.

(54) III-a) The process may comprise or consist of step a1) of reacting the wood product with a Cu(0) catalyst and oxygen gas or air in a non-aqueous and solvent-free environment (i.e. water or organic solvent), and step a2) adding a liquid base at a pH between 8 and 14 in a water-based solvent, and step b) of neutralizing the oxidized product of step a2), extracting the product with an organic phase and filtering the oxidized product, whereby the process is performed under atmospheric pressure from 100500 to 102500 kPa (about 0.1 MPa).

(55) III-b) The process may comprise or consist of step a1) of reacting the wood product with a Cu(0) catalyst and oxygen gas or air in a non-aqueous and solvent-free environment (i.e. water or organic solvent), and a co-catalyst, such as TEMPO, and step a2) adding a liquid base at a pH between 8 and 14 in a water-based solvent, and step b) of neutralizing the oxidized product of step a2), extracting the product with an organic phase and filtering the oxidized product, whereby the process is performed under atmospheric pressure from 100500 to 102500 kPa (about 0.1 MPa).

(56) The wood product in processes III-a or III-b may be selected from the groups comprising or consisting of C.sub.7-40alcohol, softwood, hardwood, polymers of lignin or derivatives thereof, paper, grass, plants, starches, grass, straw, herbaceous crops, saw dust, corn stover, other cellulose waste products and any combination thereof. The one or more wood products may be one or more softwoods. The one or more softwoods may be selected from the group comprising or consisting of pine, spruce, birch and cedar, or mixtures thereof. The wood product may be one or more hardwoods. The one or more hardwoods may be selected from the group comprising or consisting of aspen, cotton woods, poplar, beech, willow and eucalyptus, or mixtures thereof.

(57) The wood product may be lignin or oligomers of lignin or derivatives thereof. The process of the invention may also be used for oxidation of substantial pure primary, secondary and/or tertiary alcohols, in which case the wood product may be selected from the group comprising C.sub.1-6alcohol, such as ethanol, hexanol or benzyl-C.sub.1-6alcohol, or mixtures thereof. The solid material obtained after filtering may be reused in the process. The solid material may be filtered off and washed with water and then reused in the next cycle of the process.

(58) The Cu(0) catalyst may also be reused or recycled. After filtering, the Cu(0) catalyst can be cleaned by washing the catalyst with an acid, e.g. 2M HCl. A black layer formed on the catalyst may be scraped off, where after the catalyst can be washed with water before reusing the catalyst in the next process.

(59) The obtained oxidized product may comprise vanillin, vanillic acid, acetovanillone, syringaldehyde, veratraldehyde and biofuels, or mixtures thereof.

EXAMPLES

(60) Wt % is defined as a percentage of the total weight of the wood product as start material.

Example 1

(61) Oxidation of Soft and Hardwood

(62) To a 1.0-liter metal reaction vessel (laboratory digester), was charged with chips of either softwood (mixture of spruce and pine) or hardwood (e.g. beech), 24 g, 1.0 equiv.) and 200-600 mL NaOH 2-5 M. The laboratory digester was sealed, and the atmosphere changed to oxygen (0.5-1 MPa of O.sub.2 was applied). Next, the resulting mixture was allowed to blend at 70-140° C. for 8-18 h in a laboratory rotary digester.

(63) Then, the reaction temperature was decreased to room temperature. Next, the residue unreacted wood was filtered, and the reaction mixture acidified to pH=2, with 12 M HCl by slow addition of HCl. Next, the aqueous phase was extracted with an organic solvent (EtOAc). The extracted organic phase was evaporated, and the crude mixture was filtered through short silica gel column.

(64) For softwood (table 1, Entry 4), the synthesis produced 10.4 wt % vanillin, 2.2 wt % acetovanillone and 6.3 wt % vanillic acid. The calculations are based on the GC-MS analysis and confirmed by H-NMR analysis of the isolated product. See table 1.

(65) For hardwood (table 2), the synthesis produced 3.83 wt % vanillin, 0.98 wt % acetovanilone, 3.88 wt % vanillic acid, 4.05 wt % syringaldehyde, 0.58 wt % acetosyringone and 2.68 wt % syringic acid. The calculations are based on the GC-MS analysis and confirmed by H-NMR analysis of the isolated product. See table 2. Wt % are percentages of the total weight of the isolated product obtained after chromatography through the silica gel in respective to amount of lignin or wood chip.

(66) TABLE-US-00001 TABLE 1 Oxidation of softwood Entry.sup.[a] NaOH [M] Temp. [° C.] Time [h] a Wt [%].sup.[b] b Wt [%].sup.[b] c Wt [%].sup.[b] d Wt [%].sup.[b] 1 2.0 100 6.5 1.87 0.14 1.02 — 2 2.0 130 6.5 7.46 0.93 0.96 — 3 4.0 130 6.5 9.06 2.08 1.93 — 4 4.0 130 13.0 10.4 2.2 6.3 — .sup.[a]24 g, 122 mmol of soft wood were used here. Concentration, C = 0.3 M, under 10 bar O.sub.2. .sup.[b]Calculated yields based on GC-mass. 10 bar = 1 MPa

(67) TABLE-US-00002 TABLE 2 Oxidation of hardwood Entry.sup.[a] NaOH [M] Temp. [° C.] Time [h] a Wt [%].sup.[b] b Wt [%].sup.[b] c Wt [%].sup.[b] d Wt [%].sup.[b] e Wt [%].sup.[b] f Wt [%].sup.[b] 1 2.0 100 6.5 3.84 0.98 3.88 4.06 0.58 2.68 .sup.[a]24 g, 122 mmol of soft wood were used here. Concentration, C = 0.3 M, under 10 bar O.sub.2. .sup.[b]Calculated yields based on GC-mass (hard wood lignin content is 22.4%). 10 bar = 1 MPa

Example 2

(68) Large Scale Production of Oxidation of Soft and Hardwood

(69) 100 Liter Scale

(70) To a 100-liter metal reaction reactor (digester) is charged with wood (soft or hard, 10 kg, 1.0 equiv.) and 50 l NaOH 2-5 M. The reactor (digester) is then sealed and the atmosphere changed to oxygen (0.5-1 MPa of O.sub.2 is applied). Next, the resulting mixture is allowed to blend at 70-140° C. for 8-18 h.

(71) Then, the reaction temperature is decreased to room temperature. The residue of unreacted wood is filtered, and the reaction mixture is acidified to pH=2, with 12 M HCl by slowly adding HCl. Next, the aqueous phase is extracted with an organic solvent. The extracted organic phase is evaporated, distilled and re-used/recycled and vanillin is purified by recrystallization.

(72) 1000 Liter Scale

(73) To a 1000-liter metal reaction reactor (digester) is charged with wood (soft or hard, 100 kg, 1.0 equiv.) and 500 l NaOH 2-5 M. The reactor (digester) is then sealed and the atmosphere changed to oxygen (0.5-1 MPa of O.sub.2 was applied). Next, the resulting mixture is allowed to blend at 70-140° C. for 8-18 h.

(74) Then, the reaction temperature is decreased to room temperature. The residue of unreacted wood is filtered, and the reaction mixture is acidified to pH=2, with 12 M HCl by slowly adding HCl. Next, the aqueous phase is extracted with an organic solvent. The extracted organic phase is evaporated, distilled and re-used/recycled and vanillin is purified by recrystallization.

Example 3

(75) Procedure for the Cu(0)-Plate Catalyzed Catalytic Aerobic Oxidation Under Solvent-Free Conditions at Atmospheric Pressure.

(76) Ethyl Alcohol

(77) An oven-dried microwave vial (8 ml) equipped with a magnetic stir bar was charged with Cu(0)-plate (200-250 mg, 3×4 cm surface) and TEMPO (20 mg, 5 mol %). The vial was then sealed and ethyl alcohol (117 μl, 2 mmol) was added. The atmosphere was changed to oxygen and an oxygen balloon was connected to the reaction vessel. The resulting mixture was allowed to stir at 70° C. for 16 h. The reaction mixture was then diluted with CHCl.sub.3, and the formation of the corresponding acetaldehyde was confirmed by H-NMR.

(78) Benzyl Alcohol

(79) An oven-dried microwave vial (8 mL) equipped with a magnetic stir bar was charged with Cu(0)-wire (26 mg, 30 wt %, the Cu(0)-wire were cut into small pieces) and TEMPO (7 mg, 5 mol %). The vial was sealed, and the atmosphere was changed to oxygen and an oxygen balloon was connected to the reaction vessel. Next, benzyl alcohol (83 μl, 0.8 mmol) was added and the resulting mixture was allowed to stir at 70° C. for 16 h. The reaction mixture was diluted with CHCl.sub.3 and the formation of the corresponding acetaldehyde was confirmed by H-NMR.

(80) Hexanol

(81) An oven-dried microwave vial (8 ml) equipped with a magnetic stir bar was charged with Cu(0)-wire (24 mg, 30 wt %, the Cu(0)-wire cut into small pieces) and TEMPO (7 mg, 5 mol %). The vial was then sealed, the atmosphere was changed to oxygen and an oxygen balloon was connected to the reaction vessel. Next, hexanol (100 μl, 0.8 mmol) was added. The resulting mixture was allowed to stir at 100° C. for 16 h. The reaction mixture was diluted with CHCl.sub.3 and the formation of the corresponding hexanal was confirmed by H-NMR.

(82) Ethyl Alcohol

(83) An oven-dried microwave vial (8 ml) equipped with a magnetic stir bar was charged with Cu(0)-wire (11 mg, 30 wt %, the Cu(0)-wire were cut into small pieces) and TEMPO (7 mg, 5 mol %). The vial was sealed, and the atmosphere was changed to oxygen and an oxygen balloon was connected to the reaction vessel. Next, ethyl alcohol (47 μl, 0.8 mmol) was added and the resulting mixture was allowed to stir at 70° C. for 16 h. The reaction mixture was diluted with CHCl.sub.3 and the formation of the corresponding acetaldehyde was confirmed by H-NMR.

(84) Hexanol

(85) An oven-dried microwave vial (8 ml) equipped with a magnetic stir bar was charged with Cu(0)-wire (24 mg, 30 wt %, the Cu(0)-wire were cut into small pieces) and TEMPO (7 mg, 5 mol %). The vial was sealed, and the atmosphere changed to oxygen and an oxygen balloon was connected to the reaction vessel. Next, toluene (2.0 ml, C=0.4 M) and hexanol (100 μl, 0.8 mmol) was added. The resulting mixture was allowed to stir at 100° C. for 16 h. The reaction mixture was diluted with CHCl.sub.3 and the formation of the corresponding hexanal was confirmed by H-NMR.

(86) TABLE-US-00003 TABLE 3 Oxidation of primary alcohols Entry.sup.[a] R R.sup.1 Solvent Temp. (° C.) Time(h) Conversion (%).sup.[b] 1 Ph H neat 100 2 >98 2.sup.[c] H.sub.3C—CH.sub.2-4 H neat 70 16 17 3.sup.[c] Me H neat 70 16 31 4.sup.[d] H.sub.3C—CH.sub.2-4 H Toluene 100 16 26 .sup.[a]Performed under 1 atm. O.sub.2, Cu(0)-wire (10 w.t. % of Cu, the Cu(0)-wire were cut into small pieces), and TEMPO (5 mol %) at 100° C. under neat conditions. .sup.[b]Determined by .sup.1H NMR spectra on the crude reaction mixture. .sup.[c]30 w.t. % of Cu.sup.(0)-wire was used and TEMPO (5 mol %), at 70° C. .sup.[d]30 w.t. % of Cu.sup.(0)-wire was used and TEMPO (5 mol %), in toluene at 100° C., C = 0.4 M. 1 atm = about 0.1 MPa

Example 4

(87) The Oxidation Reaction of Lignin with Only 10 wt % Cu-(0)-Plate.

(88) The results are shown in table 4 below.

(89) TABLE-US-00004 TABLE 4 Entry.sup.[a] Catalyst Co-oxidant a Wt [%].sup.[b] b Wt [%].sup.[b] c Wt [%].sup.[b] d Wt [%].sup.[b] 1.sup.[c] Cu.sup.(0)-plate-(300 mg) — 2.2 0.4 0.9 — 2.sup.[d] Cu.sup.(0)-plate-(53 mg) — 1.5 0.2 1.3 — .sup.[a]Performed under 1 atm. or about 0.1.1325 MPa O.sub.2, Organo. solv. lignin were used here. Concentration, C = 0.3 M. .sup.[b]Calculated yields based on GC-mass. .sup.[c]0.6 mmol, 118 mg of org. solv. lignin were used. .sup.[d]2.4 mmol, 472 mg of org.solv. lignin were used.

Example 5

(90) 2-Oxidation of Softwood (Birch) in One-Pot:

(91) The results are shown in table 5 below.

(92) TABLE-US-00005 TABLE 5 0 Entry.sup.[a] Catalyst Co-oxidant a Wt [%].sup.[b] b Wt [%].sup.[b] c Wt [%].sup.[b] d Wt [%].sup.[b] 1 Cu.sup.(0)-plate-(300 mg) — 3.5 0.3 1.0 — .sup.[a]236 mg, 1,2 mmol of soft wood were used here. Concentration, C = 0.3 M. .sup.[b]Calculated yields based on GC-mass.

Example 6

(93) Oxidation of Softwood in Two-Step

(94) In step a) neat softwood (Birch) was reacted with copper under O.sub.2 for 16 h and next 2M NaOH was added. The reaction was stirred at 100° C. for additional 16 h. The results are shown in table 6 below.

(95) TABLE-US-00006 TABLE 6 Entry.sup.[a] Catalyst Co-oxidant a Wt [%].sup.[b] b Wt [%].sup.[b] c Wt [%].sup.[b] d Wt [%].sup.[b] 1 Cu.sup.(0)-plate-(300 mg) — 2.4 0.3 1.4 — 2 Cu.sup.(0)-plate-(300 mg) TEMPO 3.8 0.3 1.7 — .sup.[a]236 mg, 1,2 mmol of soft wood were used here. Concentration, C = 0.3 M. .sup.[b]Calculated yields based on GC-mass.

Example 7

(96) Copper Catalyzed Aerobic Oxidation of Lignin

(97) In table 7 shows selected optimizing condition reactions, whereby different co-catalysts (co-oxidants) and solvents are tested.

(98) TABLE-US-00007 TABLE 7 Entry Catalyst Co-oxidant Solvent Time [h] Conv. [%].sup.[a] 1 Cu.sup.(0)-plate (400mg) TEMPO Neat 18 32% 2 Cu.sup.(0)-plate (400mg) — Neat 18 <2% 3 Cu.sup.(0)-plate (400mg) Hydroquinone Neat 18 <2% 4 Cu.sup.(0)-plate (400mg) Lignosulfonate Neat 18 <2% 5 Cu.sup.(0)-plate (16mg) TEMPO NaOH 2M 18 7% 6 Cu.sup.(0)-plate (16mg) Hydroquinone NaOH 2M 18 26% 7 Cu.sup.(0)-plate (16mg) Lignosulfonate NaOH 2M 18 20% 8 Cu.sup.(0)-plate (16mg) — NaOH 2M 18 9% 9 — — NaOH 12M 18 <2% 10 Cu.sup.(0)-plate (400mg) TEMPO Neat 18 32% 11 Cu.sup.(0)-plate (70mg) TEMPO Neat 18 15% 12 Cu.sup.(0)-plate(20mg) TEMPO Neat 18 2% .sup.[a]mass of the vanillin formed based on GC-Mass. .sup.[a]mass of the vanillin formed based on GC-Mass.

Example 8

(99) Reaction Time Screening for the Cu(0)-Plate Oxidation Reaction of the Lignin Model.

(100) The effect of reaction time for step a) of the process was investigated. The results are shown in table 8 below.

(101) TABLE-US-00008 TABLE 8 Entry Catalyst Time [h] Conversion [%].sup.[a] 1 Cu.sup.(0)-plate (200-250mg), 0.7 × 0.3 cm 0.5 2.0 2 Cu.sup.(0)-plate (200-250mg), 0.7 × 0.3 cm 1.0 3.0 3 Cu.sup.(0)-plate (200-250mg), 0.7 × 0.3 cm 2.0 9.0 4 Cu.sup.(0)-plate (200-250mg), 0.7 × 0.3 cm 4.0 13.0 5 Cu.sup.(0)-plate (200-250mg), 0.7 × 0.3 cm 8.0 18.0 6 Cu.sup.(0)-plate (200-250mg), 0.7 × 0.3 cm 16.0 31.0 7 Cu.sup.(0)-plate (200-250mg), 0.7 × 0.3 cm 24.0 28.0 8 Cu.sup.(0)-plate (200-250mg), 0.7 × 0.3 cm 48.0 34.0 .sup.[a]mass of the vanillin formed based on GC-Mass.

Example 9

(102) Aerobic Copper Oxidation of Lignin with and without TEMPO.

(103) The effect of a co-catalyst was investigated.

(104) Procedure with TEMPO as a Mediator.

(105) To a round-bottomed flask (200 ml) equipped with a magnetic stir bar was charged with lignin (2 g, 1.0 equiv.), and Cu(0)-plate catalyst and TEMPO as co-catalyst (5 mol %). The round-bottomed flask was then sealed, and the atmosphere was then changed to oxygen and oxygen balloon was connected to the reaction vessel. Next, NaOH 2 M was added (20-40 ml) and the resulting mixture was allowed to stir at 80-140° C. for 6-12 h.

(106) After that, the reaction temperature was decreased, and the reaction mixture was neutralized with 2M HCl and extracted with an organic solvent. The extracted organic phase was evaporated, and the crude mixture was filtered through short silica gel column.

(107) The results are shown Table 9.

(108) TABLE-US-00009 TABLE 9 Entry.sup.[a] Catalyst Co-oxidant Wt [%].sup.[b] 1 Cu.sup.(0)-plate -(300mg) TEMPO 2.9 2 Cu.sup.(0)-plate-(300mg) — 3.0 3.sup.[c] Cu.sup.(0)-plate-(300mg) — 2.3 4.sup.[d] Cu.sup.(0)-plate-(300mg) — 4.1 .sup.[a]Organo.solv. lignin were used here. Concentration, C = 0.3 M. .sup.[b]Calculated yields based on GC-mass. .sup.[c]Reaction temperature at 140° C. Concentration, C = 0.3 M. .sup.[d]Reaction temperature at 140° C. Concentration, C = 0.085 M.

(109) The same results were obtained with or without TEMPO.

(110) Elevated reaction temperature did not improve the results of the oxidation reaction.

Example 10

(111) Using Different Type of Lignin

(112) Table 10 shows the result of the process of the invention, whereby different types of technical lignins have been used.

(113) TABLE-US-00010 TABLE 10 Entry Catalyst Lignin Wt [%].sup.[a] 1 Cu.sup.(0)-plate (200mg) organosolv. 3.0 2 Cu.sup.(0)-plate (200mg) kraft lignin 1.1 3 Cu.sup.(0)-plate (200mg) hydrolys lignin 0.3 4 Cu.sup.(0)-plate (200mg) sulphite lignin 0.8 5 Cu.sup.(0)-plate (200mg) Lignoboost lignin 1.8 .sup.[a]Calculated yields based on GC-mass.

Example 11

(114) Copper Catalyzed Oxidation of Lignin

(115) To a round-bottomed flask (200 ml) equipped with a magnetic stir bar was charged with lignin (2 g, 1.0 equiv.), and Cu(0)-plate catalyst. The round-bottomed flask was then sealed, and the atmosphere was changed to oxygen and oxygen balloon was connected to the reaction vessel during the whole reactions time (6-12 h). Next, NaOH 2 M was added (20-40 ml) and the resulting mixture was allowed to stir at 80-140° C. for 6-12 h.

(116) After that, the reaction temperature was decreased, and the reaction mixture was neutralized with 2M HCl and extracted with an organic solvent. The extracted organic phase was evaporated, and the crude mixture was filtered through short silica gel column. The synthesis at 100° C., 12 h, delivered 2.7 wt. % vanillin, 0.2 wt. % acetovanilone, 0.3 wt. % vanillic acid (The calculations are based on the GC-MS analysis) and were confirmed by H-NMR analysis of the isolated product.

(117) TABLE-US-00011 TABLE 11 GPC analysis for starting lignin and the recovered lignin after reaction Entry Mw Mn Mw/Mn Mp Starting lignin Peak 1 28889 28079 1.03 3117 Peak 2 4274 220 19.43 31472 Recovered lignin Peak 1 27610 26892 1.02 30397 Peak 2 5895 103 57.2 5206 Mw is 28889, Mn is 28079, Mp is 3117 Mw is molecular weight, Mn = Molecular number weight, Mp = molecular weight of peak maxima

(118) In addition, the GPC analysis of the starting lignin and the recovered lignin showed an increase of the measured mass due to the NaOH catalyzed condensations in the synthesis step a1) and during the work up step b).

(119) Further on, the GC-MS analysis confirmed the formation of the reported products (FIGS. 1 and 2).

Example 12a

(120) Copper Catalyzed Oxidation of Softwood

(121) To a round-bottomed flask (25 ml) equipped with a magnetic stir bar was charged with softwood (Birch) (1 g, 1.0 equiv.), and Cu(0)-plate catalyst. The round-bottomed flask was then sealed, and the atmosphere was then changed to oxygen and oxygen balloon was connected to the reaction vessel, during the whole reaction time (8-12 h).

(122) Next, NaOH 2 M was added (10-30 ml) and the resulting mixture was allowed to stir at 70-100° C. for 8-12 h.

(123) After that, the reaction temperature was decreased, and the reaction mixture was neutralized with 2M HCl and extracted with an organic solvent. The extracted organic phase was evaporated, and the crude mixture was filtered through short silica gel column. The synthesis delivered 1.0 wt. % vanillin, 0.1 wt. % acetovanilone, 0.3 wt. % vanillic acid (The calculations are based on the GC-MS analysis) and were confirmed by H-NMR analysis of the isolated product.

(124) In addition, we were able to recycle the start material, the softwood in several cycles.

Example 12b

(125) Metal-Free Oxidation of Softwood

(126) A round-bottomed flask (25 ml) equipped with a magnetic stir bar was charged with softwood (Birch) (1 g, 1.0 equiv.). The round-bottomed flask was then sealed, and the atmosphere was then changed to oxygen by connecting an oxygen balloon to the reaction vessel if O.sub.2 was used. Next, NaOH 2 M was added (10-30 ml) and the resulting mixture was allowed to stir at 70-100° C. for 8-12 h.

(127) After that, the reaction temperature was decreased to room temperature. Next, the residue softwood was filtered off and the reaction mixture neutralized with 2M HCl. Then, the aqueous phase was extracted with an organic solvent. The extracted organic phase was evaporated, and the crude mixture was filtered through short silica gel column.

(128) The synthesis delivered 2.1 wt. % vanillin, 0.35 wt. % acetovanilone, 1.7 wt. % vanillic acid. The calculations are based on the GC-MS analysis and were confirmed by H-NMR analysis of the isolated product.

Example 13

(129) Procedure for Recycling of the Start Material:

(130) After the neutralization step of the reaction mixture, the residue softwood (Birch) was filtered off and washed once with water. Next, the filtered material was placed in a new round-bottomed flask (25 ml) equipped with a magnetic stir bar was charged with Cu(0)-plate catalyst. The round-bottomed flask was sealed, and the atmosphere was changed to oxygen and oxygen balloon was connected to the reaction vessel, during the whole reaction time, 8-12 h. Next, the same amount of NaOH 2 M in the previous reaction was added (10-30 ml) and the resulting mixture was allowed to stir at 70-100° C. for 8-12 h. After that, the reaction temperature was decreased, and the reaction mixture was neutralized with 2M HCl. The solid material was filtered off and washed once with water and reused in the next cycle. The aqueous phase was extracted with an organic solvent. The extracted organic phase was evaporated, and the crude mixture was filtered through short silica gel column. As indicated in table 12, the same material could be recycled up to 6 cycles.

(131) TABLE-US-00012 TABLE 12 The recycling of the start material, the softwood Entry.sup.[a] Wt [%].sup.[b] 1 1.0 2 0.6 3 0.2 4 0.2 5 0.1 6 0.1 7 0.01 .sup.[a]The same start soft wood were recycled and used in the entries 1-7. .sup.[b]Calculated mass of the vanillin formed based on GC-Mass.

Example 14

(132) Recycled the Catalyst, the Cu(0)-Plate

(133) The Cu(0)-plate were removed from the reaction mixture after the neutralization with 2M HCl. The Cu(0)-plate were washed with 2M HCl once and the black layer formed on the plate were scraped off and washed with water once before the plate was reused in the next reaction.

(134) As indicated in table 13, the Cu-(0)-plate were reactive and efficiently catalyzed the oxidation reaction in many cycles.

(135) TABLE-US-00013 TABLE 13 Entry.sup.[a] Wt [%].sup.[b] 1 1.0 2 0.9 3 0.9 4 0.9 5 0.9 6 1.1 7 0.9 8 1.1 9 1.1 10 1.0 .sup.[a]The same Cu.sup.(0)-plate were recycled and used in the entries 1-10. .sup.[b]Calculated mass of the vanillin formed based on GC-Mass.

Example 15

(136) Oxidation reaction of wood in 2M NaOH as solvent using oxygen or air under atmospheric pressure, delivered vanillin in 2.1 wt %, acetovanillone in 0.35 wt % and vanillic acid in 1.7 wt % (Table 14, entry 1).

(137) TABLE-US-00014 TABLE 14 Oxidation of softwood, control experiments: 0 Entry.sup.[a] Catalyst Co-oxidant a Wt [%].sup.[b] b Wt [%].sup.[b] c Wt [%].sup.[b] d Wt [%].sup.[b] 1.sup.[c] — — 2.1 0.35 1.7 — 2.sup.[d] — — 1.0 — — — .sup.[a]236 mg, 1,2 mmol of soft wood were used here. Concentration, C = 0.3 M. .sup.[b]Calculated yields based on GC-mass. .sup.[c]Control reaction, Performed in NaOH 2M, under 1 atm. O.sub.2. .sup.[d]Control reaction, Performed in NaOH 2M, without O.sub.2.

(138) 1 atm. O.sub.2=0.1 MPa is use of oxygen gas under atmospheric pressure.

(139) without O.sub.2=use of air under atmospheric pressure.

(140) The reaction under normal atmosphere (air) delivered vanillin in 1 wt % as the only product (Table 14, entry 2).

(141) The present invention is not limited to the embodiments disclosed but may be varied and modified within the scope of the following claims.