METHOD FOR PREPARATION OF LIGNIN OLIGOMERS

Abstract

Disclosed herein is a process for depolymerization of lignin including thermally converting an aqueous mixture having a pH of at least 9 including lignin, catalyst and primary alcohol in a non-oxidizing atmosphere at a temperature of at least 280° C.

Claims

1. A process for depolymerization of lignin comprising thermally converting an aqueous mixture having a pH of at least 9 comprising lignin, catalyst and primary alcohol in a non-oxidizing atmosphere at a temperature of at least 280° C.

2. A process for depolymerization of lignin, comprising the steps of: a) Providing an aqueous mixture comprising: lignin, catalyst and primary alcohol having a pH of at least 9 in a non-oxidizing atmosphere, b) Thermally converting the lignin in the aqueous mixture at a temperature of at least 280° C., and c) Obtaining precipitated lignin oligomer.

3. The process according to claim 2, wherein the thermal conversion in step b) is performed for 3 to 7 h after precipitation of lignin oligomer starts.

4. The process of claim 2, wherein the aqueous mixture comprises 5 to 25 wt.-% lignin, 0.01 to 1.0 wt.-% catalyst, 1 to 5 wt.-% base, and 5 to 45 wt.-% primary C1 to C4-alcohol, based on the total weight of the aqueous mixture.

5. The process according to claim 2, wherein thermal conversion is conducted at 80 to 150 bar at reaction temperature of 280° C. to 400° C.

6. The process according to claim 2, wherein the catalyst selected from the group consisting of Ru, Cu, Co, Ni, Pt, sulfides of said metals, oxides of said metals and mixtures thereof.

7. The process according to claim 2, wherein the primary alcohol is selected from the group consisting of MeOH, EtOH, n-Propanol, n-Butanol and mixtures thereof.

8. The process according to claim 2, wherein the non-oxidizing gas is N.sub.2, argon, and/or H.sub.2.

9. The process according to claim 2, wherein the process provides lignin oligomers having a molecular weight of 250 to 750 g/mol, and/or having 2 to 10 aromatic moieties.

10. The process according to claim 2, wherein the process provides precipitated lignin oligomers having an oxygen content of less than 20 wt.-% based on the total weight of the precipitated lignin oligomers.

11. The process according to claim 2, wherein the catalyst, base, primary alcohol and/or unconverted lignin can be reintroduced in the process for depolymerization of lignin either in a batch or continuous process.

12. The process according to claim 2, wherein the depolymerized lignin-oligomer is further converted to polymers.

13. The process according to claim 2, wherein the depolymerized lignin-oligomer is further converted to polymers selected from the group consisting of polyesters, polyurethanes, polyamides and mixtures thereof.

14. The process according to claim 2, wherein the depolymerized lignin-oligomer is further converted to bio-based aromatics selected from the group consisting of toluene, benzene, xylenes and mixtures thereof.

15. A lignin oligomer composition comprising lignin oligomers, wherein the lignin oligomers have a number average molar mass Mn of 350 to 650 g/mol and a PDI of 1 to 3 and wherein the O/C weight ratio in the lignin oligomer is 0.13 to 0.28.

16. The lignin oligomer composition according to claim 15, wherein phenolic OH-content in the lignin oligomer is 2.0 to 1.0 mmol/g lignin oligomer.

17. The lignin oligomer composition according to claim 16, wherein the proportion of the .sup.1H-NMR signals of the aromatic C-H groups to the aliphatic CH-groups is from 3:1 to 1:8.

18. The lignin oligomer composition obtainable according to the process according to claim 2.

19. The lignin oligomer composition obtainable according to the process according to claim 2, wherein the lignin oligomers have a number average molar mass Mn of 350 to 650 g/mol and a PDI of 1 to 3 and wherein the O/C weight ratio in the lignin oligomer is 0.13 to 0.28.

20. (canceled)

21. The lignin oligomer composition obtainable according to the process according to claim 1, wherein the lignin oligomers have a number average molar mass Mn of 350 to 650 g/mol and a PDI of 1 to 3 and wherein the O/C weight ratio in the lignin oligomer is 0.13 to 0.28.

Description

FIGURES

[0054] FIG. 1 shows an overview process flow diagram how to depolymerize and deoxydehydrate lignin according to the invention including optionally recycling steps.

[0055] FIG. 2 shows IR spectrum of lignin (starting material=native lignin) and lignin oligomers (solid residue=depolymerization product) obtained by the process according to the present invention in Example 1.

[0056] FIG. 3 shows a diagram of yield of lignin oligomer (solid residue =depolymerization product) yield (wt.-%) over reaction time for Example 1.

[0057] FIG. 4 shows a comparison of different parameters of Lignin (Kraft lignin) and the hydrogenated lignin oligomer prepared according to Example 1.

[0058] FIG. 5 shows a comparison of different parameters of Lignin (Kraft lignin), the hydrogenated lignin oligomer prepared according to Example 1 and hydrogenated lignin material described in the prior art.

[0059] FIG. 6 shows a .sup.1H-NMR of the hydrogenated lignin oligomer obtained by the process according to the present invention in Example 1.

[0060] FIG. 7 shows a .sup.1H-NMR of the lignin starting material used as educt for the process according to the present invention in Example 1.

[0061] FIG. 8 shows a .sup.31P-NMR of the hydrogenated lignin oligomer obtained by the process according to the present invention in Example 1.

[0062] FIG. 9 shows a .sup.31P-NMR of the lignin starting material used as educt for the process according to the present invention in Example 1.

[0063] FIG. 10 shows a 2D .sup.1H-.sup.13C HSQC of the hydrogenated lignin oligomer obtained by the process according to the present invention in Example 1.

[0064] FIG. 11 shows a 2D .sup.1H-.sup.13C HSQC of the lignin starting material used as educt for the process according to the present invention in Example 1.

[0065] FIG. 12 shows a 2D .sup.1H-.sup.13C HMBC of the hydrogenated lignin oligomer obtained by the process according to the present invention in Example 1.

[0066] FIG. 13 shows a 2D .sup.1H-.sup.13C HMBC of the lignin starting material used as educt for the process according to the present invention in Example 1.

EXAMPLES

General Description of Experiments

[0067] Kraft-Lignin is prepared as described in US20170355723 and is used as a starting material for depolymerization reaction.

[0068] The experiments for lignin depolymerization are carried out at a temperature range of 250-350° C. in a 300 ml autoclave. 10 -25 wt.-% of lignin are dissolved in 1N NaOH aqueous solution and put in the autoclave. 0.02-0.26 wt.-% heterogeneous catalyst (Ru/C, Ni Nanoparticles, Cu/Al.sub.2O.sub.3, Ni/Al.sub.2O.sub.3) are added. A certain amount of alcohol (MeOH, EtOH, 1-Hexanol, tert-Butyl alcohol, isopropyl alcohol) relative to the NaOH solution is added (0-45 wt.-%). Wt.-% is based on the total weight of the aqueous mixture. The autoclave is flushed with H.sub.2 or N.sub.2. Then heating is started at a low speed of 80 to 120 rpm to homogenize the temperature. The reaction pressure is adjusted to 90 to 150 bar. After reaching the desired temperature, stirrer speed is adjusted to 2000 rpm. Reaction is performed for 0.5-12 h and then autoclave is cooled down to room temperature, depressurized and solid and liquid parts separated. After dissolution of the solid residue in an appropriate solvent (e.g. EtOH) the catalyst is separated by filtration. The obtained products are analyzed, usually by GPC, elemental analysis and IR-analysis.

GPC-Analysis

[0069] GPC analysis of the lignin used as starting product, the filtrate obtained after reaction as well as the solid residue (the lignin oligomers) after catalyst separation are performed. Samples are dissolved in DMSO+0.5% LiBr as solvent. DMSO+0.5% LiBr is used as eluent as well. The sample is filtered using a 0.2 μm membrane (Sartorius RC 25) before analysis. GPC analysis is performed using Agilent PolarGel M columns in DMSO/LiBr as solvent. Intensities are recorded by a UV-Vis detector (Agilent 1200 VWD 232 nm) and refractive index detector (DRI Agilent 1200 UV). Elution temperature is 35° C., flow rate is 0.5 ml/min. For DMSO+0.5% LiBr SEC calibration is carried out with narrowly distributed polystyrene sulfonate standards from the company PSS with molecular weights of M=208 to M=152,000.

Elementary Analysis (EA)

[0070] Elementary analysis is performed from freeze-dried samples to remove residual water and solvent. Elementary Analysis is performed using Elementary Microcube machines. One machine is devoted to measure sulfur content and the other one to measure the carbon, nitrogen and hydrogen values. Carbon, hydrogen, nitrogen and sulfur analysis is conducted by combustion followed by thermal conductivity and infrared detection of effluent gases. Sulfur effluent gases are adsorbed in hydrogen peroxide solution and resulting sulfuric acid is titrated with alkali base. The oxygen content was determined by considering proportional formula for organic compounds containing C, H and O.

IR Analysis

[0071] FT-IR spectra of Kraft lignin (starting material) and lignin oligomer (product) were recorded with Alpha-T Transmission FT-IR (MIR) Spectrometer equipped with universal sample module. Solid samples were deposited on a single ZnSe optical window and measured in spectral range of 600-4000 cm-1 in a transition mod.

NMR Analysis

[0072] One-dimensional direct excitation .sup.1H and .sup.13C spectra as well as .sup.1H, .sup.13C-correlation spectra (HSQC, qHSQC, and HMBC) were measured on a Bruker Avance IIIHD 700 spectrometer, operating at 700.30 MHz for .sup.1H and 176.10 MHz for .sup.13C, respectively. For all spectra, a cryogenically cooled (liquid Helium) CPTCI inverse probe was used. Samples were dissolved in DMSO-d6. Measurements were carried out in 5 mm NMR tubes.

[0073] All .sup.31P direct excitation spectra were measured on a Bruker Avance III 500 spectrometer, operating at 500.36 MHz for .sup.1H and 202.55 MHz for .sup.31P, respectively. This spectrometer was equipped with a cryogenically cooled (liquid Nitrogen) CPPBBO observe probe. Samples were dissolved in a mixture of CDCl3 and pyridine-d5, as specified in literature. Measurements were carried out in 5 mm NMR tubes.

Calculation of Polydispersity Index (PDI)

[0074] Derived from GPC-Data the Mass average molar mass (M.sub.w) is measured in [g/mol]

[0075] Derived from GPC-Data the Number average molar mass (M.sub.n) is measured in [g/mol]

[0076] PDI=M.sub.w/M.sub.n.

Example 1: Standard Experimental Conditions

[0077] Kraft-Lignin was prepared as described in US20170355723 and was used as a starting material for depolymerization reaction.

[0078] 10 g of lignin (10 wt.-%) was dissolved in a mixture of 3.2 g NaOH (3.2 wt.-%) in 76.8 g of deionized water (76.8 wt.-%) and 10 g EtOH (10 wt.-%) solution (final solution pH=13) to obtain an alkaline lignin mixture. Afterwards 260 mg of Ru/C (0.26 wt.-%) catalyst was added to the 10 wt.-% of the alkaline lignin mixture. Wt.-% is based on the total weight of the aqueous mixture. The depolymerization reaction was run for 6 h at 300° C. and 120 bar in Hz-atmosphere. Lignin depolymerization resulted in a solid residue and an aqueous reaction solution. Workup was done by depressurizing the reaction mixture at room temperature, filtering off the reaction solution. The remaining solid residue (lignin oligomer) was dissolved in EtOH. The catalyst that was trapped in the solid residue does not dissolve in EtOH and could be filtered off and recycled for the next experiment. (see FIG. 1). Both catalyst-free solution of lignin-oligomer and the filtrated reaction solution were analyzed by GPC (see Table 1).

TABLE-US-00001 TABLE 1 Molar mass and PDI of Kraft lignin (starting material), solid residue (lignin oligomer) and filtrated reaction solution determined by GPC analysis M.sub.n, M.sub.w, g/mol g/mol PDI = M.sub.w/M.sub.n Kraft lignin (starting material) 1400 10200 7.3 solid residue = lignin 581 1410 2.2 oligomer filtrated reaction solution 615 1330 2.4

[0079] Molecular masses and PDI were determined by DMSO+LiBr GPC using polystyrene sulfonate calibration

[0080] Formation of 5.9 g (59% yield) of solid residue (lignin oligomer) in the bottom of the autoclave was noticed. Obtained solid residue was well soluble in ethanol, acetone, THF, DMSO (except catalyst) and not soluble in water, toluene. Solubilization of solid residue in ethanol with subsequent filtration of Ru/C catalyst resulted in solution of lignin oligomer (see FIG. 1). No formation of insoluble char was found under applied conditions. The dissolved solid residue (lignin oligomer solution) could be dried and re-dissolved in ethanol.

[0081] The solid residue and reaction solution (the filtrate) were analyzed by GPC, elemental analysis and IR analysis.

[0082] Product Characterization:

[0083] GPC performed in DMSO+LiBr as solvent and eluent: [0084] Lignin (starting material) [0085] Solid residue, re-dissolved in EtOH (catalyst filtered off)=lignin oligomer solution [0086] Reaction solution (Filtrate, not yet depolymerized lignin, NaOH, EtOH solution) shows distinct molecular weight characteristics: [0087] Starting Lignin: Average molecular weight of 3400 g/mol and broad dispersity PDI=7.3. [0088] Solid residue=lignin oligomer: Average molecular weight of 540 g/mol and a narrow dispersity around PDI=2, preferably 2.3.  This material is fully soluble in EtOH; no traces of e.g. char-like substances are left in the reaction vessel after rinsing with EtOH. [0089] Reaction solution (Filtrate): Lower molecular weight distribution than in starting material but still high oxygen content (see Tables 1 and 3).

[0090] IR analysis of Solid residue, i.e. lignin oligomer shows similar aromatic bands to starting lignin and additionally a strong increase of aliphatic CH-signals and free aromatic OH bands (FIG. 2). Characteristic bands associated with lignin are summarized in Table 2. The bands related to aromatics C—H out of plane bending at 700-900 cm.sup.−1 and O—H stretching of hydroxyls more likely related to phenolic groups at 3000-3500 cm.sup.−1 are both present in starting lignin and lignin oligomer. The presence of three different bands for C—H out of plane bending at 867, 860, 811, 766, 750 cm.sup.−1 reveal that different substituents present in the aromatic rings. In particular, presence of 867 and 860 cm.sup.−1 band are associated with ortho- and para-substituted aromatics.

TABLE-US-00002 TABLE 2 Characteristic bands of lignin and lignin oligomer* 1/λ, cm.sup.−1 Absorption/vibration Functional group 3390 —O—H stretching * —O—H, hydrogen bonds 2940 —C—H stretching* —CH.sub.2—; —CH—; —CH.sub.3 1702 C═O stretching Carbonyl groups 1595; 1514 C═C stretching Aromatic C═C bonds (benzene ring) 1455; 1422 C—H deformation* Alkanes, —CH.sub.2— 1260-1084 C—O stretching; typical —C—O—; —C═S; vibration for sulfur —SO.sub.2— compounds* 1030 C—O stretching; —C—O—; —CH.sub.2— —CH.sub.2— bending 855; 814 C—O stretching; 1,4-substitution; —CH.sub.2— bending* 1,3,4-trisubstitution of benzene ring *Additional bands for depolymerized lignin

[0091] Table 3 shows elemental analysis of starting material (lignin) and the solid residue (lignin oligomers) obtained by the process according to the present invention and the not yet incompletely depolymerized and deoxydehydrated lignin fraction (filtrated reaction solution) that is still soluble in the aqueous reaction mixture (the filtrate).

TABLE-US-00003 TABLE 3 Elemental composition of Kraft lignin (starting material), solid residue and filtrated reaction. Sample C [%] O [%] H [%] O/C Kraft lignin (starting material) 64.3 29.7 6 0.46 filtrated reaction solution 57.5 35.7 6.8 0.55 solid residue = lignin oligomer 78.7 13.3 8 0.17

[0092] In comparison with the native lignin that contains 64.3 wt.-% of C, 29.7 wt.-% of O and 6.0 wt.-% of H the depolymerized product (lignin oligomer) exhibits significant deoxydehydration giving 13.3 wt. % of O. In parallel, the quantity of H and C increased to 8 wt.-% and 78.7 wt.-% respectively. The decrease of oxygen content is attributed to the deoxydehydration reaction catalyzed by e.g. Ru/C catalyst.

Example 2: Effect of Alcohol Addition

[0093] To evaluate the effect of alcohol these additional experiments were performed. The standard experiment (Example 1) was compared to the same experiment performed only in NaOH (no alcohol addition) and compared to an experiment performed with higher amounts EtOH content (NaOH:EtOH=1.8:45, wt. %/wt. % based on the total weight of the aqueous mixture) and smaller amounts EtOH content (NaOH:EtOH=3.6:5, wt. %/wt. % based on the total weight of the aqueous mixture).

[0094] In experiments with low or no alcohol addition no soluble solid residue was found. In pure NaOH medium char-like residue was formed. This char-like solid residue was completely insoluble in solvents like in ethanol, acetone, THF, DMSO, water and/or toluene.

[0095] In the experiment with higher EtOH content the nature of obtained solid residue=lignin oligomers is similar to the standard condition based on elemental analysis (Table 5). Both products have O/C ratio in the range of 0.16-0.17 that is significantly different from starting lignin material where O/C ratio is 0.46. However, the workup is more difficult as lower temperature below 5° C. is required for better recovery of lignin oligomer product by precipitation. Thus, addition of alcohol prevents insoluble char-like residue formation but should not be too high to allow efficient product precipitation and recovery. The results of alcohol addition and characteristics of obtained products are summarized in Tables 4 and 5.

TABLE-US-00004 TABLE 4 Experiments performed with different amounts of EtOH NaOH Lignin Soluble Lignin- Char-coal Alcohol (aq) content Ru/C Oligomers formation No 90 wt.-% 10 wt.-% 0.26 wt.-% no yes 10 wt.-% 80 wt.-% 10 wt.-% 0.26 wt.-% yes no EtOH 45 wt.-% 45 wt.-% 10 wt.-% 0.26 wt.-% yes no EtOH 5 wt.-% 90 wt.-%  5 wt.-% 0.13 wt.-% no yes EtOH

TABLE-US-00005 TABLE 5 Elemental analysis of solid residue (soluble lignin oligomers) obtained under standard conditions using 10 and 45 wt % of EtOH NaOH Alcohol (aq) C % O % S % N % H % O/C 10 wt % 80 wt.-% 74.5 12.3 0.15 <0.5 8 0.17 EtOH 45 wt % 45 wt.-% 78.8 12.3 0.13 <0.5 8.4 0.16 EtOH

Example 3: Effect of Alcohol

[0096] To determine the effect of alcohol type the lignin depolymerization was performed as described in Example 1 and additionally with MeOH, 2-Propanol, t-BuOH or n-Hexanol instead of EtOH. Results are shown in Table 6. Lignin oligomer product formation was noticed for the reaction performed in MeOH and EtOH. In case of MeOH the yield of product was 18% while for EtOH the yield was 59%. In addition, product received in case of performing depolymerization in the presence of MeOH had slightly higher O/C ratio, i.e. lower degree of deoxydehydration (Table 7). No product formation was noticed for the reaction performed with 2-Propanol, t-BuOH and n-Hexanol. The recovered liquid phase was freeze-dried and further analyzed by EA.

TABLE-US-00006 TABLE 6 Influence of alcohol nature on the lignin oligomer formation NaOH (aq) Lignin Lignin Additive content content Oligomer 10 wt % EtOH 80 wt.-% 10 wt.-% yes (59% yield) 10 wt % MeOH 80 wt.-% 10 wt.-% yes (18% yield) 10 wt % 2-Propanol 80 wt.-% 10 wt.-% no 10 wt % t-BuOH 80 wt.-% 10 wt.-% no 10 wt % n-Hexanol 80 wt.-% 10 wt.-% no Yield means: mass ratio of starting material (lignin) to dried lignin oligomer (product)

TABLE-US-00007 TABLE 7 Elemental analysis of lignin oligomer products using ethanol and methanol as an additive Alcohol C % O % S % N % H % O/C EtOH 74.5 12.3 0.15 <0.5 8 0.17 MeOH 72 17.2 0.15 <0.5 7.1 0.24

Example 4: Effect of Catalyst Addition

[0097] To determine the effect of heterogeneous catalyst the lignin depolymerization was performed without catalyst addition using EtOH or MeOH. Lignin depolymerization was performed under standard conditions at 300° C. for 6 h and 120 bar as described in Example 1 but without catalyst addition using two different alcohols (EtOH or MeOH) and two different NaOH:alcohol ratios (3.2:10 or 3.6:5, wt. %/wt. % based on the total weight of the aqueous mixture). No lignin oligomer product formation was noticed for the reaction performed without catalyst. However, some solvent-insoluble char-like residue was found. The liquid phase was freeze-dried and further analyzed by Elemental analysis. Elemental analysis reveals that nature of product obtained without catalyst addition is completely different. Indeed, all reaction products obtained without catalyst addition have high oxygen content in the range of 31-35 wt.-% which is comparable to the starting lignin (37.4 wt.-%). The calculated O/ C ratios for the products varies in the range of 0.60-0.68. In contrary depolymerization performed in the presence of a catalyst results in significant decrease of oxygen content till 12-14 wt. % that is results in 0.17 O/C ratio (Table 8). This shows that a deoxydehydration catalyst is required to obtain lignin oligomers with a molecular weight (Mw) below ˜500 and a uniform dispersity (PDI˜2). Thus, performing lignin depolymerization without a catalyst does not lead to the desired product and results in lignin oligomers with high dispersity.

TABLE-US-00008 TABLE 8 Comparison of lignin depolymerization in the presence and in the absence of Ru/C catalyst NaOH (aq) Alcohol Lignin Lignin Insoluble Catalyst content content content Oligomer char O/C Ru/C 80 wt.-% 10 wt.-% 10 wt.-% yes no 0.17 EtOH — 80 wt.-% 10 wt.-% 10 wt.-% no yes 0.61 EtOH — 80 wt.-% 10 wt.-% 10 wt.-% no yes 0.60 MeOH — 90 wt.-% 5 wt.-%  5 wt.-% no yes 0.69 EtOH — 90 wt.-% 5 wt.-%  5 wt.-% no yes 0.68 MeOH

Example 5: Using Other Catalysts

[0098] Other catalysts, like Ni nanoparticles, Ni/Al.sub.2O.sub.3/SiO.sub.2 and Cu/Al.sub.2O.sub.3/SiO.sub.2 were tested for lignin de-polymerization under standard conditions as described in Example 1 and analyzed by GCP (Table 9) and elemental analysis (Table 10). In all cases, the soluble solid residue was found after the reaction (standard reaction conditions: 6 h, 300° C., 120 bar). However, in case of using Ni Nanoparticles (NPs) the depolymerized product had higher polydispersity (PDI=2.8,) and slightly higher mass (M.sub.n=591 g/mol) in comparison with Ru/C (PDI=2.3, M.sub.n=508 g/mol) (see Table 7). The biggest difference was found in elemental analysis of obtained product. In case of using Ni NPs the amount of oxygen was higher than for Ru/C (see Table 10). Ni on alumina silica catalyst resulted in product with the same characteristics as the product received under standard conditions with Ru/C in terms of molar masses, dispersity and O/C ratio. However, the yield in this case was only 24% that is two times less than in case of Ru/C catalyst while the loading of Ni was ten times bigger in comparison with Ru. Application of Cu on alumina silica support however resulted in the lowest molar masses of depolymerized lignin (M.sub.n=473 g/mol) and dispersity (PDI=1.7). Using Cu on alumina silica support also resulted in 43% yield that is just 16% less than by using more expensive Ru/C catalyst. The loading Cu in this case was six times bigger than Ru in used in standard conditions. GPC chromatogram of product obtained by applying different catalyst are shown in the Table 9.

TABLE-US-00009 TABLE 9 Characteristics of obtained lignin oligomer product by using different catalysts Metal Yield of Het. Cat. loading, M.sub.n, M.sub.w, Lignin Catalyst loading wt % g*mol.sup.− g*mol.sup.−1 PDI Oligomer Ru/C 0.26 wt.-% 0.01 508 1160 2.3 59% Ni NPs 0.02 wt.-% 0.02 591 1640 2.8  48%* Ni/Al.sub.2O.sub.3/SiO.sub.2 0.26 wt.-% 0.12 562 1360 2.4 24% Cu/Al.sub.2O.sub.3/SiO.sub.2 0.26 wt.-% 0.06 473 789 1.7 43% Molecular masses and PDI were determined by DMSO + LiBr GPC using polystyrene sulfonate calibration Yield means: mass ratio of starting material (lignin) to dried lignin oligomer (product)

TABLE-US-00010 TABLE 10 Elemental analysis data of product obtained by using different catalysts Sample C % O % S % N % H % O/C Ru/C 74.5 12.3 0.15 <0.5 8 0.17 Ni NPs 68.1 19.5 0.22 <0.5 8.1 0.28 Ni/Al.sub.2O.sub.3/SiO.sub.2 77 11.7 0.25 <0.5 7.4 0.15 Cu/Al.sub.2O.sub.3/SiO.sub.2 75.1 12.3 0.21 <0.5 7.4 0.16

Example 6: Effect of Gas Nature and Pressure

[0099] To analyse the effect of the gas nature and pressure lignin depolymerization was performed under standard conditions (NaOH:EtOH=3.2:10 (wt. %/wt. %), 10 wt.-% Lignin, 2.6 wt.-% of Ru/C, 300° C., 6 h) using 120 bar reaction pressure in H.sub.2.Math.atmosphere as described in Example 1. Substitution of H.sub.2 with N.sub.2 also resulted in formation of a soluble solid residue (lignin oligomer). The solid residue was re-dissolved in EtOH and filtrated to remove Ru/C catalyst. Obtained products were analyzed by GPC and Elementary analysis. The GPC chromatogram of reaction product obtained with N.sub.2 was very similar to the standard conditions where 120 bar of H.sub.2 were applied (see Table 11) and resulted in low dispersity (PDI=2.3) and molar mass (M.sub.n=550 g/mol). However, decrease of pressure from 120 bar to 90 bar led to lower degree of depolymerization that resulted in slightly higher dispersity (PDI=2.5) and higher molar mass of residue (M.sub.n=678 g/mol). Performing depolymerization with N.sub.2 instead of H.sub.2 led to the higher yields of solid residue (product). The characteristics of obtained products were summarized in Table 11. Elementary analysis reveals similar nature of obtained products (see Table 12). A slight difference in composition was found in case of performing depolymerization under 90 bar of N.sub.2. No nitrogen incorporation into polymer structure was found for experiments performed under N.sub.2 pressure.

TABLE-US-00011 TABLE 11 Influence of gas nature and pressure on the residues found Reaction Yield of Non-Oxidizing pressure at. M.sub.n, M.sub.w, lignin gas. 300° C. g*mol.sup.−1 g*mol.sup.−1 PDI oligomer H2 120 bar 508 1160 2.3 59% N2 120 bar 550 1290 2.3 70% N2  90 bar 678 1680 2.5 66% N.sub.2 + H.sub.2(1:1) 120 bar 542 1270 2.4 41% Molecular masses and PDI were determined by DMSO + LiBr GPC using polystyrene sulfonate calibration Yield means: mass ratio of starting material (lignin) to dried lignin oligomer (product)

TABLE-US-00012 TABLE 12 Effect of gas nature and pressure on elemental composition of obtained products Reaction pressure at Non-oxidizing gas 300° C. C % O % S % N % H % O/C H.sub.2 120 bar 74.5 12.3 0.15 <0.5 8 0.17 N.sub.2 120 bar 74.5 13.3 0.12 <0.5 7.7 0.18 N.sub.2  90 bar 75.5 14 0.24 <0.5 7.3 0.18 N.sub.2+ H2(50%/50%) 120 bar 76 12.4 0.14 <0.5 8 0.16

Example 7: Effect of Reaction Time

[0100] To determine the effect of reaction time on product formation reaction time was monitored and product formation in Example 1 was analyzed by GPC and elementary analysis. No lignin oligomer precipitate was found within 0.5 h of depolymerization and 14 wt.-% lignin oligomer precipitate formed within 3 h (see FIG. 3). Performing reaction for 6 h delivered significant yield of lignin oligomer precipitate (51 wt.-%). However, increase of depolymerization time to 12 h lead to slight additional product yield of 55 wt.-%. Comparison of GPC chromatogram and elementary analysis of products obtained after 3, 6 and 12 h show same product characteristics (see FIG. 3 (Yield over time) & Tables 13/14). In addition, longer reaction time leads to decrease in Sulphur content. 5 h to 7 h reaction time are sufficient for obtaining desired product in high yield.

TABLE-US-00013 TABLE 13 Product PDI and yield depending on reaction time Reaction time M.sub.n, g/mol M.sub.w, g/mol PDI Yield  3 h 499 1080 2.2 14%  6 h 508 1160 2.3 51% 12 h 489 886 1.8 55% Yield means: mass ratio of starting material (lignin) to dried lignin oligomer (product)

TABLE-US-00014 TABLE 14 Comparison of elemental analysis of starting lignin with lignin depolymerized products at different time intervals Sample C % O % S % N % H % Starting lignin 61.9 28.5 1.8 >0.5 5.8 0.5 h No precipitate formed   3 h 76.6 12.3 0.16 <0.5 8.1   6 h 74 14.2 0.22 <0.5 7.6  12 h 74.3 12.5 0.11 <0.5 8.3

Example 8: Effect of Temperature

[0101] To determine the effect of applied temperature three experiments at 250° C., 280° C., 300° C. and 335° C. as described in Example 1 were performed using standard depolymerization conditions. No lignin oligomer precipitate was found after performing reaction at 250° C. for 6 h. Thus, temperature >250° C. is required for product formation within 6 h of reaction time. Increasing temperature to 335° C. resulted in formation of insoluble char (not the desired lignin oligomer). Thus, for optimized product formation and reduced or no char formation, reaction temperatures between 250 and 320° C., preferably 280° C. to 320° C., are recommended (see Table 15).

TABLE-US-00015 TABLE 15 Effect of temperature on formation of lignin oligomer and char Temperature Lignin Oligomer Insoluble char 250° C. no no 280° C. yes no 300° C. yes no 320° C. yes no 335° C. yes yes

Example 9: Effect of Base Concentration

[0102] The impact of base concentration was studied by comparing lignin depolymerization using 1.0 M NaOH (NaOH:EtOH=3.2:10, wt. %/wt. % based on the total weight of the aqueous reaction solution) and using 0.3 M NaOH (NaOH:EtOH=1:10, wt. %/wt. % based on the total weight of the aqueous reaction solution)). All other conditions were same as in standard Example 1. In both cases lignin oligomer was formed. Elemental analysis revealed similar composition of both products and identical O/C ratio (see Table 16). Both products possessed similar molar masses between 450-550 g/ mol and dispersity in the range of 1.8-2.7. The yield of product obtained using 0.3 M NaOH was 6.0 g compared to 5.9 g of product obtained with 1.0 M NaOH.

TABLE-US-00016 TABLE 16 Elemental analysis of tar-like precipitated products obtained under standard conditions using 1.0M NaOH and 0.3M NaOH Base C % O % S % N % H % O/C 1.0M NaOH 74.5 12.3 0.15 <0.5 8 0.17 0.3M NaOH 76.8 13.5 0.21 <0.5 7.9 0.17

Example 10: Effect of Lignin Loading

[0103] To determine the effect of lignin loading on product formation of lignin oligomer, the depolymerization under standard conditions (10 wt.-% of lignin using NaOH:EtOH=3.2:10 wt. %/wt. % based on the total weight of the aqueous reaction solution) was compared with a reaction using double amount of lignin (20 wt.-% of lignin, NaOH:EtOH=2.8:10 wt. %/wt. % based on the total weight of the aqueous reaction solution). An increased yield of solid residue product from 59% for standard experiment with 10 wt.-% lignin content to 76% in case of 20 wt.-% lignin content was observed. The yield was calculated by (weight of product/weight of starting lignin)*100%. All other conditions were same as in standard Example 1.

[0104] The product was dissolved in EtOH and characterized by GPC and elemental analysis. Both products exhibited similar elemental composition.

Example 11: Recycling

[0105] A recycling experiments was done by applying 90 bar reaction pressure in N.sub.2-Atmosphere, the other reaction conditions were kept constant (see Example 1).

[0106] The reaction solution (filtrate) obtained after first cycle of lignin conversion, together with recovered Ru/C catalyst were re-used for a second cycle. In this case a new portion of lignin equal to the mass of recovered product in the first catalytic cycle was added. Thus, concentration of lignin was kept constant in first and second cycles. The reaction solution, containing the base and the alcohol and not yet precipitated lignin was recycled as well.

[0107] In both cycles similar yields of residue were obtained. Characteristics of obtained products are summarized in the Table 17.

TABLE-US-00017 TABLE 17 Comparison of products obtained in I and II cycles under recycling conditions described in method B M.sub.n, M.sub.w, Yield Lignin Sample g*mol.sup.−1 g*mol.sup.−1 PDI O/C Oligomer I cycle 678 1680 2.5 0.18 70% II cycle 504 1060 2.1 0.14 66% Molecular masses and PDI were determined by DMSO + LiBr GPC using polystyrene sulfonate calibration

[0108] The recycling procedure showed that Ru/C catalyst, the reaction solution comprising alcohol, base and residual lignin can be recycled. A schematic recycling procedure is presented in FIG. 1.

Example 12 (.SUP.1.H-NMR Spectra of the Lignin Oligomer Obtained According to Example 1 and the Lignin Starting Material)

[0109] 155 mg/ml sample (Lignin or lignin oligomer) were dissolved in deuterated DMSO. The Sample was fully soluble.

[0110] Comparing the 1H-NMR spectra of the lignin oligomer (obtained according to example 1) relative to the starting lignin material shows less aromatic signals in the hydrogenated lignin oligomer sample. The proportion of C—H-aromatics signals to the C—H-aliphatic signals in the lignin oligomer sample is 1:7 (FIG. 6) compared to 2:1 in the lignin starting material (FIG. 7). In the range of 3.5 to 4 ppm a strong decrease of the CH.sub.2—OH and Aromatic-O—CH.sub.3 is observed due to hydrogenation of the lignin oligomer. Exception is a quartet-signal, that can be attributed to residual reaction solvent Ethanol, which was not completely removed from the lignin oligomers. The corresponding triplet in the aliphatic region of the spectrum increases the integral over the aliphatic region relative to the aromatic region.

Example 13 (.SUP.31.P-NMR Spectra of the Lignin Oligomer Obtained According to Example 1 and the Lignin Starting Material)

[0111] .sup.31P-NMR Analysis: 15 mg sample (lignin or lignin oligomer) were treated w/50 μl 2-Chlor-4,4,5,5-tetramethyl-1,3,2-dioxaphospholan in 400 μl Pyridine and CDCl3 (1,6:1 v/v). Additionally, cyclohexanol as internal standard and Cr(III)-Acetylacetonat (as relaxation agent) were added in 150 μl Pyridine/CDCl3. The sample was analyzed as “quantitative 31P-NMR”. The .sup.31P-NMR signals were attributed according to literature: J. Agric. Food Chem. Vol. 43, No. 6, 1995—Granata and Argyropoulos). The sample shows signals for aliphatic-OH, phenolic-OH and carboxylic acids. Syringyl. And Guaiacyl-rings can be distinguished. The total amount of aliphatic, phenoic and carboxylic OH were determined. Table 18 shows the differences in the signals between lignin (starting material, FIG. 9) and lignin oligomer (product, FIG. 8).

TABLE-US-00018 TABLE 18 Calculation .sup.31P-NMR beta M m [mg] in [mg/mg] [g/mol] V [μl] 150 μl N [mmol] Cyclo- 6.38 100.158 150 0.957 0.009554903 hexanol Cr(III) 5.8 acac Results Sample OH-Content in M [mg] [mmol/g] Syringyl and Total Aliph.- phenolic phenolic OH OH Guaiacyl Carboxyl-OH OH Total-OH Lignin 14.16 0.93 0.61 0.62 0.46 1.23 2.62 Oligomer Lignin 15.03 1.54 1.26 1.86 0.32 3.12 4.98

Example 14 (2D 1H-13C HSQC NMR Spectra of the Lignin Oligomer Obtained According to Example 1 and the Lignin Starting Material)

[0112] 155 mg/ml sample (lignin or lignin oligomer) were dissolved in deuterated DMSO. The Sample was fully soluble.

[0113] 2D .sup.1H-.sup.13C HSQC NMR of initial Kraft lignin (FIG. 11) shows the aromatic protons of the monomer units by cross-correlation peaks at δ.sub.c/δ.sub.H 110-118/6.7-6.9 ppm. These units are linked in a 3D polymer network by different binding motifs which the ß-O-4 linkage (A) and is most pronounced. The cross peaks at δ.sub.c/δ.sub.H 60-65/3.2-3.7 ppm are attributed to the protons linked to ß and γ carbons in (A). Other structures like resignol (C) (series of cross peaks at δ.sub.c/δ.sub.H 85.03/4.63, 53.69/3.07 and 70.98/4.17 attributed to protons linked to α, β, and γ carbons accordingly) and phenylcumaran (B) (δ.sub.c/δ.sub.H 86.72/5.48 attributed to proton at α position) were detected as well. The integration of protons attached to α carbon in each structure allowed to calculate the relative ratio of linkages: 42% of A (ß-O-4 linkage), 37% of C (ß-ßlinkage) and 21% of B (ß-5 linkage).

[0114] 2D .sup.1H-.sup.13C HSQC NMR_of ‘Lignin oligomer’ product (FIG. 10) shows significant difference in comparison to the starting Kraft lignin. A major difference is the absence of x-correlation peaks in the region of δ.sub.C/δ.sub.H 50-90/3.0-4.5 ppm. These signals in Kraft-Lignin were associated to ß-O-4, ß-ß and ß-5 linkages. This indicates an almost quantitative cleavage of ether linkages under the applied reaction conditions and proving the lignin depolymerization. Additionally, the signal associated with —OCH.sub.3 group of aromatic cores (δ.sub.C/δ.sub.H 56/3.8 ppm) is absent as well.

[0115] More considerable differences were found in the aromatic regions. The starting Kraft lignin (FIG. 1) displayed aromatics signals in the region of δ.sub.C/δ.sub.H 105-120/6.2-7.7, caused by the presence of electron withdrawing methoxy groups at the aromatic cores. The aromatic signals of the lignin oligomer are instead shifted to δ.sub.c/δ.sub.H 120-130/6.8-8.0, which is caused by the absence of electron withdrawing —OCH.sub.3 groups attached to aromatic cores. Comparison of chemical shifts of the obtained lignin-oligomer and monomers resembling lignin repeating units (e.g. 4-propylphenol and 2-methoxy-4-propylphenol, inset in FIG. 10) revealed significant similarity. The shifts of 4-propylphenol seem to fit best to the obtained structure.

[0116] The strong correlation at 55 ppm in .sup.13C spectrum and 3.5-4.5 ppm in .sup.1H spectra is related to the —OCH.sub.3 groups of the aromatic cores. Alkyl-chains, resulting from the p-propyl-group are found at δC/δH 13-45/0.8-3.0 ppm.

Example 15 (2D .SUP.1.H-.SUP.13.C HMBC NMR Spectra of the Lignin Oligomer Obtained According to Example 1 and the Lignin Starting Material)

[0117] 2D .sup.1H-.sup.13C HMBC NMR 155 mg/ml sample (lignin or lignin oligomer) were dissolved in deuterated DMSO. The Sample was fully soluble.

[0118] 2D .sup.1H-.sup.13C HMBC NMR of Kraft lignin (FIG. 13) possess a high number of cross-correlation peaks due to the complex structure of the polymer. The most pronounced correlation are at δC/δH 150/6.5-7.5 ppm (2) which are assigned to aromatic protons in proximity to quaternary, heteroatom bound aromatic carbon (CH—C(OH)—CH). This proves the presence of phenolic groups in the polymer structure. The cross peaks δC/δH 150/6.5-3.9 ppm result from correlation of protons of—−OCH.sub.3 group with quaternary, heteroatom bound aromatic carbon (CH—C(OH)—CH).

[0119] 2D .sup.1H—.sup.13C HMBC NMR of ‘Lignin oligomer’ (FIG. 12) is less busy in comparison to starting lignin, which indicates a more uniform structure. The presence of phenolic OH could be confirmed by cross peak at δC/δH 150/6.8 ppm (1), which displays interaction of aromatic protons to aromatic, quaternary, heteroatom bound carbon. The additional cross peaks at δC/δH 150/2.2 ppm and δC/δH 150/2.6 ppm are attributed to correlation of the same quaternary carbon atom with —CH2-groups of alkyl chains (2). These kinds of correlations haven't been seen in the starting kraft lignin, indicating methoxy group elimination and alkylation. Additional cross peaks at δC/δH 128/2.2 ppm (4) and δC/δH 128/2.6 ppm (3) show correlation of alkyl protons with aromatic carbons in position 3, 4, 5. The absence of a correlation between -CH3 group and aromatic carbons (δC/δH 125-150/0.8-0.9 ppm) shows elimination of methoxy groups.

[0120] In the HMBC, no additional signals of acids, esters or aldehydes relative to the starting material were observed.

[0121] NMR Interpretation

[0122] The hydrogenated lignin oligomer sample has a lower total-OH content than the starting materials. Both aliphatic-OH and aromatic OH are reduced relative to the starting material. Ethanol can be distinguished as residual solvent left in the sample. The content of carboxylic-OH does not rise significantly. However, methoxy groups are drastically reduced beyond detection limit. The ratio of aromatic CH to aliphatic CH is decreased significantly from 2:1 to 1:7.