CATALYTIC FUNNELING OF PHENOLICS

Abstract

In general, present invention concerns an integrated wood-to-xylochemicals biorefinery, enabling production of renewable phenol, phenolic oligomers, propylene, and carbohydrate pulp from lignocellulosic biomass.

Claims

1. A method comprising the steps of: a) providing a mixture of compounds of formula (I): ##STR00005## wherein: each occurrence of R.sub.1 and R.sub.2 is independently selected to be —O—CH.sub.3 or —H; each occurrence of R.sub.3 is independently selected to be —H, or -methyl, or -ethyl, or -propyl, or -propylene, or -1-alkoxypropyl, or -3-hydroxypropyl; b) preparing a reaction mixture by contacting the mixture of compounds of step a) in gas phase, with a reaction mixture containing a metal-based catalyst, under a hydrogen containing gas atmosphere; wherein step b) is carried out at a temperature of at least 265° C. and a partial hydrogen pressure of at least 0.2 bar; and c) obtaining from step b) products comprising a mixture of compounds of formula (Ia), as well as methane or methanol or both ##STR00006## wherein: R.sub.1 is independently selected to be —CH.sub.3 or —H; R.sub.2 is independently selected to be —H, or -methyl, or -ethyl, or -propyl; and m and n represent the position on the aromatic ring, with m being any one of the numbers 2-6 and with n being any one of the numbers 3-5, with m not being equal to n.

2. The method according to claim 1, wherein the metal-based catalyst comprises metal attached on a support material.

3. The method according to claim 1, wherein the metal-based catalyst comprises metal attached on a support material and wherein the metal is nickel and the support is silica.

4. The method according to claim 1, wherein the metal-based catalyst is a promoter-modified nickel catalyst.

5. The method according to claim 1, wherein in step b) a partial pressure of 0.2-10 bar H.sub.2 is used.

6. The method according to claim 1, wherein in step b) a partial pressure of 0.2-1 bar H.sub.2 is used.

7. The method according to claim 1, wherein a complete removal of methoxy substituents is obtained with >70% molar yield to propyl phenols or ethyl phenols or a combination of both, based on a mixture of compounds with formula I.

8. The method according to claim 1, wherein the resulting products with formula Ia obtained in step c) in claim 1 are subjected to a dealkylation process comprising the steps of: d) providing the mixture of compounds of formula (Ia); e) preparing a reaction mixture by contacting the mixture of compounds of step d) in gas phase, with an acidic zeolite, and water and wherein step e) is carried out at a temperature of at least 260° C.; and f) obtaining from step e) products comprising a mixture of compounds of formula (Ib) as well as olefins comprising propylene or ethylene or a combination of both, ##STR00007## wherein: R.sub.1 is independently selected from —CH.sub.3 or —H; and p represents the position on the aromatic ring, with p being any one of the numbers 2-6.

9. The method according to claim 8, wherein the acidic zeolite belongs to the pentasil family of zeolites.

10. The method according to claim 8, wherein the acidic zeolite is a ZSM-5 zeolite.

11. The method according to claim 8, wherein the acidic zeolite is a hierarchical version of a ZSM-5 zeolite with Si/Al ratio of 140.

12. The method according to claim 8, wherein a partial pressure of 0.2-1 bar H.sub.2 in step b) is used and wherein the metal-based catalyst comprises metal attached on a support material wherein the metal is nickel and the support is silica.

13. The method according to claim 8, wherein the mixture of compounds with formula Ib and olefins are obtained in a molar yield of >40% based on the mixture of compounds with formula I.

14. The method according to claim 1, wherein the produced mixture of compounds with formula Ia is further converted to a mixture of compounds with formula Ic: ##STR00008## wherein: R.sub.1 is independently selected to be —CH.sub.3 or —H; R.sub.2 is independently selected to be -propyl or -ethyl; and q represents the position on the aromatic ring, with q being any one of the numbers 2-6.

15. The method according to claim 14, wherein the catalyst comprises a platinum group metal (PGM) selected from the group consisting of platinum and palladium, and wherein this metal is on a titanium oxide support.

16. The method according to claim 14, wherein the catalyst is selected from the group consisting of a promoter-modified platinum catalyst and a promoter-modified palladium catalyst.

17. The method according to claim 14, wherein the catalyst achieves a constant conversion of the mixture of compounds with formula I for a time on stream of at least 5 hours, measured at a conversion level below full conversion.

18. The method according to claim 14, wherein a mixture of compounds with formula Ic is obtained in >60% molar yield based on a mixture of compounds with formula I.

19. The method according to claim 14, wherein n-propylbenzene is obtained in >40% molar yield based on a mixture of compounds with formula I.

20. The method according to claim 14, wherein a partial pressure of 0.2-1 bar H.sub.2 in step b) is used.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0022] This disclosure will become more fully understood from the detailed description given herein below and the accompanying drawings, which are given by way of illustration only, and thus are not limitative of this disclosure, and wherein:

[0023] FIG. 1. Routes to phenol from (i) fossil oil by the current industrial Hock process, (ii) technical (isolated) lignin by the Lignol™ process, and (iii) in planta lignin by the proposed process.

[0024] FIG. 2. Box plots showing the distribution of monomer yields for different lignin depolymerization methods. Methods that do not yield phenolic compounds are indicated in white. These include bifunctional hydroprocessing, which targets alkanes, and oxidation to non-phenolic acids, which yields small carboxylic acids (e.g., formic acid, acetic acid) and dicarboxylic acids (e.g., succinic acid).

[0025] FIGS. 3A-3C. Hydroprocessing of 4-n-propylguaiacol to n-propylphenols and ethylphenols. FIG. 3A: Influence of different metal catalysts (285° C. and 4.5 h.sup.−1 WHSV, unless indicated otherwise). FIG. 3B: Influence of different nickel catalysts (285° C., unless indicated otherwise). FIG. 3C: Gas chromatograms of conversion of 4-n-propylguaiacol over 17 wt. % Ni/Al.sub.2O.sub.3 and 64 wt. % Ni/SiO.sub.2 (at similar conversion, ca. 62%). Reaction conditions: 1 bar of total pressure (0.4 bar H.sub.2 partial pressure). The data are taken at time-on-stream of 5 h.

[0026] FIGS. 4A-4D. Catalytic evaluation of the hydroprocessing step to funnel lignin-derived monomers toward few alkylphenols. FIG. 4A: Activity of nickel catalyst (PG at 285° C. with low conversion<20%, time-on-stream of 3 h). FIG. 4B: Selectivity to PPs versus PG conversion (285° C. at different WHSV). FIG. 4C: Evolution of conversion and products selectivity with time-on-stream over 64 wt. % Ni/SoO.sub.2 (PG at 285° C. and 6.0 h.sup.−1 WHSV). FIG. 4D: Different lignin-derived phenolics (over 64 wt. % Ni/SiO.sub.2: EG, PG, isoeugenol and pine-derived monomers at 285° C. and 8.2, 6.0, 4.4 and 6.0 h.sup.−1 WHSV, respectively; PS(I), PS(II) and birch-derived monomers at 305° C. and 7.1, 5.3 and 5.3 h.sup.−1 WHSV, respectively). Constant reaction conditions: 1 bar of total pressure (0.4 bar H.sub.2 partial pressure). The data in FIGS. 4B and 4D are taken at time-on-stream of 5 h.

[0027] FIGS. 5A-5H. Catalytic evaluation of the dealkylation step to funnel alkylphenols toward phenol and olefins. Dealkylation of the hydroprocessing products from the extracted monomers of pine wood lignin oil over Z140-H (FIG. 5A) at different temperature. Dealkylation of the hydroprocessing products from (FIG. 5B) PG, the extracted monomers of (FIG. 5C) pine and (FIG. 5D) birch wood lignin oils at 410° C. over Z140-H with TOS. Conversion (rate) and selectivity versus (FIG. 5E) temperature and (FIG. 5F) TOS (305° C. and 395° C., respectively) over Z140-H and Z140-P for conversion of isopropylcresols with 4.1 h.sup.−1 WHSV. Conversion (rate) and selectivity versus (FIG. 5G) temperature and (FIG. 5H) TOS (395° C.) for conversion of n-propylphenols over Z140-H. C-mol yield represents the carbon molar yield in the product stream. Ramping rate is 1° C. min.sup.−1 in FIGS. 5A, 5E, and 5G. 2.8 and 3.7 h.sup.−1 WHSV for FIGS. 5D and 5A-5C, 5G-5H, respectively. The theoretical yield (84.5%) in FIG. 5D is the maximum combined yield of phenol and olefins based on the substrate composition.

[0028] FIGS. 6A-6E. Dealkylation of n-propylbenzene over Z140-H. FIG. 6A: Conversion rate of n-propylbenzene and selectivity to benzene and propylene as a function of temperature (ramping rate=1° C. min.sup.−1, no water); FIG. 6B: The products distribution as a function of temperature (ramping rate=1° C. min.sup.−1, no water); FIG. 6C: Gas chromatogram at low and high temperature (conversion); Conversion of n-propylbenzene as a function of time-on-stream (TOS) over (FIG. 6D) Z140-H (410° C.) and (FIG. 6E) Z12-P (350° C.) without water. WHSV=3.2 h.sup.−1. In FIG. 6B others include toluene, ethylene, and some unidentified products, 1 bar.

[0029] FIGS. 7A-7F. Catalytic conversion of cresols over zeolites. FIG. 7A: Conversion of cresols and selectivity to phenol in the conversion of cresols over Z140-H; FIG. 7B: The catalytic stability of Z140-H in the conversion of cresols. Isomerization was used as the criterion for measuring the stability; FIG. 7C: The conversion of cresols and selectivity to phenol in the conversion of cresols over Z40-P (Si/Al=40); FIG. 7D: Gas chromatogram of cresols conversion over Z40-P; FIG. 7E: The conversion of cresols and selectivity to phenol in the conversion of cresols over USY-40 (Si/A=40); FIG. 7F: Gas chromatogram of cresols conversion over USY-40. Selectivity (%)=yield of products/theoretical yield×100%. Ramping rate=1° C. min.sup.−1 in FIGS. 7A, 7C, and 7E. Temperature in FIG. 7B is 410° C., temperature in FIGS. 7D and 7F is 470° C. 2.9 g h.sup.−1 WHSV, molar ratio of H.sub.2O to 4-methylphenol=6, 1 bar.

[0030] FIG. 8. Proposed integrated biorefinery process flow diagram. Overview of the process to produce carbohydrate pulp, phenol, propylene, phenolic oligomers from lignocellulose.

[0031] FIGS. 9A-9B. FIG. 9A: Mass balance of this integrated biorefinery (assuming the conversion of 1 ton birch wood); FIG. 9B: Mass balance of monomers conversion (1 ton birch wood basis). The amount of hydrogen and methanol in the scheme is the consumed amount and not the loaded ones.

[0032] FIGS. 10A-10B. GWP of (FIG. 10A) phenol, phenolic oligomers, (FIG. 10B) propylene, and carbohydrate pulp in this biorefinery with different scenarios (i.e., several hydrogen sources and/or forest management strategies). The GWP of H.sub.2 is, respectively, 11.89 kg CO.sub.2 equivalent, 8.20 kg CO.sub.2 equivalent, and 0.97 kg CO.sub.2 equivalent for non-renewable H.sub.2 I, non-renewable H.sub.2 II, and renewable H.sub.2 III. The GWP of phenolic oligomers from oil refinery is GWP of nonylphenol (>1.58 kg CO.sub.2 equivalent).

[0033] FIG. 11. Carbon flow of this biorefinery. Numbers in red represent carbon from methanol

[0034] FIGS. 12A-12D. Dealkylation of 4-n-propylphenol over Z140-H. FIG. 12A: The products distribution as a function of temperature, ramping rate=1° C. min.sup.−1; FIG. 12B: Gas chromatogram at low and high temperature (conversion); FIG. 12C: Conversion rate and selectivity to phenol and propylene as a function of temperature in the dealkylation of n-propylphenols over Z140-H; FIG. 12D: Stability of Z140-H for dealkylation of n-propylphenols (395° C.). In FIG. 12A, others include cresols, alkylbenzenes, and some unidentified products. Reaction conditions: WHSV=3.7 h.sup.−1, molar ratio of H.sub.2O to 4-n-propylphenol is 6, 1 bar. Since 4-n-propylphenol undergoes not only dealkylation but also isomerization (FIG. 12A), and all isomers can be dealkylated, the reported conversion rate and conversion in FIGS. 12C and 12D are based on the conversion of all isomers.

[0035] FIGS. 13A-13C. Dealkylation of 4-ethylphenol over Z140-H. FIG. 13A: The products distribution as a function of temperature, ramping rate=1° C. min.sup.−1; FIG. 13B: Gas chromatogram at low and high temperature (conversion); FIG. 13C: Conversion of ethylphenols and selectivity to phenol and ethylene as a function of time-on-stream (TOS) at 420° C.; In FIG. 13A others include cresols, alkylbenzenes, and some unidentified products. Reaction conditions: 3.3 h.sup.−1 WHSV, molar ratio of H.sub.2O to 4-ethylphenol is 6, 1 bar. Since 4-ethylphenol undergoes not only dealkylation but also isomerization (FIG. 13A), and all isomers can be dealkylated, the reported conversion in FIG. 13C is the conversion of all isomers.

[0036] FIG. 14. The stability of 5 wt % Pt/TiO.sub.2 in conversion of 4-propylguaiacol. WHSV=6.1 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure).

[0037] FIG. 15. The stability of 5 wt % Pd/TiO.sub.2 in conversion of 4-propylguaiacol. WHSV=9.0 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure).

[0038] FIG. 16. The stability of 5 wt % Pt/γ-Al.sub.2O.sub.3 in conversion of 4-propylguaiacol. WHSV=6.1 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure).

DETAILED DESCRIPTION

[0039] The following detailed description of this disclosure refers to the accompanying drawings. The same reference numbers in different drawings identify the same or similar elements. Also, the following detailed description does not limit this disclosure. Instead, the scope of this disclosure is defined by the appended claims and equivalents thereof.

[0040] The following detailed description of this disclosure refers to the accompanying drawings. The same reference numbers in different drawings identify the same or similar elements. Also, the following detailed description does not limit this disclosure. Instead, the scope of this disclosure is defined by the appended claims and equivalents thereof.

[0041] Several documents are cited throughout the text of this specification. Each of the documents herein (including any manufacturer's specifications, instructions etc.) are hereby incorporated by reference; however, there is no admission that any document cited is indeed prior art of the present invention.

[0042] The present invention will be described with respect to particular embodiments and with reference to certain drawings but this disclosure is not limited thereto but only by the claims.

[0043] The drawings described are only schematic and are non-limiting. In the drawings, the size of some of the elements may be exaggerated and not drawn to scale for illustrative purposes. The dimensions and the relative dimensions do not correspond to actual reductions to practice of this disclosure.

[0044] Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of this disclosure described herein are capable of operation in other sequences than described or illustrated herein.

[0045] Moreover, the terms top, bottom, over, under and the like in the description and the claims are used for descriptive purposes and not necessarily for describing relative positions. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of this disclosure described herein are capable of operation in other orientations than described or illustrated herein.

[0046] It is to be noticed that the term “comprising,” used in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It is thus to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression “a device comprising means A and B” should not be limited to the devices consisting only of components A and B. It means that with respect to the present invention, the only relevant components of the device are A and B.

[0047] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments.

[0048] Similarly it should be appreciated that in the description of exemplary embodiments of this disclosure, various features of this disclosure are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment.

[0049] Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment.

[0050] Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of this disclosure, and form different embodiments, as would be understood by those in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination.

[0051] In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of this disclosure may be practiced without these specific details. In other instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.

[0052] Other embodiments of this disclosure will be apparent to those skilled in the art from consideration of the specification and practice of this disclosure disclosed herein.

[0053] It is intended that the specification and examples be considered as exemplary only.

[0054] Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are part of the description and are a further description and are in addition to the preferred embodiments of the present invention.

[0055] Each of the claims set out a particular embodiment of this disclosure.

[0056] The following terms are provided solely to aid in the understanding of this disclosure.

Definitions

[0057] A “small molecule” is broadly used herein to refer to an organic compound typically having a molecular weight of less than about 250

[0058] “Oligomers” are broadly used herein to refer to organic compounds, obtained after lignin depolymerization, typically having a molecular weight between 250-5000 g/mol.

DESCRIPTION

[0059] Production of chemicals is rapidly becoming the single largest driver of global oil consumption in the future..sup.1, 2 To reduce the oil consumption and the resulting greenhouse gas emission, a shift from non-renewable fossil to renewable carbon resources is required.

[0060] Lignocellulose, as an abundant feedstock of renewable carbon, can be used for production of bio-fuels, bio-chemicals and bio-materials..sup.3, 4 However, most of the proposed lignocellulose biorefineries cannot economically compete with oil refineries due, in part, to incomplete utilization of feedstock. Therefore, it is imperative to maximize feedstock utilization to be not only cost but also environmentally competitive with fossil oil-based processes..sup.5 There is thus a need for new integrated biorefinery concepts that offer biomass refining with low energy requirements and high feedstock utilization (carbon and mass) efficiency, providing multiple products stream into markets. The inherent heterogeneity of lignocellulose, comprising entangled sugar-based (i.e., (hemi-cellulose) and aromatic (i.e., lignin) biopolymers, complicates its valorization into high value products. In particular, production of high value chemicals from lignin—a methoxylated phenylpropanoid biopolymer—is challenging due to its inherent recalcitrance and heterogeneity..sup.6-9 In contrast to relatively oxygen-free fossil oil, oxygen-containing functional groups are plentiful in lignocellulose. Therefore, functionalized aromatics, such as phenol are among the most suggested chemicals from lignin, but product yields on lignin weight basis are currently low. Hence, an integrated lignocellulose biorefinery was invented that simultaneously produces phenol, propylene, and phenolic oligomers from in planta wood lignin, and a carbohydrate pulp, with an overall carbon efficiency of up to 76% and mass efficiency of up to 78%.

[0061] The first step of our approach rests on a specific type of lignin-first biorefining, termed reductive catalytic fractionation (RCF)..sup.14, 45, 64-66 RCF of lignocellulose yields a solid carbohydrate pulp and a lignin-oil by cleavage of ester and ether bonds as a result of tandem high-temperature solvolysis, hydrogenation and hydrogenolysis either in batch or in (semi-)continuous mode over a metal catalyst in the presence of a reducing agent, such as hydrogen. The general consensus is that stabilization of the reactive intermediates formed by depolymerization of in planta lignin prevents the formation of unreactive condensed lignin derivatives..sup.14 Near-complete delignification of hardwoods, such as birch and poplar, can be achieved without significant carbohydrate degradation..sup.45 Besides low molecular weight oligomers, the lignin-oil contains few phenolic monomers in close-to-theoretical yields, viz. 50 wt. % for hardwoods..sup.45 However, maximal valorization of this lignin-oil into high value products, such as phenol or other aromatics, by technology that is not only profitable but, most importantly sustainable, has not yet been demonstrated, and is key in demonstrating the potential of biorefineries.

[0062] The high degree of delignification for hardwoods toward phenolic monomers enables us to propose an integrated process for transformation of wood lignin to phenol and propylene. Typical phenolic monomers composition (50.5 wt. % on lignin basis, Table 3) of RCF, from birch wood in MeOH over commercial Ru/C, shows 4-n-propylguaiacol (PG; 19 wt. %) and -syringol (PS; 67 wt. %), besides few others like 4-ethylguaiacol (EG) and -syringol as major products. While alkyl is the main substituent of the guaiacol/syringol monomers, considerably more polar groups containing primary alcohols remain in the oligomers structure. This polarity difference facilitates their practical separation; a simple extraction in n-hexane under reflux allows the isolation of the phenolic monomers. This work demonstrates that a less than six-fold mass of n-hexane to lignin-oil cost-efficiently extracts more than 90 wt. % of the phenolic monomers, and is therefore selected as the optimum trade-off between extraction efficiency, solvent usage, and oligomer co-extraction. Further (costly) separation of the individual phenolic monomers is not necessary as the crude will be completely funneled to phenol and propylene, or to n-propylbenzene.

[0063] The next step in our integrated refinery is hydrotreating of the monomers stream into n-propylphenols and ethylphenols, and optionally further hydrotreating of these alkylphenols to n-propylbenzene. In contrast to reported (batch) liquid phase approaches or using sulfide catalysts,.sup.15, 59, 60 continuous gas-phase hydroprocessing was conducted without solvent- and sulfur, to avoid product contamination and additional cost due to solvent loss and recovery from the engineering point of view. Hydroprocessing of 4-propylguaiacol—one of the dominant monomers in the lignin-oil—was tested initially to achieve high selectivity to n-propylphenols and ethylphenols. Several commercial catalysts including supported Pt, Pd, Ru, Rh, Cu, Co, Ni catalysts were evaluated under atmospheric pressure with 0.4 bar H.sub.2 partial pressure (FIG. 3). Nickel catalyst shows the highest PPs selectivity compared to other metals. The selectivity was not significantly influenced by nickel content (FIG. 3), Ni catalysts that contain high surface nickel are preferred as a result of high activity (FIG. 4A). Catalysts including supported Pt, Pt, Ru, Ni catalysts were evaluated for n-propylbenzene production from propylguaiacol and 4-propylsyringol via n-propylphenol under atmospheric pressure with 0.98 bar H.sub.2 partial pressure.

[0064] Since acidic supports such as silica/alumina led to more (propyl)cresols—stable compounds (and thus undesired) in the dealkylation step to phenol (FIG. 3)—and redox-active supports like anatase TiO.sub.2 form fully deoxygenated products such as n-propylbenzene and n-propylcyclohexane, Ni is preferably supported on inert materials such as silica or carbon. 64 wt. % Ni/SiO.sub.2 is thus selected for the rest of this disclosure when targeting selective production of n-alkylphenols. It can achieve 86% yields to n-propylphenols and ethylphenols at 4.5 kg per kg catalyst per hour at optimized conditions. Note that other Ni catalysts can also be used for the hydroprocessing step, but with somewhat lower selectivity. By-products include n-propylbenzene, propylcresols, besides some others such as cresols and propylanisole. The Ni catalyst only shows slight deactivation without loss of the selectivity (FIG. 4C). Alternatively, when targeting the production of n-propylbenzene, through hydrotreating of lignin monomers via n-alkylphenols, Pt/TiO.sub.2 is preferred as it shows both high selectivity and stability.

[0065] In an alternative embodiment, promoter-modified Ni catalysis or support modification is used to further enhance the catalytic performance in terms of both selectivity and stability. Promoter species such as V, Ce, La, and Mn, could have similar roles in the enhancement of catalytic performance for the Ni-based catalyst supported on silica.

[0066] Hydroprocessing of other pure monomers such 4-ethylguaiacol, isoeugenol, 4-propylsyringol were tested next. All compounds can be selectively converted to n-propylphenols and ethylphenol (ca. 80%) at (near) complete conversion (FIG. 4D). Hydroprocessing of 4-propylsyringol to n-propylphenols and ethylphenols needs higher temperature and contact time, showing 77% selectivity at full conversion. Propylguaiacol and 3-methoxyl-5-n-propylphenol are the key intermediates (FIG. 4D). The n-propylphenols were formed by both direct demethoxylation and cascade demethylation/dehydroxylation).

[0067] Based on the preceding results of hydroprocessing of pure compounds, hydroprocessing of crude monomers stream (obtained from the extraction) was investigated. The selectivity to n-propylphenols and ethylphenols remain similarly high (ca. 80%) at the same conditions for both softwood and hardwood derived crude monomers stream (FIG. 4D). This demonstrates robustness of the Ni based catalysts for conversion of real biomass feedstock. The hydroprocessing products were condensed at 0-5° C. The liquid product stream contains mainly n-propylphenols and ethylphenols, with minor side products such as (propyl)cresols and n-propylbenzene in addition to water, and this stream is used entirely in the dealkylation step without separation and purification steps.

[0068] Previous reports proved stable continuous gas-phase dealkylation of pure 4-n-propyl and 4-ethylphenol to phenol and olefins over a commercial microporous ZSM-5 zeolite..sup.62 Since co-feeding of water was crucial to maintain robust catalytic activity, the presence of water in the crude alkylphenol stream is beneficial for the dealkylation. Given the complexity of the crude alkylphenols stream (Table 4), similar use of commercial ZSM-5 is not preferred. It was reported that microporous ZSM-5 cannot selectively dealkylate 3-ethylphenol into phenol..sup.63 Sterically demanding alkylphenols, here demonstrated with conversion of 4-isopropyl-3-methylphenol (4-iPMP, model compound of bulky molecules—propylcresols—in the crude alkylphenols), are indeed harder to convert due to pore restriction. Besides, it was reported that presence of n-propylbenzene leads to microporous ZSM-5 deactivation due to coking..sup.67 To address the site-access restriction and cokes formation, hierarchical ZSM-5 catalysts (such as Z140-H) with balanced network of micro- and mesopores are preferred. High phenol and propylene (ethylene) yields from the crude alkylphenols streams were achieved under stable continuous catalytic operation (FIG. 5). FIGS. 5A-5D display the near-quantitative and selective conversion of the crude alkylphenols to produce 82% phenol and propylene (ethylene) stream. Stability of Z140-H is demonstrated, deliberately performed at incomplete conversion, not only for model compounds, but also for biomass-derived crude stream (FIGS. 5A-5D). Side-products are cresols, benzene, and trace amount of some others (FIG. 5D).

[0069] Detailed kinetic studies (using model substrates) demonstrated that tuning of pore structure is indeed highly preferred to maximize the products yield and catalysts life time. This is illustrated for conversion of sterically hindered 4-iPMP; Z140-H clearly outperforms commercial ZSM-5 catalyst (ZSM-5-P) regarding conversion rate (4.1 kg per kg catalyst per h, 380° C.), selectivity to the corresponding phenol and propylene (≥97%), and stability (FIGS. 5E-5F).

[0070] Similarly, (bulky) isomers of n-PP and n-EP present in the crude stream undergo selective dealkylation to phenol and corresponding olefin over Z140-H at full conversion (FIG. 5G).

[0071] The importance of pore structure and acidity modification is verified by the stable catalytic performance of hierarchical zeolites for conversion of n-propylbenzene—a major impurity in the alkylphenols (FIG. 6).

[0072] Cresols are another group of by-products in the crude alkylphenols stream. It was shown with pure cresols that their conversion in the dealkylation step is suboptimal (FIG. 7). Dealkylation of cresols is much more difficult than cleaving propyl/ethyl off. Cresols are thus best separated via existing technology such as batch distillation as applied in coal tar processing..sup.11 Optionally, the separated cresols stream can be converted in an additional step through bimolecular pathways such as disproportionation/transalkylation by using a large pore acidic zeolite such as USY, to produce phenol and xylenols..sup.68 For instance, use of commercial USY zeolite (USY-40, Si/Al=40) shows up to 90% of the theoretical selectivity with a (thermodynamic limited) conversion of about 57% (FIG. 7). Integration of this cresols conversion step can improve the phenol yield for 5%, while the obtained xylenols can be separated and used as antioxidants..sup.69

[0073] The extracted crude phenolic monomers can thus be transformed into phenol and propylene with 20 and 9 wt. % yields, respectively. The markets of phenol and propylene are established, and this invention may supply them with bio-derived alternatives. Anticipating a future post-bisphenol A era, phenol may be considered for production of aniline and caprolactam in existing facilities,.sup.48, 70 while propylene without further purification may be suitable to produce chemicals like isopropanol, given the uncertainty today of its purity for material production. Reductive catalytic fractionation also produces a carbohydrate pulp and phenolic oligomers stream. Carbohydrate pulp is amenable for bioethanol production, while other applications such as newspaper and cardboard are possible..sup.71 A titer of 40.2 g L.sup.−1 ethanol was reached via a semi-simultaneous saccharification-fermentation process using CTEC 2 saccharification enzyme and engineered yeast MDS130 (to ferment both glucose and xylose). Presence of catalyst impurity (from the reductive catalytic fraction) was endurable for this biological conversion.

[0074] Phenolic oligomers contain high functionality (3.46 mmol phenolic OH per gram, 2.48 mmol aliphatic OH per gram) and almost no original phenolic interlinkages. Next to the high functionality, other potential advantage are a low MW, compared to technical lignins (e.g., Kraft, Organosolv), and good solubility in various solvents at room temperature (e.g., acetone, ethanol, ethylacetate, DCM, DMSO, acetonitrile)

[0075] On the basis of the experimental data, an integrated process was designed (FIG. 8) and performed a techno-economic analysis. The process integrates the three catalytic steps. First, lignin-oil and pulp are produced by reductive catalytic fraction wood processing in either batch or (semi-)continuous reactor. After the liquid/solid separation, monomers isolation from lignin-oil is readily achieved in a liquid extraction unit, followed by flash distillation to remove n-hexane. Thereafter, the crude extract (monomers fraction), together with RCF off gas containing H.sub.2 and some methane impurities (from MeOH in RCF) are fed into the gas-phase fixed-bed setup, containing Ni catalyst to form alkylphenols (i.e., hydroprocessing). Since the presence of hydrogen has no impact on the olefins formation, this alkylphenolics crude, containing water (supporting stable catalysis), hydrogen and methane impurities (inert components) is fed without intermediate purification to the second fixed-bed reactor for conversion to phenol and olefins over preferred (hierarchical) ZSM-5. Next, product separation is foreseen in a gas-liquid separator, producing a liquor of phenol, and a gaseous mixture of water, olefins, H.sub.2 and CH.sub.4. Finally, to obtain highly pure phenol and propylene, impurities like cresol and benzene in the phenol fraction and H.sub.2/CH.sub.4 in gas fraction can be removed by distillation. The degraded sugars (from RCF) and side products like benzene and cresols are treated in the waste water. Methyl acetate from the acetyl group of birch wood, which is largely separated in the methanol recovery distillation, excess H.sub.2, CH.sub.4, C.sub.2H.sub.4, and small amounts of methanol (from distillation) are sent to the incineration/trigeneration to foresee heating, cooling and electricity. The whole process can convert 1 MT of biomass into 653 kg of raw pulp for bioethanol, 64 kg of lignin oligomers, 42 kg of phenol and 20 kg of propylene (>99%), corresponding to 78 wt. % of biomass converted into isolated products (FIG. 9). Addition of external energy is not required to operate the integrated biorefinery. Loss of solvent was studied critically, showing a total loss of 1.4% due to distillation, consumption in RCF and incorporation in chemicals.

[0076] The techno-economic analysis of the proposed biorefinery is studied with an annual production of 100 ktonnes of bio-phenol (i.e., average scale for fossil-based phenol production). Among the different process units, RCF and incineration/trigeneration are the highest contributors toward CAPEX due to the high cost of pressure reactors and energy integration, respectively. Investing in an incineration/trigeneration unit however is justified by its positive impact on the manufacture cost because of the strongly reduced energy costs. The highest contribution to the manufacture cost is the feedstock (birch wood, 158€.Math.tonne.sup.−1). Given the current pricing of phenol (1300€.Math.tonne.sup.−1), propylene (830 €.Math.tonne.sup.1) and crude pulp (400 €.Math.tonne.sup.−1), and using an estimate for the oligomers (1750€.Math.tonne.sup.−1, approaching that of nonylphenol), this resulted in an internal rate of return (RR) of 23.33% and a payout time of approximately four years for a plant with a 20 year lifetime). A sensitivity study indicated that feedstock and product prices have the largest economic impact while the influence of catalyst cost is negligible as long as the catalyst is sufficiently recyclable/reusable. In terms of RCF process parameters, shorter contact times and higher biomass concentrations are crucial factors to improve the profitability of this biorefinery, although development of a dedicated reactor will be necessary.

[0077] Because production of chemicals from biomass only makes sense if a lower CO.sup.2 footprint is achieved, besides TEA, life-cycle assessment (LCA) was done. LCA of our proposed integrated biorefinery showed reduced global warming potentials (GWPs) for phenol (0.736 kg CO.sub.2 equivalent) and propylene (0.469 kg CO.sub.2 equivalent) compared to their fossil-based counterparts (1.73 kg and 1.47 kg CO.sub.2 equivalent, respectively; open and red symbols in FIG. 10). Moreover, the GWP of the oligomers (proposed as substitute for para-nonylphenol with a GWP of >1.58 kg CO.sub.2 equivalent) and the carbohydrate pulp were calculated to be −0.949 and −0.217 kg CO.sub.2 equivalent, respectively (open symbols in FIG. 10). These latter negative values actually implicate a net consumption of CO.sub.2, i.e., a net carbon capturing effect. Finally, to indicate opportunities to further improve overall sustainability, additional scenarios were analyzed as well, e.g., (i) the substitution of non-renewable H.sub.2, which has a high CO.sub.2 contribution, by renewable H.sub.2, and (ii) inclusion of more sustainable forest management (FIG. 10). Such integrations reveal the possibility of CO.sub.2 neutral lignocellulosic biorefineries with a total net consumption of CO.sub.2 (i.e., negative GWP values) for each targeted product.

[0078] Overall, according to the proposed holistic biorefinery, 78% of initial mass content (FIG. 9) of birch wood (76% carbon content, FIG. 11) can be economically and sustainably converted into high-value products (pulp, oligomers, phenol and propylene).

[0079] Particular and preferred aspects of this disclosure are set out in the accompanying independent and dependent claims. Features from the dependent claims may be combined with features of the independent claims and with features of other dependent claims as appropriate and not merely as explicitly set out in the claims.

[0080] Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.

[0081] General Experimental Procedure

[0082] I. Reductive Catalytic Fractionation of Lignocellulose:

[0083] For the production of the lignin-derived phenolic monomers, oligomers, and carbohydrate pulp, a 2 L stirred batch reactor (Parr Instruments Co.) was loaded with 150 g of wood chips (particle size: <10 mm), 800 mL of organic solvent and 15 g of catalyst. The reaction vessel was closed and flushed three times with N2 (8 bar) in order to remove the residual oxygen. High pressure H.sub.2 was applied on the reaction mixture before heating, and the reactor is stirred at 720 rpm. The reaction was performed at 235° C. After several hours, the reaction was terminated by rapid cooling with compressed air flow and water. The reactor content was filtered in order to separate the solid fraction, containing the carbohydrate pulp and the catalyst, and the liquid fraction, containing the lignin oil and some soluble sugar products. To collect all liquid fraction, the solid residue was washed with EtOH. Afterwards, organic solvent used in the reaction and EtOH were removed from the liquid phase by rotary evaporation to yield a crude brownish colored lignin oil, containing some soluble sugar products next to phenolic monomers and oligomers.

[0084] A threefold liquid-liquid extraction with water and dichloromethane (DCM) at a mass ratio of 1/3/3 (crude lignin oil/DCM/water) was performed to separate the soluble sugar products from the lignin-derived products, prior to gas chromatographic analysis and lignin monomers separation (vide infra). Note that >99 wt. % of the lignin derived monomers in the lignin oil is present in the DCM phase, while >99 wt. % of sugar products is presented in water phase. Evaporation of DCM yielded the sugar-free lignin oil, consisting of phenolic monomers and oligomers. The weight of the sugar-free lignin oil was used to calculate the degree of delignification (on the basis of the Klason lignin weight) and to quantify the lignin products. The phenolic monomers were quantified using a Gas Chromatograph (GC, Agilent 6890) equipped with a HP5 column and a FID. 2-Isopropylphenol was used as the internal standard. The following parameters were used in the GC analysis: injection and detection temperature of 300° C., column temperature program: 50° C. (2 min), 15° C. min.sup.−1 to 150° C., 10° C. min.sup.−1 to 220° C. and 20° C. min.sup.−1 to 290° C. (12 min).

[0085] II. Lignin Monomers Extraction

[0086] To isolate the lignin-derived phenolic monomers from the sugar-free lignin oil, liquid-liquid extraction was applied. After removal of the soluble sugars (RCF part), the purified lignin oil was subjected to a three or fourfold reflux extraction with alkane (at 80° C. of oil bath for 3 h), and the extract was distilled in vacuo to obtain a transparent yellowish oil. This oil presents the concentrated fraction of the phenolic monomers.

[0087] III. Demethoxylation or Demethylation/Dihydroxylation

[0088] In a typical experiment, certain amount of catalyst, pelletized to a 0.125-0.25 mm fraction, was loaded into the four quartz reactor tubes and held by two layers of quartz wool. The catalyst was diluted with quartz powder (0.125-0.25 mm) to reduce the local hot spots and to improve the temperature distribution, yielding a catalyst bed with a height of ca. 15 mm. Reactor temperature in axial direction of the oven at height of the catalyst bed is homogeneous. The gas phase substrate, H.sub.2, and N.sub.2 were mixed in a mixer before feed into the reactor. Typically, the molar composition of the gas mixture in the reactor before reaction is 0.02/0.4/0.58 (for substrate/H.sub.2/N.sub.2) or 0.2/0.98 (for substrate/H.sub.2). The effluent gases were analyzed using an online GC (HP4890D) equipped with two parallel columns (HP1 column and Porapolt Q column), both connected with a FID. The products of demethoxylation or demethylation/dehydroxylation of phenolic monomers were collected and used to undergo catalytic dealkylation to form biophenol and biopropylene. The unit of WHSV is g g.sub.eatal.sup.−1 h.sup.−1 (i.e., h.sup.−1).

[0089] IV. Dealkylation

[0090] In a typical dealkylation experiment, 120 mg of zeolite catalyst, pelletized to a 0.125-0.25 mm fraction, was loaded into the four quartz reactor tubes (30 mg catalyst per tube) and held by two layers of quartz wool, yielding a catalyst bed of ca. 13 mm. Water was also fed into reactor. The gas substrate, water, and N.sub.2 were mixed in a mixer before fed into the reactor. The molar composition of the gas-phase before reaction is 0.02/0.12/0.86 (alkylphenols/water/N.sub.2). Dealkylation of 4-n-propylphenol in the presence of H.sub.2 was also conducted (as test reaction) by replacing N.sub.12 with H.sub.2. The effluent gases were characterized by the above mentioned online GC equipped with two FIDs, a HP column and a Porapolt Q column. The unit of WHSV is g g.sub.eatal.sup.−1 h.sup.−1 (i.e., h.sup.−1).

[0091] Some embodiments of this disclosure are set forth in “claim” format directly below:

[0092] 1. A method comprising the steps of: a) providing a mixture of compounds of formula (I):

##STR00001##

[0093] wherein: each occurrence of R1 and R2 is independently selected to be —O—CH.sub.3 or —H; each occurrence of R3 is independently selected to be —H, or -methyl, or -ethyl, or -propyl, or -propylene, or -1-alkoxypropyl, or -3-hydroxypropyl; b) preparing a reaction mixture by contacting the mixture of compounds of step a) in gas phase, with a reaction mixture containing a metal-based catalyst, under a hydrogen containing gas atmosphere; wherein step b) is carried out at a temperature of at least 265° C. and a partial hydrogen pressure of at least 0.2 bar; c) obtaining from step b) products comprising a mixture of compounds of formula (Ia), as well as methane or methanol or both,

##STR00002##

[0094] wherein: R1 is independently selected to be —CH3 or —H; R2 is independently selected to be —H, or -methyl, or -ethyl, or -propyl; m and n represent the position on the aromatic ring, with m being any one of the numbers 2-6 and with n being any one of the numbers 3-5, with m not being equal to n.

[0095] 2. The method as in embodiment 1 here above in paragraph [0093], wherein the metal catalyst comprises metal attached on a support material.

[0096] 3. The method as in any of the embodiments 1-2 (paragraphs [0093]-[0094]), wherein the metal catalyst comprises metal attached on a support material whereby the metal is nickel and the support is silica.

[0097] 4. The method as in any of the embodiments 1-3 (paragraphs [0093]-[0094]-[0095]), wherein the metal catalyst is a promoter-modified nickel catalyst.

[0098] 5. The method as in any of the 1-4 embodiments (paragraphs [0093]-[0094]-[0095]-[0096]), wherein in step b) a partial pressure of 0.2-10 bar H.sub.2 is used.

[0099] 6. The method as in any of the embodiments 1-5 (paragraphs [0093]-[0094]-[0095]-[0096]-[0097]), wherein in step b) a partial pressure of 0.2-1 bar H.sub.2 is used.

[0100] 7. The method as in any of the embodiments 1-6 (paragraphs [0093]-[0094]-[0095]-[0096]-[0097]-[0098]), wherein a complete removal of methoxy substituents is obtained with >70% molar yield to propyl phenols or ethyl phenols or a combination of both, based on a mixture of compounds with formula I.

[0101] 8. The method as in any of the embodiments 1-7 (paragraphs [0093]-[0094]-[0095]-[0096]-[0097]-[0098]-[0099]), wherein the resulting products with formula Ia obtained in step c) in embodiment 1 are subjected to a dealkylation process comprising the steps of: d) providing the mixture of compounds of formula (Ia); e) preparing a reaction mixture by contacting the mixture of compounds of step d) in gas phase, with an acidic zeolite, and water and wherein step e) is carried out at a temperature of at least 260° C.; and f) obtaining from step e) products comprising a mixture of compounds of formula (Ib) as well as olefins comprising propylene or ethylene or a combination of both,

##STR00003##

[0102] wherein: R1 is independently selected to be —CH3 or —H; p represents the position on the aromatic ring, with p being any one of the numbers 2-6.

[0103] 9. The method as in any of the embodiments 1-8 (paragraphs [0093]-[0094]-[0095]-[0096]-[0097]-[0098]-[0099]-[0100]), wherein the acidic zeolite belongs to the pentasil family of zeolites.

[0104] 10. The method as in any of the embodiments 1-9 (paragraphs [0093]-[0094]-[0095]-[0096]-[0097]-[0098]-[0099]-[0100]-[0101]), wherein the acidic zeolite is a ZSM-5 zeolite

[0105] 11. The method as in any of the embodiments 1-10 (paragraphs [0093]-[0094]-[0095]-[0096]-[0097]-[0098]-[0099]-[0100]-[0101]-[0102]), wherein the acidic zeolite is a hierarchical version of a ZSM-5 zeolite with Si/Al ratio of 140.

[0106] 12. The method as in any of the embodiments 1-11 (paragraphs [0093]-[0094]-[0095]-[0096]-[0097]-[0098]-[0099]-[0100]-[0101]-[0102]-[0103]), wherein the mixture of compounds with formula Ib and olefins are obtained in a molar yield of >40% based on the mixture of compounds with formula I.

[0107] 13. The method as in any of the embodiments 1, 5, 6, (paragraphs [0093], [0097], [0098]) wherein the produced mixture of compounds with formula Ia is further converted to a mixture of compounds with formula Ic.

##STR00004##

[0108] wherein: R1 is independently selected to be —CH3 or —H; R2 is independently selected to be -propyl or -ethyl; q represents the position on the aromatic ring, with q being any one of the numbers 2-6.

[0109] 14. The method as in any of the embodiments 1, 5, 6, 13, (paragraphs [0093], [0097], [0098]), [0105]) wherein the catalyst comprises a platinum group metal (PGM) selected of platinum or palladium, and whereby this metal is on a titanium oxide support.

[0110] 15. The method as in any of the embodiments 1, 5, 6, 13, 14 (paragraphs [0093], [0097], [0098]), [0105], [0106]), wherein the catalyst is selected of a promoter-modified platinum catalyst or a promoter-modified palladium catalyst.

[0111] 16. The method as in any of the embodiments 1, 5, 6, 13-15 (paragraphs [0093], [0097], [0098]), [0105], [0106], [0107]), wherein the catalyst achieves a constant conversion of the mixture of compounds with formula I for a time on stream of at least 5 hours, measured at a conversion level below full conversion.

[0112] 17. The method as in any of the embodiments 1, 5, 6, 13-16 (paragraphs [0093], [0097], [0098]), [0105], [0106], [0107], [0108]), wherein a mixture of compounds with formula Ic is obtained in >60% molar yield based on a mixture of compounds with formula I.

[0113] 18. The method as in any of the embodiments 1, 5, 6, 13-17 (paragraphs [0093], [0097], [0098]), [0105], [0106], [0107], [0108], [0109]), wherein n-propylbenzene is obtained in >40% molar yield based on a mixture of compounds with formula I.

[0114] 19. The method according to anyone of embodiments 1-18 (paragraphs [0093]-[0110]; wherein the mixture of compounds of formula (I) are derived from lignocellulose.

[0115] 20. The method as in any of the embodiments 1-19 (paragraphs [0093]-[0111]; wherein the mixture of compounds of formula (I) are derived from lignocellulose feedstock and are present in the lignin monomers enrich fraction obtained via a lignocellulose biorefinery process comprising the following steps: 1) reductive catalytic fractionation (biomass fractionation with lignin depolymerization) of lignocellulose, forming two fractions, a carbohydrate pulp and lignin oil, 2) separating the carbohydrate pulp and lignin oil fractions, 3) separating the monomer and oligomer fractions present in the lignin oil.

[0116] 21. The method as in any of the embodiments 1-20 (paragraphs [0093]-[0112]), wherein the mixture of compounds of formula (I) are derived from lignocellulose feedstock, being present in the lignin monomers fraction obtained via a lignocellulose biorefinery process comprising the following steps: 1.a) subjecting a lignocellulose mass in contact with a metal catalyst, H.sub.2 and solvent to reductive catalytic fractionation to produce a carbohydrate pulp and a liquid, b) solvent evaporation from the liquid to obtain lignin oil, hereby recycling the solvent for reuse in step a, and recycling H.sub.2 and formed methane for reuse in step d. c) contacting the lignin oil to a two-step liquid extraction with first H.sub.2O and CH.sub.2Cl.sub.2H.sub.2O or ethylacetate to isolate 1) a sugar water stream, and subsequently an extraction of the sugar-free lignin oil with an alkane solvent, such as hexane, heptane or octane, whereby are separated 2) lignin oligomers and 3) lignin monomers.

[0117] 22. The method as in any of the embodiments 1-12 (paragraphs [0093]-[0104]) and embodiments 19-21 (paragraphs [0111]-[0113]; wherein the lignin monomers fraction, together with an H.sub.2-gas stream, such as the gas stream from reductive catalytic fractionation, containing amongst others methane impurities (from methane formation during RCF) are fed into the gas-phase fixed-bed setup, containing Ni catalyst to form alkylphenols by demethoxylation and/or cascade demethylation/dehydroxylation 2) this alkylphenolics crude, containing water (supporting stable catalysis), hydrogen and methane impurities is fed without intermediate purification to the second fixed-bed reactor for conversion to phenol and olefins over an acidic zeolite, 3) product separation is carried out in a gas-liquid separator, producing a liquor of phenol, and a gaseous mixture of water, olefins, H.sub.2 and CH.sub.4.

[0118] 23. The method as in any of the embodiments 1-12 (paragraphs [0093]-[0104]) and embodiments 19-22 (paragraphs [0111]-[0114]); wherein >35% of the lignin present in the lignocellulose is converted into phenol, propylene, phenolic oligomers.

[0119] 24. The method as in any of the embodiments 1-12 (paragraphs [0093]-[0104]) and embodiments 19-23 (paragraphs [0111]-[0115]); whereby to obtain highly pure phenol and propylene, impurities like cresol and benzene in the phenol fraction and H.sub.2/CH.sub.4 in gas fraction are removed by distillation.

[0120] 25. The method as in any of the embodiments 1-12 (paragraphs [0093]-[0104]) and embodiments 19-24 (paragraphs [0111]-[0116]); to produce phenol, propylene, phenolic oligomers and a carbohydrate pulp from inplanta lignin with an overall carbon efficiency of >60%.

[0121] 26. The method as in any of the embodiments 1-12 (paragraphs [0093]-[0104]) and embodiments 19-25 (paragraphs [0111]-[0117]); whereby >35% of the lignin is converted into >95% pure phenol and >95% propylene fraction, and lignin oligomers.

[0122] 27. The method as in any of the embodiments 1-26 (paragraphs [0093]-[0118]); whereby the lignocellulose biorefinery process comprises lignocellulose fractionation with lignin depolymerization.

[0123] 28. The method as in any of the embodiments 1-27 (paragraphs [0093]-[0119]); whereby the lignin oil formed is rich in extractable phenolic monomers.

[0124] 29. The method as in any of the embodiments 1-28 (paragraphs [0093]-[0120]); wherein the lignocellulose mass comprises hardwood, softwood, herbaceous biomass, straw, bark, waste wood, flax shives, sugar cane bagasse, corn stover or crop residues.

[0125] 30. The method as in any of the embodiments 1-29 (paragraphs [0093]-[0121]); whereby methyl acetate from the acetyl group of lignocellulose, separated in the solvent recovery distillation, together with excess H.sub.2, CH.sub.4, C.sub.2H.sub.4, and small amounts of solvent, are sent to the incineration/trigeneration to foresee heating, cooling and electricity.

[0126] 31. The method as in any of the embodiments 1-30 (paragraphs [0093]-[0122]); whereby more than 2-fold and less than six-fold mass of n-hexane to lignin-oil extracts more than 70 wt. % of the phenolic monomers.

[0127] 32. The method as in any of the embodiments 1-7 (paragraphs [0093]-[0099]), whereby the mixture of compounds of formula (I) is subjected to demethoxylation or cascade demethylation-dehydroxylation or both.

Examples

[0128] Example 1. Reductive catalytic fractionation of birch wood. This experiment was performed according to experimental procedure I. birch wood (150 g) was used as the feedstock, 5 wt % Ru/C as a catalyst, and methanol as the solvent. The reaction was conducted at 235° C. for 3 h under 30 bar of H.sub.2 (room temperature). Conversion of lignin: 80.69%. Monomers yield (on the basis of Klason lignin): 4-propylguaiacol (9.71 wt %), isoeugenol (0.49 wt %), 4-(3-methoxypropyl)-guaiacol (<0.19 wt %), 4-n-prop-1-anolguaiacol (0.89 wt %), 4-ethylguaiacol (0.30 wt %), 4-propylsyringol (33.85 wt %), 4-prop-1-enylsyringol (0.32 wt %), 4-n-prop-1-anolsyringol (2.21 wt %), syringol (0.43 wt %), 4-methylsyringol (0.28 wt %), 4-ethylsryingol (1.03 wt %), 4-(3-methoxypropyl)-syringol (0.79 wt %), others (<0.02 wt %), total monomers (50.51 wt %). Oligomers (30.18 wt %).

[0129] Example 2. Reductive catalytic fractionation of pine wood. This experiment was performed according to experimental procedure I. pine wood (150 g) was used as the feedstock, 5 wt % Ru/C as a catalyst, and methanol as the solvent. The reaction was conducted at 235° C. for 3 h under 30 bar of H.sub.2 (room temperature). Conversion of lignin: 37.30%. Monomers yield (on the basis of Klason lignin): 4-propylguaiacol (9.97 wt %), isoeugenol (0.83 wt %), 4-n-prop-1-anolguaiacol (1.96 wt %), 4-ethylguaiacol (0.21 wt %), 4-propylsyringol (0.02 wt %), 4-prop-1-enylsyringol (0.40 wt %), 4-n-prop-1-anolsyringol (0.01 1 wt %), 4-methylsyringol (0.02 wt %), 4-ethylsryingol (0.21 wt %), others (<0.42 wt %), total monomers (14.05 wt %). Oligomers (23.25 wt %).

[0130] Example 3. Monomers extraction. This experiment was performed according to experimental procedure II. n-Hexane was used as the solvent with a threefold reflux extraction at n-hexane/lignin=3:1 (mass ratio). The extract efficiency for the extractable monomers is 93.9%.

[0131] Example 4. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Rh/Al.sub.2O.sub.3 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3A.

[0132] Example 5. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pt/Al.sub.2O.sub.3 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3A.

[0133] Example 6. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 17 wt % Ni/Al.sub.2O.sub.3 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3A.

[0134] Example 7. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3A.

[0135] Example 8. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 17 wt % Ni/Al.sub.2O.sub.3 as a catalyst. WHSV=2.7 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3A.

[0136] Example 9. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=9.0 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3A.

[0137] Example 10. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 20 wt % Ni/TiO.sub.2 as a catalyst. WHSV=2.7 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3B.

[0138] Example 11. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 21 wt % Ni/Al.sub.2O.sub.3 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3B.

[0139] Example 12. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 16 wt % Ni/SiO.sub.2 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3B.

[0140] Example 13. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 20 wt % Ni/TiO.sub.2 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3B.

[0141] Example 14. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 50 wt % Ni/Kieselguhr-Cr.sub.2O.sub.3 as a catalyst. WHSV=9.0 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3B.

[0142] Example 15. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 65 wt % Ni/SiO.sub.2-Al.sub.2O.sub.3 as a catalyst. WHSV=9.0 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3B.

[0143] Example 16. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 55 wt % Ni/Kieselguhr as a catalyst. WHSV=9.0 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3B.

[0144] Example 17. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 60 wt % Ni/Kieselguhr-Al.sub.2O.sub.3 as a catalyst. WHSV=9.0 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3B.

[0145] Example 18. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=6.0 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 4C.

[0146] Example 19. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-ethylguaiacol was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=8.2 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 4D.

[0147] Example 20. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. Isoeugenol was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=4.4 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 4D.

[0148] Example 21. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylsyringol was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=7.1 h.sup.−1. Reaction temperature: 305° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 4D.

[0149] Example 22. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylsyringol was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=5.3 h.sup.−1. Reaction temperature: 305° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 4D.

[0150] Example 23. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. Lignin monomers obtained reductive catalytic fractionation of pine wood (example 2) after extraction was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=6.0 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 4D.

[0151] Example 24. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. Lignin monomers obtained reductive catalytic fractionation of birch wood (example 1 and example 3) after extraction was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=5.3 h.sup.−1. Reaction temperature: 305° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 4D.

[0152] Example 25. Dealkylation. This experiment was performed according to experimental procedure VI. 4-isopropyl-3-methylphenol was used as feedstock, ZSM-5 (parent microporous ZSM-5, Si/Al=140, code: Z140-P) as a catalyst. WHSV=4.1 h.sup.−1. Reaction temperature: 200-500° C. 1 bar. molar ratio of water to 4-isopropyl-3-methylphenol is 6. The results were shown in FIG. 5E.

[0153] Example 26. Dealkylation. This experiment was performed according to experimental procedure VI. 4-isopropyl-3-methylphenol was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=4.1 h.sup.−1. Reaction temperature: 200-500° C. 1 bar. molar ratio of water to 4-isopropyl-3-methylphenol is 6. The results were shown in FIG. 5E.

[0154] Example 27. Dealkylation. This experiment was performed according to experimental procedure VI. 4-isopropyl-3-methylphenol was used as feedstock, ZSM-5 (parent microporous ZSM-5, Si/Al=140, code: Z140-P) as a catalyst. WHSV=4.1 h.sup.−1. Reaction temperature: 395° C. 1 bar. molar ratio of water to 4-isopropyl-3-methylphenol is 6. The results were shown in FIG. 5F.

[0155] Example 28. Dealkylation. This experiment was performed according to experimental procedure VI. 4-isopropyl-3-methylphenol was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=4.1 h.sup.−1. Reaction temperature: 305° C. 1 bar. molar ratio of water to 4-isopropyl-3-methylphenol is 6. The results were shown in FIG. 5F.

[0156] Example 29. Dealkylation. This experiment was performed according to experimental procedure VI. 4-methylphenol was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=2.9 h.sup.−1. Reaction temperature: 400-500° C. 1 bar. molar ratio of water to 4-methylphenol is 6. The results were shown in FIG. 7A.

[0157] Example 30. Dealkylation. This experiment was performed according to experimental procedure VI. 4-methylphenol was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=2.9 h.sup.−1. Reaction temperature: 410° C. 1 bar. molar ratio of water to 4-methylphenol is 6. The results were shown in FIG. 7B.

[0158] Example 31. Dealkylation. This experiment was performed according to experimental procedure VI. 4-methylphenol was used as feedstock, ZSM-5 (parent microporous ZSM-5, Si/Al=40, code Z40-P) as a catalyst. WHSV=2.9 h.sup.−1. Reaction temperature: 300-500° C. 1 bar. molar ratio of water to 4-methylphenol is 6. The results were shown in FIG. 7C.

[0159] Example 32. Dealkylation. This experiment was performed according to experimental procedure VI. 4-methylphenol was used as feedstock, USY (parent microporous USY, Si/Al=40, code: USY-40) as a catalyst. WHSV=2.9 h.sup.−1. Reaction temperature: 300-500° C. 1 bar. molar ratio of water to 4-methylphenol is 6. The results were shown in FIG. 7E.

[0160] Example 33. Dealkylation. This experiment was performed according to experimental procedure VI. n-propylbenzene was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.2 h.sup.−1. Reaction temperature: 300-500° C. 1 bar. No water. The results were shown in FIG. 6A.

[0161] Example 34. Dealkylation. This experiment was performed according to experimental procedure VI. n-propylbenzene was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.2 h.sup.−1. Reaction temperature: 410° C. 1 bar. No water. The results were shown in FIG. 6D.

[0162] Example 35. Dealkylation. This experiment was performed according to experimental procedure VI. n-propylbenzene was used as feedstock, ZSM-5 (parent microporous ZSM-5, Si/Al=12, code: Z12-P) as a catalyst. WHSV=3.2 h.sup.−1. Reaction temperature: 350° C. 1 bar. No water. The results were shown in FIG. 6E.

[0163] Example 36. Dealkylation. This experiment was performed according to experimental procedure VI. The products obtained from example 23 was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.7 h.sup.−1. Reaction temperature: 200-500 C. 1 bar. molar ratio of water to alkylphenol is around 6. The results were shown in FIG. 5A.

[0164] Example 37. Dealkylation. This experiment was performed according to experimental procedure VI. The products obtained from example 18 was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.7 h.sup.−1. Reaction temperature: 410° C. 1 bar. molar ratio of water to alkylphenol is around 6. The results were shown in FIG. 5B.

[0165] Example 38. Dealkylation. This experiment was performed according to experimental procedure VI. The products obtained from example 23 was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.7 h.sup.−1. Reaction temperature: 410° C. 1 bar. molar ratio of water to alkylphenol is around 6. The results were shown in FIG. 5C.

[0166] Example 39. Dealkylation. This experiment was performed according to experimental procedure VI. The products obtained from example 24 was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=2.8 h.sup.−1. Reaction temperature: 410° C. 1 bar. molar ratio of water to alkylphenol is around 6. The results were shown in FIG. 5D.

[0167] Example 40. Dealkylation. This experiment was performed according to experimental procedure VI. 4-n-propylphenol was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.7 h.sup.−1. Reaction temperature: 200-500° C. 1 bar. molar ratio of water to alkylphenol is 6. The results were shown in FIG. 12A.

[0168] Example 41. Dealkylation. This experiment was performed according to experimental procedure VI. 4-n-propylphenol was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.7 h.sup.−1. Reaction temperature: 395° C. 1 bar. molar ratio of water to alkylphenol is 6. The results were shown in FIG. 12D.

[0169] Example 42. Dealkylation. This experiment was performed according to experimental procedure VI. 4-ethylphenol was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.3 h.sup.−1. Reaction temperature: 200-500° C. 1 bar. molar ratio of water to alkylphenol is 6. The results were shown in FIG. 13A.

[0170] Example 43. Dealkylation. This experiment was performed according to experimental procedure VI. 4-ethylphenol was used as feedstock, hierarchical ZSM-5 (obtained from post modification of Z140-P, code:Z140-H) as a catalyst. WHSV=3.3 h.sup.−1. Reaction temperature: 420° C. 1 bar. molar ratio of water to alkylphenol is 6. The results were shown in FIG. 13C.

[0171] Example 45. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pd/Al.sub.2O.sub.3 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 285° C. 0.4 bar H.sub.2 (1 bar of total pressure). The results were shown in FIG. 3A.

[0172] Example 46. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 64 wt % Ni/SiO.sub.2 as a catalyst. WHSV=9.0 h.sup.−1. Reaction temperature: 285° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol=72.4%, selectivity to n-propylphenols=86.10%.

[0173] Example 47. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pt/TiO.sub.2 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol>99%, yield of n-propylbenzene=86.5%.

[0174] Example 48. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 0.5 wt % Pt/TiO.sub.2 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol=81.3%, yield of n-propylphenols=52.6%.

[0175] Example 49. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 10 wt % Pt/TiO.sub.2 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol>99%, yield of n-propylbenzene=85.6%.

[0176] Example 50. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pd/TiO.sub.2 as a catalyst. WHSV=4.5 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol>99%, yield of n-propylbenzene=73.3%.

[0177] Example 51. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Ni/TiO.sub.2 as a catalyst. WHSV=3 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol>99%, yield of n-propylphenols=57.7%.

[0178] Example 52. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Ru/TiO.sub.2 as a catalyst. WHSV=2.25 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol=97.9%, yield of n-propylphenols=66.2%.

[0179] Example 53. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pt/γ-Al.sub.2O.sub.3 as a catalyst. WHSV=3.0 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol=88.4%, yield of n-propylphenols=52.5%.

[0180] Example 54. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pt/ZrO.sub.2 as a catalyst. WHSV=2.25 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-n-propylguaiacol=70.7%, yield of n-propylphenols=43.4%.

[0181] Example 55. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pt/TiO.sub.2 as a catalyst. WHSV=6.1 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). The stability of catalyst can be found in FIG. 14.

[0182] Example 56. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pd/TiO.sub.2 as a catalyst. WHSV=9.0 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). The stability of catalyst can be found in FIG. 15.

[0183] Example 57. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylguaiacol was used as feedstock, 5 wt % Pt/γ-Al.sub.2O.sub.3 as a catalyst. WHSV=6.1 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). The stability of catalyst can be found in FIG. 16.

[0184] Example 58. Demethoxylation and demethylation/dihydroxylation. This experiment was performed according to experimental procedure III. 4-propylsyringol was used as feedstock, 5 wt % Pt/TiO.sub.2 as a catalyst. WHSV=7.1 h.sup.−1. Reaction temperature: 325° C. 0.98 bar H.sub.2 (1 bar of total pressure). Conversion of 4-propylsyringol>99%, yield of n-propylphenols=75%.

[0185] Legend to the Tables

[0186] Table 1. One step conversion of lignin into phenol.

[0187] Table 2. Multiple-steps conversion of lignin into bio-phenol.

[0188] Table 3. Monomer yield and distribution obtained from RCF of birch wood and

[0189] Table 4: The composition of condensed hydroprocessing products.

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