CATALYTIC CONVERSION OF LIGNIN

Abstract

A process for depolymerization of lignin, the process including using at least one catalyst internal to a pulp mill for performing catalytic treatment and separation of biomass components into cellulose and lignin rich material is provided.

Claims

1-19. (canceled)

20. A process for depolymerization of lignin, the process comprising: utilizing at least one catalyst internal to a pulp mill, the at least one catalyst occurring naturally in the pulp mill, for performing catalytic treatment and separation of biomass components into cellulose and lignin rich material; utilizing green liquor dregs or electrofilter ash as source of extraction for one or more of the catalyst components Co, Mo, Mn, Fe, Mg, W, Cd, As, Cu, Cr, Nb, Ni, Pd, Zn, Sr or V; wherein the process is performed on a black liquor or black liquor retentate obtained from a kraft process; wherein the process comprises utilizing one or more of the following substances; Fe, Mg, W, Cd, As, Cu, Cr, Nb, Ni, Pd, Zn, Sr and V, in levels higher than naturally occurring in weak black liquor.

21. The process according to claim 20, further comprising utilizing one or more of the following substances; Co, Mo and Mn, in levels higher than naturally occurring in weak black liquor.

22. The process according to claim 20, further comprising utilizing hydrogen or hydrogen donors in support of depolymerization, the depolymerization performed in an aqueous phase of black liquor or black liquor retentate in a presence of alkali and/or in a presence of a solvent.

23. The process according to claim 20, the process utilizing separation of a lignin-rich organic phase from an aqueous phase forming spontaneously upon hydrogen assisted heat treatment at 250-360 C.

24. The process according to claim 20, the process utilizing separation of a lignin-rich organic phase from an aqueous phase, the separation forming spontaneously upon hydrogen assisted heat treatment at 300-350 C.

25. The process according to claim 20, wherein side products that have a stabilizing effect on lignin are decomposed trough heat treatment at 170-190 C. so that a level in total of sugars composed of arabinose, galactose, glucose, xylose and mannose does not exceed 10 mg/g.

26. The process according to claim 20, wherein the catalyst is directly or indirectly recycled to and at least partly regenerated in a unit operation in the pulp mill.

27. The process according to claim 26, wherein the unit operation is a recovery boiler.

28. The process according to claim 20, wherein the lignin to be treated is in black liquor with additional biomass.

29. The process according to claim 20, wherein the lignin to be treated is concentrated using membrane filtration of black liquor.

30. The process according to claim 20, wherein the lignin in black liquor is first separated from water and cooking chemicals and then mixed into a hydrocarbon phase before depolymerization.

31. The process according to claim 20, wherein the lignin is first depolymerized and then treated in a second step with hydrogen and a heterogeneous catalyst in a hydrocarbon phase, either at the pulp mill or on another site, the other site being a petroleum refinery.

32. The process according to claim 31, wherein the heterogeneous catalyst has a mean pore diameter larger than 60 .

33. The process according to claim 22, wherein hydrogen is produced via electrolysis and the co-product oxygen is used in bleaching the pulp or paper.

34. The process according to claim 20, wherein the catalytic treatment, separation or purification operations reduces the Na content to below 10 ppm.

35. The process according to claim 20, wherein a produced final product is used as a raw material for fine chemicals production or as a fuel component in transportation fuel.

Description

BRIEF DESCRIPTION

[0032] Some of the embodiments will be described in detail, with reference to the following figures, wherein like designations denote like members, wherein:

[0033] FIG. 1a shows a lignin-rich organic phase at room temperature, in accordance with embodiments of the present invention;

[0034] FIG. 1b shows the lignin-rich organic phase at room temperature, in accordance with embodiments of the present invention;

[0035] FIG. 1c shows the lignin-rich organic phase at room temperature, in accordance with embodiments of the present invention;

[0036] FIG. 1d shows a see-through aquatic phase with a submerged pH probe, in accordance with embodiments of the present invention;

[0037] FIG. 2 shows an analysis through size exclusion chromatography, in accordance with embodiments of the present invention;

[0038] FIG. 3a shows a first process in accordance with embodiments of the present invention;

[0039] FIG. 3b shows a second process in accordance with embodiments of the present invention; and

[0040] FIG. 3c shows a third process in accordance with embodiments of the present invention.

DETAILED DESCRIPTION

Example 1

[0041] In this example, a lignin-rich organic phase is separated from an aquatic phase starting from black liquor or membrane filtered black liquor.

[0042] It was surprisingly discovered that a lignin-rich organic phase separated from an aquatic phase upon heat treatment of black liquor or membrane filtered black liquor at 300-350 C. and in a hydrogen atmosphere in batch autoclave experiments. The starting material, black liquor or membrane filtered black liquor is completely opaque before treatment. During treatment, the starting material was separated into one see-through aquatic phase and one opaque lignin-rich organic phase dark in color with higher density than the aquatic phase (FIGS. 1a-d). FIGS. 1a-c shows the lignin-rich organic phase at room temperature and FIG. 1d shows the see-through aquatic phase with a submerged pH-probe. The lignin-rich organic phase is liquid at temperatures above 130 C. and partly solidified at room temperature.

Example 2

[0043] In this example, the hydrogen consumption in heat treatment of black liquor or membrane filtered black liquor at 300-350 C. under hydrogen atmosphere is increased by the addition of Co and/or Mo.

[0044] In batch autoclave experiments, the hydrogen consumption without any addition of catalyst was 0.39 mol H.sub.2 per mol of lignin monomer. The addition of Co in relation to lignin monomer 1:700 on a molar basis increased the hydrogen consumption to 0.58 mol H.sub.2 per mol of lignin monomer which correspond to an increase of 49%. The addition of Mo in the same relation, 1:700 to lignin monomers on a molar basis, showed no increase in the total consumption, but an increase of the consumption rate. The combination of the two catalysts in relation 1:1:700 (Co:Mo:lignin monomers) on a molar basis gave a synergetic effect and resulted in a total consumption of 0.78 mol H.sub.2 per mol of lignin monomer which correspond to an increase by 100% compared to the experiment without any catalyst added. These conditions were tested at 350 C. which showed yet higher consumption, 1.18 mol H.sub.2 per mol of lignin monomer.

TABLE-US-00003 TABLE 3 Approximate hydrogen consumption of varying catalyst and temperature Approx. H.sub.2-consumtion Temperature (mol H.sub.2/mol lignin Catalyst added ( C.) monomer) No catalyst 300 0.39 Co 300 0.58 Mo 300 0.39 Co, Mo 300 0.78 Co, Mo 350 1.18

Example 3

[0045] In this example, polysaccharides in black liquor or membrane filtered black liquor are decomposed during heat treatment above 170 C. In one specific embodiment of the process, lignin in black liquor or membrane filtered black liquor is separated through formation of a liquid lignin phase through CO.sub.2-acidulation. The decomposition of polysaccharides is vital to this specific embodiment.

[0046] Experiments of separation through CO.sub.2-acidulation was performed in batch autoclave on two different materials of membrane filtered black liquor, referred to as BLR #1 and BLR #2. None of the materials were able to form a liquid lignin phase unless it had first undergone heat treatment. The same phenomenon has been observed for black liquor. Analyses showed that the heat treatment lowered the total amount of polysaccharides of BLR #1 and BLR #2 from 34.7 mg/g to 9.9 mg/g and 16.6 to 8.4 respectively.

TABLE-US-00004 TABLE 4 Content of saccharides in membrane filtered black liquor, BLR. Sepa- Ara ration (mg/ Gal Glu Xyl Man Sum suc- Material g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) cessful BLR #1 4.83 4.90 2.74 22.26 34.73 No Heat 1.54 2.31 1.38 4.63 9.86 Yes treated BLR #1 BLR #2 3.57 3.76 0.72 8.53 16.58 No Heat 1.67 2.51 0.45 3.37 0.36 8.36 Yes treated BLR #2

Example 4

[0047] In this example, a lignin-rich organic phase originating from any of the embodiments regarding separation of lignin within the process is converted to a bio-oil through hydrogenation over a heterogeneous catalyst. The bio-oil is free of water and has properties suitable for fuel production.

[0048] Catalytic hydrogenation experiments have been performed in a batch autoclave. A mixture of lignin material and hydrocarbon carrier was either heated together with the catalyst from room temperature or fed to a preheated catalyst in hydrocarbon carrier. The lignin feed material was either separated trough high temperature treatment in the presence of hydrogen explained in Example 1 or separated through CO.sub.2-acidulation described in Example 3. The product of every feed material was a color-less hydrocarbon liquid comprising both the carrier hydrocarbon and a bio-oil originating from the lignin material. By a gravimetrical method the yield of lignin material to this bio-oil was determined, ranging from 61 to 99%. A majority of the product oil was within the gasoline or diesel boiling range. The remainder of the material was heavier hydrocarbons that could be refined into gasoline and diesel. Bi-products of the reaction are short carbons in gas phase and coke. It was found that the coke formation was much lower in the preheated setup compared to the system heated from room temperature. The catalytic conversion of aromatic to aliphatic structures was efficient and phenolic hydroxyls were very low making the quality of the product suitable for fuel production.

TABLE-US-00005 TABLE 5 Characteristics of the product after hydrogenation Aliphatic-H to Lignin separation Yield Coke Aromatic-H Phenolic-OH method described in (%) (%) (H:H) (mmol/g) Example 1 68 27 41:1 0.003 Example 3 58 10 136:1 0.019 Example 3 80 <1 99:1 0.011 Example 3 85 3 99:1 0.010 Example 3 61 <1 99:1 0.014 Example 3 88 4 131:1 0.010 Example 3 99 3 61:1

Example 5

[0049] In this example, partial deoxygenation is performed of lignin in membrane filtered black liquor through heat treatment alone or heat treatment in hydrogen atmosphere.

[0050] The chemical composition of lignin in membrane filtered black liquor is altered during heat treatment with or without hydrogen atmosphere. Analyses of carbon, hydrogen, nitrogen, sulfur and oxygen was performed on 5 samples that had undergone different treatment. Mild heat treatment reduced the oxygen content was reduced from 27 to 22% (w/w), while severe heat treatment in combination with hydrogen atmosphere reduced the oxygen content from 27 to 12% (w/w).

TABLE-US-00006 TABLE 6 Chemical composition of lignin in membrane filtered black liquor after various treatments (% w/w on dry basis) Treatment C H N S O No treatment 63.5 5.80 0.16 1.58 26.6 Mild heat treatment 67.9 5.55 0.20 1.01 22.1 Mild heat treatment with hydrogen 67.5 5.57 0.19 1.06 22.3 Severe heat treatment with hydrogen 78.3 5.55 0.40 0.72 12.0 Severe heat treatment with hydrogen 76.9 5.77 0.33 0.59 12.2 and catalyst internal to a pulp mill

Example 6

[0051] In this example, the average molecular weight of lignin in membrane filtered black liquor is reduced through heat treatment alone or catalytic heat treatment in hydrogen atmosphere with catalyst internal to a pulp mill.

[0052] The molecular weight distribution of lignin in membrane filtered black liquor is ranging from 1 to 100 kDa with a substantial proportion above 10 kDa. This is shown by BLR in FIG. 2 (analysis through size exclusion chromatography). After low temperature heat treatment, no catalyst added, the majority of the molecular weight distribution is below 10 kDa with an average around 2-3 kDa. This is shown by LT no catalyst in FIG. 2. After treatment at high temperature with hydrogen and addition of catalysts internal to a pulp mill, the molecular weight average is around 1 kDa, and the majority of the molecules is below 3 kDa, shown by HT PMC in FIG. 2.

Example 7

[0053] In this example, the drawings of the process are described. In FIGS. 3a-c there are shown block diagrams or flow charts of different embodiments according to the present invention. The different routes according to these embodiments are explained below by viewing the tables.

[0054] According to FIG. 3a, process A can be performed either with black liquor (dotted line, A1-A5) or on membrane filtered black liquor (solid line A6-A12). According to this design, heat treatment (II) is performed at 170-240 C. followed by separation through CO.sub.2-acidulation (III).

[0055] According to FIG. 3b process B can be performed either with black liquor (dotted line, B1-B5) or on membrane filtered black liquor (solid line B6-B12). According to this design, heat treatment (II) is performed at 300-350 C. in combination with catalysts internal to a pulp mill and hydrogen followed by spontaneous separation (III).

[0056] According to FIG. 3c, process C can be performed either with black liquor (dotted line, C1-C5) or on membrane filtered black liquor (solid line C6-C12). According to this design, heat treatment (II) is performed at 300-350 C. without pulp mill catalyst or hydrogen or followed by spontaneous separation (III).

[0057] Purification (IV) and hydrogenation (V) is alike for all designs A-C.

TABLE-US-00007 Explanation Stream A1 black liquor A2 heat treated black liquor A3 lignin-rich organic phase separated trough CO2-acidulation A4 lignin-rich organic phase after purification A5 product after hydrogenation A6 black liquor A7 permeate of membrane filtered black liquor, water, cooking chemicals and small lignin fragments A8 membrane filtered black liquor A9 heat treated membrane filtered black liquor A10 lignin-rich organic phase separated trough CO.sub.2-acidulation A11 lignin-rich organic phase after purification A12 product after hydrogenation A13 CO.sub.2 A14 aquatic phase from CO.sub.2 separation A15 effluents returned to pulp mill chemical recovery cycle A16 H.sub.2 A17 hydrocarbon carrier Unit operation AI membrane filtration AII heat treatment 170-240 C. AIII separation with CO.sub.2 AIV Purification AV Hydrogenation Stream B1 black liquor B2 heat treated black liquor with hydrogen B3 lignin-rich organic phase B4 lignin-rich organic phase after purification B5 product after hydrogenation B6 black liquor B7 permeate of membrane filtered black liquor, water, cooking chemicals and small lignin fragments B8 membrane filtered black liquor B9 membrane filtered black liquor heat treated with hydrogen B10 lignin-rich organic phase B11 lignin-rich organic phase after purification B12 product after hydrogenation B13 H.sub.2 B14 aquatic phase from spontaneous phase separation B15 Effluents returned to pulp mill chemical recovery cycle B16 H.sub.2 B17 hydrocarbon carrier Unit operation BI membrane filtration BII heat treatment 300-350 C. BIII spontaneous phase separation BIV Purification BV Hydrogenation Stream C1 black liquor C2 heat treated black liquor C3 lignin-rich organic phase C4 lignin-rich organic phase after purification C5 product after hydrogenation C6 black liquor C7 permeate of membrane filtered black liquor, water, cooking chemicals and small lignin fragments C8 membrane filtered black liquor C9 heat treated membrane filtered black liquor C10 lignin-rich organic phase C11 lignin-rich organic phase after purification C12 product after hydrogenation C13 aquatic phase from spontaneous phase separation C14 effluents returned to pulp mill chemical recovery cycle C15 H.sub.2 C16 hydrocarbon carrier Unit operation CI membrane filtration CII heat treatment 300-350 C. CIII spontaneous phase separation CIV Purification CV Hydrogenation

[0058] Although the invention has been illustrated and described in greater detail with reference to the preferred exemplary embodiment, the invention is not limited to the examples disclosed, and further variations can be inferred by a person skilled in the art, without departing from the scope of protection of the invention.

[0059] For the sake of clarity, it is to be understood that the use of a or an throughout this application does not exclude a plurality, and comprising does not exclude other steps or elements.