PROCESS FOR PREPARING PRODUCT OIL FROM PEAT, COIR OR PEAT-LIKE SUBSTANCES

Abstract

The present invention refers to a process for catalytic fractionation of peat, coir, peat-like materials or mosses into a non-pyrolytic bio-oil and a sterile solid fraction with similar volume and structural function to the starting material. The inventive process is useful for a variety of interesting applications, starting from raw peat with a water content of up to 80% resulting in a an oil, rich in polyols and aliphatic molecules.

Claims

1. Process for catalytic fractionation of peat or peat-like substrates for the production of product oil in addition to a solid capable of high water retention with a high volume, the process comprising the steps of: a. subjecting optionally particulate peat material to a treatment at the temperature range from 130 C. to 300 C., in a solvent system comprising an organic solvent or mixture of solvents in the presence of a transition metal in absence of externally supplied molecular hydrogen, under autogeneous pressure in a reaction vessel for a reaction time of 0.01 to 8 hours, b. removing the catalyst from the reaction mixture, c. filtering the reaction mixture to separate the raw product oil from the solid fraction, and optionally d. removing the solvent system from the filtrate to concentrate the product oil.

2. Process according to claim 1, wherein the material is a peat.

3. Process according to claim 1, wherein the solvent system comprises an organic solvent that is miscible with water.

4. Process according to claim 1, wherein the solvent system can be a solvent mixture of a lower aliphatic alcohol having 1 to 6 carbon atoms and water.

5. Process according to claim 1, wherein the solvent system is a solvent mixture of secondary alcohols and water in a v/v-ratio of alcohol/water of 80/20 to 20/80.

6. Process according to claim 1, wherein the solvent system additionally comprises at least one further solvent selected from the group consisting of: aliphatic or aromatic ketones having 1 to 10 carbon atoms, ethers having 2 to 10 carbon atoms, cyclohexanols, cyclic ethers, and esters.

7. Process according to claim 6, wherein the volume fraction of a modifier in the solvent mixture, also containing secondary alcohol or mixture thereof and eventually water, ranges from 0.1 to 99.9%.

8. The process as claimed in claim 1, wherein the metal catalyst can be a skeletal transition metal catalyst or supported transition metal catalyst or mixture thereof.

9. The process as claimed in claim 8, wherein the metal is selected from the group consisting of: nickel, iron, cobalt, copper, ruthenium, palladium, rhodium, osmium iridium, rhenium and mixtures thereof.

10. The process as claimed in claim 1, wherein the catalyst is a bifunctional solid comprising metal functionality and acid sites, said acid sites being optionally functional sites having acidic Brnsted or Lewis functionality or both.

11. The process as claimed in claim 1, wherein the catalyst is a transition metal oxide as in any oxide form of nickel, iron, cobalt, copper, ruthenium, palladium, rhodium, osmium iridium, rhenium or mixtures thereof.

12. The process as claimed in claim 1, wherein the catalyst is co-catalyzed by a base comprising of alkali metals, alkali earth metals, or any organic base which includes nitrogen in the organic structure.

13. Process according to claim 1, wherein the catalyst is used at weight ratio of catalyst-to-substrate from 0.001 to 10.

Description

EXAMPLES

[0041] The following examples are intended to illustrate the present invention without limiting the invention in any way.

Example 1

Reference Process (Ordanosolv Process)

[0042] Peat (10 g, 14% H.sub.2O, H3-H4, Terracult) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The autogenous pressure at 180 C. is 25 bar. The suspension was processed at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown solid was obtained (FIG. 1A). In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 8.6 g of peat, 3.15 g of solid product leached from peat and 5.18 g solid fraction were obtained.

Example 2

Reference Process (Ordanosolv Process)

[0043] Peat (10 g, 14% H.sub.2O, H7-H8, Terracult) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The autogenous pressure at 180 C. is 25 bar. The suspension was processed at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown solid was obtained (FIG. 1A). In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 8.6 g of peat, 2.52 g of solid product leached from peat and 5.65 g solid fraction were obtained.

Example 3

Reference Process (Ordanosolv Process)

[0044] Coir (15 g, 57% H.sub.2O, Terracult) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) (inclusive of the original H.sub.2O content in the peat) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The autogenous pressure at 180 C. is 25 bar. The suspension was processed at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown solid was obtained (FIG. 1A). In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 6.4 g of peat, 2.52 g of solid product leached from peat and 4.76 g solid fraction were obtained.

Example 4

Inventive Process (Catalytic Fractionation of Peat)

[0045] Peat (15 g, 14% H.sub.2O, H3-H4, Terracult) and skeletal Ni catalyst (10 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 12.9 g of Peat, 5.15 g of product oilproduct oil and 6.98 g solid fraction were obtained (Table 1, entry 1).

Example 5

Inventive Process (Catalytic Fractionation of Peat)

[0046] Peat (10 g, 14% H.sub.2O, H3-H4, Terracult) and skeletal Ni catalyst (8 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 200 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 200 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 8.6 g of Peat, 4.15 g of product oilproduct oil and 4.16 g solid fraction were obtained (Table 1, entry 1).

Example 6

Inventive Process (Catalytic Fractionation of Peat)

[0047] Peat (15 g, 14% H.sub.2O, H5-H6, Terracult) and skeletal Ni catalyst (10 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 12.9 g of Peat, 3.69 g of product oil and 7.84 g solid fraction were obtained (Table 1, entry 1).

Example 7

Inventive Process (Catalytic Fractionation of Peat)

[0048] Peat (15 g, 14% H.sub.2O, H6-H7, Terracult) and skeletal Ni catalyst (10 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 12.9 g of Peat, 4.36 g of product oil and 7.5 g solid fraction were obtained (Table 1, entry 1).

Example 8

Inventive Process (Catalytic Fractionation of Peat)

[0049] Peat (37.5 g, 61.2% H.sub.2O, H6-H7, Terracult) and skeletal Ni catalyst (10 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) (inclusive of the original H.sub.2O content in the peat) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 15.3 g of Peat, 4.27 g of product oil and 8.96 g solid fraction were obtained (Table 1, entry 1).

Example 9

Inventive Process (Catalytic Fractionation of Peat)

[0050] Peat (15 g, 14% H.sub.2O, H7-H8, Terracult) and skeletal Ni catalyst (10 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) (inclusive of the original H.sub.2O content in the peat) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 12.9 g of Peat, 4.79 g of product oil and 7.6 g solid fraction were obtained (Table 1, entry 1).

Example 10

Inventive Process (Catalytic Fractionation of Peat)

[0051] Peat (48.6 g, 69.6% H.sub.2O, H7-H8, Terracult) and skeletal Ni catalyst (10 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) (inclusive of the original H.sub.2O content in the peat) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 14.8 g of Peat, 4.99 g of product oil and 8.73 g solid fraction were obtained (Table 1, entry 1).

Example 11

Inventive Process (Catalytic Fractionation of Peat)

[0052] Peat (18.25 g, 54.8% H.sub.2O, H3-H4, Terracult) and skeletal Ni catalyst (8 g, skeletal NiO prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich and left in air for oxidation) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) (inclusive of the original H.sub.2O content in the peat) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 8.25 g of Peat, 2.89 g of product oil and 4.64 g solid fraction were obtained (Table 1, entry 1).

Example 12

Inventive Process (Catalytic Fractionation of Peat)

[0053] Peat (18.25 g, 54.8% H.sub.2O, H3-H4, Terracult) and skeletal Ni catalyst (8 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) with 0.6186 g KOH as a co-catalyst, was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) (inclusive of the original H.sub.2O content in the peat) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 8.25 g of Peat, 2.92 g of product oil and 4.74 g solid fraction were obtained (Table 1, entry 1).

Example 13

Inventive Process (Catalytic Fractionation of Peat)

[0054] Coir (15 g, 57% H.sub.2O, Terracult) and skeletal Ni catalyst (10 g, Raney Ni prepared from NiAl alloy 50/50 w/w %, Sigma-Aldrich) was suspended in a 150 mL solution of 2-PrOH:water (7:3, v/v) in a 250 mL autoclave equipped with a mechanical stirrer. The suspension was heated from 25 to 180 C. within 1 h under mechanical stirring. The suspension was processed under autogeneous pressure at 180 C. for 3 h. In sequence, the mixture was left to cool down to room temperature. A brown solution was obtained after filtering off the peat fibers (solid fraction). The solvent was removed at 60 C. using a rotoevaporator. After solvent removal, a brown oil (product oil) was obtained. In turn, the solid fraction was washed with acetone, and then dried under vacuum evaporation. From 6.4 g of Peat, 2.24 g of product oil and 3.96 g solid fraction were obtained (Table 1, entry 1).

Example 14

Distillation of the Oil

[0055] Vacuum distillation of an 11.6048 g product oil was carried out in a Buchi Glass Oven B-585 with two fractions collected at 100 C. 120 C., 140 C., 160 C., 180 C., 200 C. and 250 C. From the starting oil mixture 5.6371 g was not distilled below 250 C., 4.116 g and 0.5700 g of oil was distilled in fraction 1 and 2 at 100 C. respectively, 0.2808 g and 0.4888 g of oil was distilled in fraction 1 and 2 at 120 C. respectively, 0.1104 g and 0.5363 g of oil was distilled in fraction 1 and 2 at 140 C. respectively, 0.1692 g and 0.4063 g of oil was distilled in fraction 1 and 2 at 160 C. respectively, 0.0653 g and 0.6563 g of oil was distilled in fraction 1 and 2 at 180 C. respectively, 0.0616 g and 0.5453 g of oil was distilled in fraction 1 and 2 at 250 C. respectively, 0.0784 g and 0.9297 g of oil was distilled in fraction 1 and 2 at 250 C. respectively. The char fraction with a distillation value above 250 C. was 5.6371 g. From the char fraction an extraction with toluene yielded a 0.9361 g toluene soluble fraction. The results are summarized in table 2.

[0056] Analysis of the Products

[0057] The determination of humidity of the solid fraction and starting material was determined on a thermobalance (Ohaus MB25). Typically, the samples (2 to 3 g) were heated up to 105 C. for 20 min. The humidity was determined as the weight loss after 20 min.

[0058] The reaction mixtures were analyzed using 2D GCGC-MS (1st column: Rxi-1 ms 30 m, 0.25 mm ID, df 0.25 m; 2nd column: BPX50, 1 m, 0.15 mm ID, df 0.15 m) in a GC-MS-FID 2010 Plus (Shimadzu) equipped with a ZX1 thermal modulation system (Zoex). The temperature program started with an isothermal step at 40 C. for 5 min. Next, the temperature was increased from 40 to 300 C. by 5.2 C. min.sup.1. The program finished with an isothermal step at 300 C. for 5 min. The modulation applied for the comprehensive GCGC analysis was a hot jet pulse (400 ms) every 9000 ms. The 2D chromatograms were processed with GC Image software (Zoex). The products were identified by a search of the MS spectrum with the MS library NIST 08, NIST 08s, and Wiley 9. Summary of the compounds identified by MS spectrum comparison are in table 5.