SYSTEM AND METHOD FOR THE CONVERSION OF BIOMASS, AND PRODUCTS THEREOF

Abstract

The present invention relates to a system and method for converting biomass and the products obtained therefrom. The system comprises a conversion unit (1) provided with an inlet (5) for introducing biomass, an inlet (6) for introducing a gas stream, an outlet (8) for removing carbonized material (9), and an outlet (10) for releasing a fluid (F3), the system further comprising a first separation unit (11), a second separation unit (15), a condensing unit (18).

Claims

1. System for converting biomass, the system comprising: A) a conversion unit (1) provided with an inlet (5) for introducing biomass, an inlet (6) for introducing a gas stream, an outlet (8) for removing carbonized material (9), and an outlet (10) for releasing a fluid (F3), said conversion unit comprising: a first heat transfer zone (1A) for heating the gas stream by direct contact between the gas stream and carbonized biomass having a first temperature level (CT1), resulting in the at least partial combustion thereof and a first fluid (F1) having a first temperature level (T1); a second heat transfer zone (1B) for heating dried biomass by direct contact between the first fluid (F1) having a first temperature level (T1) and the dried biomass, resulting in the at least partial conversion thereof and the release of a second fluid (F2) having a second temperature level (T2); a drying zone (1C) for drying a fresh biomass by direct contact between the second fluid (F2) having a second temperature level (T2) and the fresh biomass, resulting in a dried biomass and the release of a third fluid (F3) having a third temperature level (T3), a discharge zone (1D) provided with outlet (8) for continuously removing carbonized material (9), said system further comprising: B) a first separation unit (11), for separating solids and tar from the third fluid (F3) by direct contact between the fluid (F3) and a first liquid, resulting in a fourth outlet fluid (F4) having a fourth outlet temperature level (F4) and a first outlet fraction (FR1), comprising essentially tar and solids; C) a second separation unit (15) for separating an oil from the fourth outlet fluid (F4) by subjecting same to centrifugal forces, resulting in a fifth outlet fluid (F5) having a fifth outlet temperature level (T5) and a second outlet fraction (FR2) essentially comprising an oil; D) condensing unit (18), for condensing and separating residual liquids from the fifth outlet fluid (F5) by direct contact between the fifth outlet fluid (F5) and a second liquid and indirect contact with a cooling medium, resulting in a sixth outlet fluid (F6) having a sixth temperature level (T6) and a third fraction (FR3), essentially comprising a mixture of water and acids.

2. System according to claim 1, wherein the system is provided with a heat exchanger for preheating the gas stream prior to introducing the gas stream to the first heat transfer zone (1A).

3. System according to one claim 1 or claim 2, characterized in that the gas stream is ambient air.

4. System according to any one of the previous claims, wherein that the second separation unit (15) comprises at least one horizontal rotatable disk comprising at least one blade extending at least partly from the periphery towards the centre of the disk, whereby the intersection of blade and disk is at an angle with the disk radius of between 0 and 180 degrees, and extending at least partly from the disk in vertical direction, whereby the line extending from the peripheral intersection of blade and disk in a direction perpendicular to the blade is at an angle with the horizontal plane of between 0 and 90 degrees.

5. System according to claim 4, wherein the second separation unit (15) comprises one or multiple sequential units wherein the outlet temperature of the last unit equals the fifth temperature level and the inlet temperature of the first unit equals the fourth temperature level in order to separate the second fraction in one or multiple sub-fractions.

6. System according to any one of the previous claims, wherein the system comprises a ventilator (22) for creating a gas stream, the ventilator being located downstream relative to the condensing unit (18).

7. System according to one any one of the previous claims, wherein the system comprises a third separation unit (24) for separating residual liquids from the sixth fluid, resulting in a gas stream and a fourth fraction, essentially comprising a mixture of oil and water.

8. System according to claim one any one of the previous claims, wherein in that the first liquid is water.

9. System according to anyone of the previous claims, wherein the second liquid at least partly comprises the first fraction collected from the first separation unit (11).

10. System according to one of the claim 9, characterized in that the cooling medium is water or ambient air.

11. System according to any one of the previous claims, the system further comprising: an engine (30), for converting a pyrolysis gas to mechanical power; a generator (33), for converting the mechanical power provided by the engine (30) through a first drive shaft (32) into electrical power; a compressor (35), for compressing ambient air to a first pressure level, using mechanical power provided by the engine (30) through a second drive shaft (34), which is directly connected to the first drive shaft (32); a membrane separation unit (38), for separating the compressed air having a first pressure level into a first gas fraction, comprising essentially pure nitrogen at a second pressure level, and a second gas fraction, comprising ambient air having an increased oxygen level and a third pressure level.

12. System according to any one of claims 1-11, further comprising a drying unit (41), said drying unit comprising an inlet for bio-oil (42), optionally an inlet for drying additives (43) and an outlet (44) for the dried bio-oil.

13. Method for converting biomass into carbonized material and fluids, the method comprising the steps of: i) heating a gas stream by direct contact in a first heat transfer zone (1A) in a conversion reactor between the gas stream and carbonized biomass having a first temperature level (CT1), resulting in the at least partial combustion thereof and a first fluid (F1) having a first temperature level (T1); ii) heating dried biomass by direct contact in a second heat transfer zone (1B) between the first fluid (F1) having a first temperature level (T1) and the dried biomass, resulting in the at least partial conversion thereof and the release of a second fluid having a second temperature level; iii) drying fresh biomass by direct contact in a drying zone (1C) between the second fluid having a second temperature level and the fresh biomass, resulting in a dried biomass and the release of a third fluid having a third temperature level, iv) continuously removing carbonized biomass from a discharge zone (1D), v) continuously providing the third fluid released from outlet 10 of conversion unit 1 to the first separation unit 11 to provide a fourth fluid (F4) a first fraction (FR1) being essentially tar and solids, and vi) introducing the fourth fluid (F4) to the second separation unit 15, wherein the fourth fluid is subjected to centrifugal forces to provide a second fraction comprising bio-oil and a fifth fluid (F5) having a fifth temperature level (F5).

14. Method according to claim 13, further comprising the step vii) of condensing and separating residual liquids from the fifth fluid (F5) by direct contact between the fifth fluid (F5) and a second liquid and indirect contact with a cooling medium in a condensing unit (18), resulting in a sixth fluid (F6) having a sixth temperature level (T6) and a third fraction (FR3) comprising a mixture of water and acids.

15. Method according to claim 14 or claim 13, further comprising the step vii) of subjecting the bio-oil obtained in step vi) to a drying step to provide a bio-oil having a water content of less than 1% w/w. Method according to claim 1, wherein step vii) is carried out in the presence of an amine, selected from the group consisting of ammonia, primary, secondary and tertiary amines.

17. Method according to claim 15, wherein the carbonized material 9 has a carbon content of between 70 and 100% by weight based on the dried mass of the carbonized material, preferably between 80 and 90% by weight based on the dried mass of the carbonized material 9.

18. Method according to claim 14, wherein said acids are pyroligneous acids (FR3) having a water content of between 70 and 90% w/w and an oxygenated hydrocarbon content of between 30 and 10% w/w.

19. Method according to any one or more of claims 13-17, wherein gas emitted from the conversion unit is collected and supplied to a burner to be used as energy generation for the pyrolysis reactor.

20. Method according to any one of claims 13-19, wherein the biomass is selected from the group of wood, energy crops, agricultural residues, food waste, post-consumer waste and industrial waste, preferably wood.

21. System according to claims 1-12 for carrying out the method of claims 13-20.

22. Bio-oil derived from biomass having a water content of less than 5% w/w, a total acid number of 80-150 mg KOH/g, an oxygen content of less than 35% w/w and a stability of less than 10 mPa.Math.s/h, and a viscosity 400-1600 mPa.Math.S.

23. Bio-oil according to claim 22, wherein the water content is less than 1% w/w, preferably less than 0.5% w/w.

24. Bio-oil according to any one claims 22-23, having a total acid number of between 0-80 mg KOH/g, preferably 10-70, more preferably 15-60 mg KOH/g, even more preferably 20-40 mg KOH/g, most preferably 20-30 mg KOH/g.

25. Bio-oil according to any one of the claims 22-24, having a total acid number of between 0 to 30 mg KOH/g, preferably 0 to 20, more preferably 0-10 mg KOH/g.

26. Bio-oil according to any one of claims 22-25, having an oxygen content of 30-35% w/w, preferably 25-30, more preferably 15-25, even more preferably less than 15% w/w.

27. Bio-oil according to any one of claims 22-26 having a stability of less than 5 mPa.Math.s/h, preferably less than 2 mPa.Math.s/h, more preferably less than 1 mPa.Math.s/h, even more preferably less than 0.5 mPa.Math.s/h and most preferably zero mPa.Math.s/h.

28. Bio-oil according to any one of claims 22-27, further comprising an amine, selected from the group consisting of ammonia, primary, secondary and tertiary amines.

29. Bio-oil according to claim 28, the primary amine being selected from the group consisting of monoalkylamines, monoalkanolamines and polyalkylamines.

30. Bio-oil according to claim 28, the secondary amine being selected from the group consisting of dialkylamines, dialkanolamines and poly-dialkylamines.

31. Bio-oil according to claim 28, the tertiary amine being selected from the group consisting of trialkylamines, trialkanolamines and poly-trialkylamines.

32. Bio-oil according to any one or more of claims 23-31, wherein the biomass is selected from the group of industrial waste, garden waste and municipal waste, wherein said biomass preferably comprises wood, said wood preferably being a hardwood.

33. Carbonized material obtainable by the method according to any one of claims 13-21.

34. Bio-oil obtainable by the method according to any one of claims 13-21.

35. Pyroligneous acid obtainable by the method according to any one of claims 13-21.

36. Pyrolysis gas obtainable by the method according to any one of claims 13-21.

37. Fuel composition comprising a bio-oil according to any one or more of claims 22-32 or a bio-oil obtainable by a method according to any one or more of claims 13-21.

38. Use of a carbonized material, tar, bio-oil or pyroligneous acid according to any one or more of claims 33-36 or obtainable by a method according to any one or more of claims 13-21 as a component in a fuel composition or as feedstock for the preparation of adhesives, coatings, binders, sealants, bitumen and chemicals.

39. Use of a system according to any one or more of claims 1-12 for the production of at least a carbonized material and a bio-oil.

Description

BRIEF DESCRIPTION OF FIGURES

[0186] FIG. 1 diagrammatically shows an overview of a system for converting biomass into fluids by means of an airstream and separating the fluids according to an embodiment of the invention.

[0187] FIG. 2 diagrammatically shows an overview of a system for enhancing the conversion of biomass into fluids by means of an oxygen enriched airstream according to an embodiment of the invention.

[0188] As shown in FIG. 1, the system comprises a conversion unit 1 comprising a first heat transfer zone 1A, a second heat transfer zone 1B, a drying zone 10 and a discharge zone 1D. The conversion unit 1 is further provided with an inlet 5 for introducing biomass, an inlet 6 for introducing an airstream, an auger 8 for removing carbonized material, having an outlet 9 to a storage container (not shown) and an outlet 10 for releasing a fluid. The system further comprises a hopper 2, provided with an inlet 3 and an auger 4 which is connected to and in open or closed communication with inlet 5 of conversion unit 1.

[0189] The outlet 10 is connected to and in open communication with a first separation unit 11, which is provided with an inlet 12, a first outlet 13, and a second outlet 14, which is connected to and in fluid communication with a second separation unit 15.

[0190] The second separation unit 15 is further provided with means for exerting centrifugal forces on the introduced fluids (not shown), a first outlet 16 and a second outlet 17, which is connected to and in fluid communication with a condensing unit 18.

[0191] The condensing unit 18 is further provided with an inlet 19, means for introducing and releasing cooling media (not shown), a first outlet 20 and a second outlet 21, which is connected to and in fluid communication with a ventilator 22, having a ventilator outlet 23, which is connected to and in fluid communication with a third separation unit 24, which is provided with a first outlet 25, and a second outlet 26, which is connected to and in fluid communication with a gas burner or engine (not shown).

[0192] Also shown in FIG. 1 is an optional drying unit (41), comprising an inlet for receiving bio-oil (42), optionally an inlet for drying additives (43) and an outlet (44) for the dried bio-oil.

[0193] FIG. 2 shows an engine 30, which is connected to and in fluid communication with outlet 26 of separation unit 24. The engine is provided with outlet 31 and is connected to generator 33 through drive shaft 32, which is also in direct connection with compressor 35 through drive shaft 34. Compressor 35 has an inlet 36 and an outlet 37, which is connected to and in fluid communication with a membrane separation unit 38. The membrane separation unit 38 is provided with outlet 39 and outlet 40.

[0194] Pyrolysis gas, released from outlet 26 of separation unit 24, is introduced to engine 30 where it is mixed with ambient air and combusted in order to provide the energy for driving generator 33, through drive shaft 32. The formed combustion gases are released from outlet 31. The generator 33 provides electrical power to the system of the invention. In this way the system of the invention may be operated as an autonomous unit, which solely relies on the supply of biomass.

[0195] At the same time, drive shaft 34, which is in direct connection with drive shaft 32, drives compressor 35. Ambient air is introduced to inlet 36 and compressed to a first pressure level e.g. 10 bars before being released from outlet 37 and introduced into membrane separation unit 38, which separates the compressed air into a first gas fraction released from outlet 39, comprising essentially pure nitrogen at a second pressure level e.g. 9.7 bars, and a second gas fraction released from outlet 40, which essentially comprises ambient air enriched with oxygen at a third pressure level e.g. approximately ambient pressure. The oxygen content of the second gas fraction is between 28% and 40%.

[0196] The present invention is hereby further exemplified by means of the following non-limiting examples.

EXAMPLES

1.1 Materials

[0197] Bio-oils produced by the pyrolysis of beech wood biomass using the process according to the present invention were used for all experiments. In the examples of section 1.2, the bio-oil is referred to as crude bio-oil. All other chemicals were analytical grade and used as commercially available.

1.2 Methods

1.2.1 Azeotropic Distillation

[0198] All distillations were carried out in a three-neck round bottom connected to a Dean-Stark trap and cooler. During distillation, pressure was ambient whilst temperature was maintained at 80-90 C. using a temperature-controlled oil bath. Iso-Octane was used as entrainer at a 1:1-4:1 oil:solvent weight ratio.

1.2.2 Vacuum Flashing

[0199] The setup for this method comprised a four-neck resin-pot connected to a Dean-Stark trap and cooler. Dry N.sub.2 was introduced at a constant pressure of about 0.2-0.5 bar in the oil by means of a sparger made from a perforated PE tube. During experiments, pressure was maintained at 500-800 mbar and Temperature at about 80 C. by using a vacuum pump, connected to the cooler via a cold-trap at 0 C.

1.2.2 Blending Experiments

[0200] Samples of known weight (about 20 g) in closed vials were first heated to 80 C. in an oven for at least 30 minutes. Known amounts of additive(s) were then weighed in, either dropwise (liquids) or with a spatula (solids) until a desired content was reached. The vials were closed, alternately heated and swirled until complete mixing was observed by visual inspection. An alternative option comprises addition of amine(s) to oil in the reaction vessel immediately after azeotropic distillation or vacuum flashing, optionally followed by restarting the process in order to remove any volatiles produced by amine addition.

1.2.2 Titrations

[0201] About 100-200 mg aliquots of crude oil, dried oil or oil-containing mixtures were diluted 100 fold with a 50/50 Ethanol/H.sub.2O blend to a final weight of about 10-20 g in order to obtain 1% w/w solutions. After monitoring the pH of this solution using a pH-meter from Hanna Instruments, these solutions were further diluted with 50/50 Ethanol/H.sub.2O to a final weight of about 40-50 g and titrated potentiometrically with 0.1 N NaOH in H.sub.2O. Total Acid Numbers (TAN) were calculated as mg KOH/g from the amount of 0.1 N NaOH needed to reach the endpoint of the titration which was detected from the maximum of the first derivative of the titration curve, as usual.

1.2.3 H.SUB.2.O Content

[0202] Karl Fischer titration was applied to measure H.sub.2O content of both crude and dried oil samples.

1.2.4 Viscosity

[0203] Viscosity measurements were carried out at 50 C. with a Brookfield type RVDV-II+ viscometer in thermostatted small sample holders using spindle type SC-4-34. After equilibrating for at least 1 hour, several readings were taken to determine the reported viscosity, including its standard deviation. The viscometer was calibrated for the 900-25000 mPa.Math.ss range with 4 standard calibration liquids obtained from Brookfield using the standard Brookfield setup. Corrections were made for the small sample cup size, an indicated in the Brookfield handbook More solutions to sticky problems, 2014, page 13, section 3.4.10.

1.3.1 Drying by Azeotropic Distillation

Example 1

[0204] 398.1 g hot crude bio-oil was mixed with 129.5 g iso-Octane in a 1 ltr. three-neck round bottom as described in section 1.2.1. After distillation at 80-85 C., a slightly yellow, transparent distillate with pH=1.64 was obtained at a yield of 33.51 g or 8.42% of initial mass. The TAN value of the oil was reduced from 114.8 mg KOH/g for crude bio-oil to 37.6 mg KOH/g for the dried oil. The H.sub.2O content of the dried oil was 0.3% w/w versus 3.1% w/w for crude bio-oil.

[0205] Comparative example 1-A: bio-oil was produced using fast pyrolysis according to WO2012027428 in a riser reactor in the presence of a kaolin catalyst. Subsequent to condensing, the bio-oil had a bound water content of 9.99 weight percent after removal of the free water phase and a TAN value of 110.14 mg KOH/g. The bio-oil (166 g) was subjected to azeotropic distillation in the presence of 40.6 g of toluene at a pressure of about 210 mmHg and a maximum temperature of 105.3 C. After azeotropic distillation, the bio-oil had a bound water content of 0.22 weight percent, a TAN value of 55.14 mg KOH/g, and was miscible with about 10 weight percent of toluene.

[0206] This result proves that azeotropic distillation of the bio-oil according to the present invention can be used to remove H.sub.2O from pyrolysis oil while simultaneously reducing its acidity. A greater reduction in acidity is seen in the inventive method compared to that of the prior art. Addition of amine (5 or 10% w/w monoethanolamine, MEA) leads to an even greater reduction in acidity, as shown in Table 1.

TABLE-US-00001 TABLE 1 Reduction of TAN by azeotropic distillation and amine addition Water % w/w TAN % reduction TAN Example 1-A (crude) 3.1 114.8 Example 1-B (after 0.3 37.6 66% azeotroptic distillation) Example 1-B (after 0.3 16.8 85% azeotroptic distillation + 5% MEA) Example 1-B (after 0.3 8.8 93% azeotroptic distillation + 10% MEA) Comparative example 1- A 9.99 110 Comparative example 1 - B 0.22 55.1 50%

1.3.2 Drying by Vacuum Flashing

Example 2

[0207] 436.3 g hot crude bio-oil was introduced into a four-neck resin-pot as described in section 1.2.2. Dry N.sub.2 was sparged into the mixture at 80 C. and 700 mbar to yield 43.7 g or 10.0% w/w slightly yellow distillate. The dried oil had a TAN=60.1 mg KOH/g versus 114.8 mg KOH/g for crude bio-oil, showing that vacuum flashing can reduce the acid content of pyrolysis oil significantly.

1.3.2 Amines and Urea Addition

Introduction

[0208] Blends were made by mixing various liquid amines and urea at increasing concentration with pyrolysis oil, optionally dried by vacuum flashing or azeotropic distillation. Purpose of these experiments was to show that the TAN of pyrolysis oil can be reduced to sufficiently low levels, as required by application of the oil as eg. marine fuel. This is demonstrated by the following examples. It should be noted that measurement of TAN by titration is no longer possible beyond its stoichiometric point at pH=7.6 on average. Therefore, the initial pH value of the 1% w/w solutions used for titrations are reported in the examples too.

Example 3

[0209] Increasing amounts of Monoethanolamine (MEA) were mixed with pyrolysis oil (crude bio-oil), as indicated in section 1.2.2. After overnight storage at 80 C., 1% w/w solutions in 50/50 Ethanol/H.sub.2O were prepared, their pH and TAN was measured by titration as indicated in section 1.2.2. The results in table 2 demonstrate that the acidity of pyrolysis oil can be removed completely.

TABLE-US-00002 TABLE 2 Acidity of Pyrolysis oil (crude bio-oil) at increasing MEA content Initial pH of TAN % w/w MEA 1% w/w solution (mg KOH/g) 0.00 3.92 114.8 6.32 4.61 89.3 13.19 6.35 23.9 17.51 6.92 20.7 22.91 8.20 () 27.58 8.85 ()

[0210] Where (-) means not measured due to no acid being present

Example 4

[0211] The experiment of example 3 was repeated with the vacuum-flash dried crude bio-oil sample of example 2. with similar results; see table 3.

TABLE-US-00003 TABLE 3 Acidity of vacuum-flash dried Pyrolysis oil (crude bio-oil) at increasing MEA content Initial pH of TAN % w/w MEA 1% w/w solution (mg KOH/g) 0.00 4.20 60.1 7.06 4.99 47.1 18.95 9.43 () 29.43 9.85 () 30.54 9.75 () 43.23 10.20 ()

Example 5

[0212] The experiment of example 4 was repeated with crude bio-oil and Diethanolamine (DEOA) instead of MEA. The results in table 4 show that the acidity of crude bio-oil can be eliminated by DEOA as well.

TABLE-US-00004 TABLE 4 Acidity of Pyrolysis oil (crude bio-oil) at increasing DEOA content Initial pH of TAN % w/w DEOA 1% w/w solution (mg KOH/g) 0.00 4.16 98.8 10.09 5.50 50.9 20.09 6.59 8.8

Example 6

[0213] The experiment of example 4 was repeated with crude bio-oil and Diethylamine (DEA) instead of MEA. The results in table 5 show that the acidity of crude bio-oil can be eliminated by DEA as well.

TABLE-US-00005 TABLE 5 Acidity of Pyrolysis oil (crude bio-oil) at increasing DEA content Initial pH of TAN % w/w DEA 1% w/w solution (mg KOH/g) 0.00 4.16 98.8 10.17 6.20 25.4 12.00 6.61 16.2 12.99 9.82 () 13.99 10.32 () 20.12 9.31 () 25.39 10.15 ()

Example 7

[0214] The experiment of example 4 was repeated with crude bio-oil and urea instead of MEA. The results in table 6 show that the acidity of crude bio-oil can be eliminated by Urea as well.

TABLE-US-00006 TABLE 6 Acidity of Pyrolysis oil (crude bio-oil) at increasing Urea content Initial pH of TAN % w/w Urea 1% w/w solution (mg KOH/g) 0.00 4.16 98.8 9.44 4.91 61.6 15.03 5.38 46.1 19.28 5.76 33.8 23.01 5.90 27.2 26.81 6.04 24.3

Example 8

[0215] The experiment of example 4 was repeated with crude bio-oil and Triethylamine (TEA) instead of MEA. The results in table 7 show that the acidity of crude bio-oil can be eliminated by TEA as well.

TABLE-US-00007 TABLE 7 Acidity of Pyrolysis oil (crude bio-oil) at increasing TEA content Initial pH of TAN % w/w TEA 1% w/w solution (mg KOH/g) 0.00 4.16 98.8 10.19 5.66 47.7 20.02 8.41

Example 9

[0216] Liner regression analysis was applied to establish a quantitative relationship between TAN and initial pH for all samples with pH values below the stoichiometric point, including the virgin oil samples without amines. The resulting regression equation reads:

TAN=28.55*pH+204.5 with N=23, R=0.91, S.E.=12, F=101

where N, R, S.E. and F represent: number of observations, correlation coefficient, standard error of estimate and Fisher's variance ratio, respectively. FIG. 1 shows this equation in graphical form. It is concluded that the initial pH gives a good indication of the TAN that is otherwise difficult to measure using the rather time consuming titration technique.

Example 13

[0217] The impact of amine addition on the properties of pyrolysis oil is very clear from the viscosity data given by table 8. The more than 5-fold increase in crude bio-oil viscosity upon addition of amines strongly suggests that additional reactions beyond simple acid-base neutralisation have occurred. The strong dependence of all viscosities measured on Temperature furthermore demonstrates that amine-modified oils should be manageable by applying elevated Temperature during handling in practice.

TABLE-US-00008 TABLE 8 Viscosities of Amine-modified Pyrolysis oil (crude bio-oil) Temperature of % w/w measurement Viscosity Sample ID Amine ( C.) (mPa .Math. s) crude 2 775 crude bio-oil + 14.24 50 6970 MEA crude bio-oil + 14.24 60 3370 MEA crude bio-oil + 14.24 70 1824 MEA crude bio-oil + 20.09 50 9829 DEOA crude bio-oil + 20.09 60 3823 DEOA crude bio-oil + 12.00 40 13705 DEA crude bio-oil + 12.00 50 5379 DEA crude bio-oil + 12.00 60 2199 DEA crude bio-oil + 12.00 70 1020 DEA

Example 14

[0218] Stability of crude bio-oil was measured by recording viscosities of samples aged at 90 C. as a function of time up to 48 hours. The best-fitting equation of the viscosity vs time (in hours) plot obtained by linear regression reads as follows:

Viscosity (mPa.Math.s)=8.82*Time (hours)+825 with R.sup.2=0.999 F=2047 st.er.=6.6

where R.sup.2, F and st.er. represent the correlation coefficient squared, Fisher's variance ration and standard error of estimate, respectively. 95% confidence levels of the slope being 7.98 and 9.66, this result indicate that crude bio-oil of the present invention is a highly stable oil. The (average) stability of a sample of crude bio-oil according to the present invention is therefore (7.98+9.66)/2=8.82 mPa.Math.s/h, ie. Highly stable.

Example 15

Pyroligneous Acid

[0219] Pyroligneous acid produced simultaneously with the bio-oil used in examples 1-13 was analysed for its chemical composition using infrared spectroscopy and gas chromatography.

[0220] Near-infrared (NIR) were recorded on an Antaris NIR-Analyser from ThermoNicolet with pyroligneous acid samples dissolved in THF solution using 1 cm cuvets. The method compared the absorbance at 7035 cm.sup.1 of H.sub.2O in the samples with that of a series of THF-H.sub.2O mixtures of known composition that were used to construct a calibration plot.

[0221] All GC-TOFMS experiments were performed on an Agilent technologies 6890GC equipped with a PTV injector containing a baffled liner and the JEOL Time-of-Flight Mass Spectrometer (JMS GCv-100). GC analyses were performed on an Agilent 25 m0.25 mm i.d. CP-Wax 58 (FFAP) CB column with a film thickness of 0.20 m (Part no. CP7717).

[0222] For the GC-HRTOFMS characterization of the Wood acid and oil sample a programmed oven temperature was used. The GC oven was programmed from 50 C. (2 min. initial) to a final temperature of 275 C. (5.50 min.) at a programming rate of 6 C./min. The total GC run time is 45 minutes.

[0223] The Time-of-Flight detector was operated in electron impact mode and scanned over the mass range of 19-800 amu.

TABLE-US-00009 TABLE 9 Composition of pyroligneous acid prepared using the method of the present invention Quantitative: Component % w/w Measurement technique H.sub.2O 75.4 NIR-peak at 70.5 cm1 of solution in THF Acetic Acid 6.8 GC with calibration Formic Acid 2.2 By subtraction of TAN = 90.59 mg KOH/g and % w/w Acetic acid from GC (no other acids) Hydroxyacetone 2.0 GC with calibration Phenolic Rest 13.6 By subtraction from GC chromatogram

[0224] A typical pyroligneous acid as the result of the pyrolysis of wood has a composition of 80-90% water and 10-20% organic content. As can be seen by the quantitative analysis in Table 9, the pyroligneous acid of the present invention has an increased total organic content of circa 25%. The increased organic content makes the pyroligneous acid of the present invention an improved source of chemical compounds which can be extracted and purified or used in further transformations in the preparation of adhesives, coatings and speciality chemicals.

Example 16

Biochar

[0225] Properties of biochar produced simultaneously with the bio-oil of examples 1-13 was analysed. (after grinding using a commercially available, high shear grinding device, as is well known to the skilled person).

[0226] Particle size distribution was determined using Laser Light Scattering (LLS) Malvern Mastersizer 2000 (Samples were cut to size, ultratoming at 120 C. Staining: 6.5 min OsO4; 6.5 min RuO.sub.4.

[0227] The results show a broad distribution peak having a maximum at 500-600 m. Average mean volume diameter was found to be 360 m.

[0228] Surface area according to the Brunauer-Emmett-Teller (BET) method was measured according to ASTM (2016) method nr. D16556-16 on a Micromiretics instrument.

[0229] Brunauer-Emmett-Teller (BET)=N.sub.2 multilayer adsorption measured as a function of relative pressure. BET surface area=170 m.sup.2/g.

[0230] Thermogravimetric analysis (TGA) was performed on a Discovery TGA from TA Instruments under a N.sub.2 flow of 25 ml/min at a heating rate of 20 C./min from 30-1000 C.

[0231] ThermoGravimetricAnalysis (TGA) shows a gradual Wt. loss of 7.0% up to 950 C.

[0232] Thermal desorption GC/MS up to 320 C. shows mainly release of water in addition to very small quantities of volatile aromatics.

[0233] Elemental analysis gave C:N:H of 80.8:0.4:2.0;