Derivatizing of thermochemical oil

Abstract

A process for obtaining an oil derivative. The process comprises the following steps: providing a thermochemical oil comprising a compound having a hydroxyl group, wherein the thermochemical oil is crude or refined oil resulting from thermochemical conversion of organic material; additionally providing a compound having an acyl group by feeding the compound having an acyl group, or a carboxylic acid or an ester as starting material for conversion to the compound having an acyl group, to the thermochemical oil; and reacting the compound having a hydroxyl group with the compound having an acyl group, thereby forming an ester between said compounds. A process for obtaining an intermediate composition, the process comprising blending the oil derivative with a refinery feedstock. An oil derivative or an intermediate composition. A process for obtaining a fuel component, the process comprising hydrotreating or hydrocracking the oil derivative or intermediate composition. A process for obtaining a fuel composition, the process comprising blending the fuel component with another component of a refinery fuel component pool. A fuel component or a fuel composition.

Claims

1. A process for obtaining an oil derivative, the process comprising the following steps: providing a thermochemical oil comprising a compound having a hydroxyl group, wherein the thermochemical oil is crude or refined oil resulting from thermochemical conversion of organic material; additionally providing a compound having an acyl group by feeding the compound having an acyl group, or a carboxylic acid or an ester as starting material for conversion to the compound having an acyl group, to the thermochemical oil; and reacting the compound having a hydroxyl group with the compound having an acyl group, thereby forming an ester between said compounds, wherein the compound having a hydroxyl group is an alcohol or phenol.

2. The process according to claim 1, wherein the thermochemical oil is a pyrolysis oil, a hydrothermal liquefaction oil, or a blend thereof.

3. The process according to claim 1, wherein the compound having an acyl group is a carboxylic acid, an ester or a carboxylic acid anhydride.

4. The process according to claim 1, wherein the compound having an acyl group is provided by conversion of a carboxylic acid to a symmetrical or unsymmetrical carboxylic acid anhydride.

5. The process according to claim 1, wherein the acyl group has a straight or branched, saturated or unsaturated, carbon chain with at least 2 carbons.

6. The process according to claim 3, wherein the carboxylic acid or the carboxylic acid anhydride is a fatty acid or a fatty acid anhydride, respectively.

7. The process according to claim 3, wherein the ester is a triglyceride or a fatty acid ester.

8. The process according to claim 3, wherein the carboxylic acid is provided as renewable feedstock; and/or the ester is provided as renewable feedstock.

9. The process according to claim 1, wherein water and/or volatile compounds are removed from the thermochemical oil or the oil derivative before, during and/or after reacting the compound having a hydroxyl group with the compound having an acyl group.

10. A process for obtaining an intermediate composition, the process comprising the following steps: obtaining an oil derivative by the process according to claim 1; and blending the oil derivative with a refinery feedstock being more lipophilic than the thermochemical oil, or a renewable feedstock.

11. An oil derivative produced by the process according to claim 1, wherein the compound having an acyl group is a carboxylic acid or an ester and wherein the carboxylic acid is provided as renewable feedstock being raw tall diesel, tall oil fatty acids, palm fatty acid distillate, algae oil fatty acids or volatile fatty acids having 3 to 6 carbons, or a blend thereof; and/or the ester is provided as renewable feedstock being vegetable oil, animal fat, marine oil, algae oil, used cooking oil or fatty acid methyl esters, or a blend thereof.

12. A process for obtaining a fuel component, the process comprising the following steps: obtaining an oil derivative by the process according to claim 1; and hydrotreating or hydrocracking the oil derivative.

13. A process for obtaining a fuel composition, the process comprising the following steps: obtaining a fuel component by the process according to claim 12; and blending the fuel component with another component of a refinery fuel component pool.

14. A fuel component produced by the process according to claim 12, wherein the compound having an acyl group is a carboxylic acid or an ester and wherein the carboxylic acid is provided as renewable feedstock being raw tall diesel, tall oil fatty acids, palm fatty acid distillate, algae oil fatty acids or volatile fatty acids having 3 to 6 carbons, or a blend thereof; and/or the ester is provided as renewable feedstock being vegetable oil, animal fat, marine oil, algae oil, used cooking oil or fatty acid methyl esters, or a blend thereof.

15. An intermediate composition produced by the process according to claim 10, wherein the compound having an acyl group is a carboxylic acid or an ester and wherein the carboxylic acid is provided as renewable feedstock being raw tall diesel, tall oil fatty acids, palm fatty acid distillate, algae oil fatty acids or volatile fatty acids having 3 to 6 carbons, or a blend thereof; and/or the ester is provided as renewable feedstock being vegetable oil, animal fat, marine oil, algae oil, used cooking oil or fatty acid methyl esters, or a blend thereof.

16. A process for obtaining a fuel component, the process comprising the following steps: obtaining an intermediate composition by the process according to claim 10; and hydrotreating or hydrocracking the intermediate composition.

17. A fuel composition produce by the process of claim 13, wherein the compound having an acyl group is a carboxylic acid or an ester and wherein the carboxylic acid is provided as renewable feedstock being raw tall diesel, tall oil fatty acids, palm fatty acid distillate, algae oil fatty acids or volatile fatty acids having 3 to 6 carbons, or a blend thereof; and/or the ester is provided as renewable feedstock being vegetable oil, animal fat, marine oil, algae oil, used cooking oil or fatty acid methyl esters, or a blend thereof.

18. A fuel component produced by the process of claim 16, wherein the compound having an acyl group is a carboxylic acid or an ester and wherein the carboxylic acid is provided as renewable feedstock being raw tall diesel, tall oil fatty acids, palm fatty acid distillate, algae oil fatty acids or volatile fatty acids having 3 to 6 carbons, or a blend thereof; and/or the ester is provided as renewable feedstock being vegetable oil, animal fat, marine oil, algae oil, used cooking oil or fatty acid methyl esters, or a blend thereof.

Description

EXAMPLES

(1) Analyses

(2) Hydroxyl numbers related to aliphatic alcohols (ROH), phenols (ArOH) and carboxylic acids (COOH) were determined by .sup.31P—NMR. .sup.1H—NMR was used to characterize relative amounts of aromatic, aliphatic, ether/alcohol, aldehyde, ketone, carboxylic acid and olefin functionalities of the obtained product mixtures.

(3) Molecular weight distributions, i.e. number average molecular weight M.sub.n, weight average molecular weight M.sub.w and size average molecular weight M.sub.z were determined by gel permeation chromatography.

(4) Elemental analysis was used to determine content of carbon, hydrogen, nitrogen and sulfur. Elemental analysis was performed by Micro-analytisches Laboratorium Kolbe, Mülheim an der Ruhr, Germany. The oxygen content was calculated by difference.

(5) Depending on which product samples, other analyses which are not shown here have been performed (e g trace element analyses).

(6) Raw Materials

(7) Wood oil characterization: Pyrolysis oil produced by fast pyrolysis of wood material and subsequent condensation of the vapors was obtained from BTG Biomass Technology Group BV, Netherlands. Water content was determined by Karl Fisher titration and found to be 21% w/w. For further analytical characterization, a wood oil sample was dried over MgSO.sub.4 after dilution in 10 volumes of ethyl acetate. After filtration and evaporation, the remaining sample weight was 60% of the input weight of wood oil. Hydroxyl numbers (Table 1) and molecular weight distributions (Table 2) were determined. .sup.1H-NMR data are listed in Table 5. The interpretation of the weight reduction observed during dried wood oil sample preparation is that together with the water another 19% w/w of small, volatile components from the wood oil were adsorbed on the drying agent or removed during the solvent evaporation. More volatile components are not expected to contribute to the final biodiesel after hydrotreatment, as their carbon chain length are likely between one and four carbons only. The distillate from the derivatization below was analyzed with GC-MS, confirming acetic acid and acetic anhydride as major components.

(8) Raw tall diesel characterization: Tall oil is a by-product from the pulp and paper industry and mainly consists of resin acids and free fatty acids. Raw tall diesel (RTD) is produced from tall oil through a (vacuum) distillation process, during which the content of free fatty acids is increased relative to the resin acids and other components. Raw tall diesel was obtained from Sunpine AB, Sweden. Hydroxyl numbers (Table 1) and molecular weight distributions (Table 2) were determined.

(9) Rapeseed oil characterization: Rapeseed oil is a source of triglycerides and is assumed to contain negligible amounts of free hydroxyl groups. Molecular weight distributions were determined (Table 2).

(10) TABLE-US-00001 TABLE 1 Hydroxyl numbers for raw materials Raw material ROH (mmol/g) ArOH (mmol/g) COOH (mmol/g) Wood oil 3.0 2.5 0.4 RTD 0.04 0.05 3.75

(11) TABLE-US-00002 TABLE 2 Molecular weight distributions for raw materials Raw material M.sub.n M.sub.w M.sub.z Wood oil 269 467 916 RTD 337 367 392 Rapeseed oil 1344 1469 2025
Oil Derivatization

Example 1

(12) Anhydride method: Wood oil (50.1 g) and RTD (124.5 g) were mixed at room temperature (rt). The mixture was pretreated by distilling off water and low boiling components (end conditions: 25 mbar/130° C.). A substantial amount of the mixture solidified. Acetic anhydride (32.4 g, ˜2 equiv.) and N-methyl imidazole (NMI) (2.6 g, 0.2 equiv) were added and the resulting mixture was heated to 170° C. The temperature was decreased to 130° C. before distillation recommenced (end conditions: 30 mbar/150° C.). The product mixture obtained was in the form of a homogeneous dark syrup. Hydroxyl numbers were determined for the product oil (Table 3). The results correlate with a 93% derivatization of the alcohol functionalities. Molecular weight distributions were determined (Table 4). The results indicate a molecular weight distribution increase from M.sub.w 467 (wood oil) to M.sub.w 1502 for the product mixture. .sup.1H-NMR-data are listed in Table 5 below. Elemental analysis data are shown in Table 6. The product mixture was subsequently blended with LGO (ratio 1:9, 1:4 or 3:7), providing homogeneous feeds suitable for hydrotreatment.

Example 2

(13) The anhydride method described in Example 1 was used to prepare a derivatized wood oil mixture, using RTD as the carboxylic acid component. Upon completed esterification, the product mixture (61 g) was kept at 110° C. Hydroxyl numbers are shown in Table 3 and elemental analysis data are shown in Table 6. Further, RTD (61 g) and LGO (62 g) were charged to the product mixture to reach a ratio of derivatized wood oil/RTD/LGO of 1:1:1. This provided a homogeneous mixture, which was stable after cooling to ambient temperature. The resulting mixture is suitable as a feed for hydrotreatment.

Example 3

(14) Wood oil (12.4 g) and oleic acid (44 g) were mixed at room temperature. The mixture was pretreated by distilling off water and low boiling components under reduced pressure (end conditions 130° C.). A substantial amount of the mixture solidified. Acetic anhydride (7.5 g) and N-methyl imidazole (NMI) (0.62 g) were added at 120° C. The resulting mixture was heated to 170° C. and was then kept at 170° C. for 20 min. The temperature was decreased to 110° C. before vacuum distillation recommenced at 110° C. The product mixture obtained was in the form of a homogeneous dark syrup. Hydroxyl numbers are shown in Table 3 and elemental analysis data are shown in Table 6. Additional oleic acid (22 g) was charged at 110° C., producing a homogeneous mixture, which was stable after cooling to ambient temperature. The resulting product mixture is suitable as feed for hydrotreatment.

Example 4

(15) Fisher esterification: Wood oil (51.9 g) and RTD (100.6 g) were mixed at rt. The mixture was pretreated by distilling off water and low boiling components (end conditions: 22 mbar/130° C.). The temperature was lowered to 70° C. before sulfuric acid (98% w/w, 0.5 mL) was added and distillation recommenced (end conditions: 20-30 mbar/130° C.) for removal of water. The product consisted of a two phase mixture: a solid phase of 13 g and a liquid phase of 120 g. The hydroxyl numbers were determined separately for the two phases, and are also presented as a weighted result representing the product as a whole (Table 3). The results correlate with a 43% derivatization of the alcohol functionalities. Molecular weight distributions were determined separately for the two phases (Table 4). The results verify a molecular size increase from M.sub.w 467 (wood oil) to M.sub.w 2288 for the solid fraction and M.sub.w 725 for the liquid fraction. Solid phase and liquid phase were sampled for elemental and trace analysis (see Table 6). Representative samples of solid and liquid fractions were withdrawn (ratio solid fraction to liquid fraction 1:9. total weight 6.0 g), and incorporated into LGO (24 g) to provide a feed suitable for hydrotreatment.

Example 5

(16) Acid catalyzed trans-esterification: Wood oil (51.7 g) and rapeseed oil (98.7 g) were mixed at rt. The mixture was pretreated by distilling off water and low boiling components (end conditions: 24 mbar/142° C.). The temperature was lowered to 100° C. before sulfuric acid (98% w/w, 0.1 mL) was added and distillation recommenced (end conditions: 22 mbar/142° C.) for 17 h to remove volatile components released during the reaction. The product consisted of a two phase mixture: a solid phase of 30 g and a liquid phase of 97 g. The hydroxyl numbers were determined separately for the two phases and are also presented as a weighted result representing the product as a whole (Table 3). The results correlate with a 43% derivatization of the alcohol functionalities. Molecular weight distributions were determined separately for the two phases (table 4). The results verify a molecular size increase from M.sub.w 467 (wood oil) to M.sub.w 2332 for the solid fraction and M.sub.w 1464 for the liquid fraction. Solid phase and liquid phase were sampled for elemental and trace analysis (Table 6). Representative samples of solid and liquid fractions were withdrawn (ratio solid fraction to liquid fraction 1:3.2, total weight 6.0 g), and incorporated into LGO (24 g) to provide a feed suitable for hydrotreatment.

(17) TABLE-US-00003 TABLE 3 Hydroxyl numbers for oil derivatives ROH ArOH COOH Material (mmol/g) (mmol/g) (mmol/g) Example 1 0.06 0.02 1.7 Example 2 0 0.02 4.02 Example 3 0 0.03 9.16 Example 4 Liquid 0.16 0.49 2.43 Example 4 Solid 0.48 1.39 1.30 Example 4 Weighted 0.19 0.58 2.32 Example 5 Liquid 0.12 0.23 0.07 Example 5 Solid 0.82 1.27 0.14 Example 5 Weighted 0.29 0.49 0.09

(18) TABLE-US-00004 TABLE 4 Molecular weight distributions for oil derivatives Material M.sub.n M.sub.w M.sub.z Example 1 473 1502 6584 Example 4 Liquid 384 725 3304 Example 4 Solid 612 2288 7472 Example 5 Liquid 613 1464 2585 Example 5 Solid 796 2332 6932

(19) TABLE-US-00005 TABLE 5 .sup.1H-NMR (CDCl.sub.3) results for wood oil and for Examples 1-3 (normalized integrals) ppm Integral Wood oil: .sup.1H-NMR signals Carboxylic acid H (COOH) and 12-9  3.10 aldehyde H (CHO) Aromatic H   9-6.2 11.82 Olefin H 6.2-4.5 12.74 Alifatic alcohol H, —CHOH or 4.5-3.3 23.53 alifatic ether —CHOR Alifatic H 3.3-0   48.82 Example 1: .sup.1H-NMR signals Carboxylic acid H (COOH) and 12-9  0.10 aldehyde H (CHO) Aromatic H   9-6.2 1.78 Olefin H 6.2-4.5 11.74 Alifatic alcohol H, —CHOH or 4.5-3.3 2.26 alifatic ether —CHOR Alifatic H 3.3-0   84.12 Example 2: .sup.1H-NMR signals Carboxylic acid H (COOH) and 12-9  0.02 aldehyde H (CHO) Aromatic H   9-6.2 3.17 Olefin H 6.2-4.5 5.58 Alifatic alcohol H, —CHOH or 4.5-3.3 0.70 alifatic ether —CHOR Alifatic H 3.3-0   90.53 Example 3: .sup.1H-NMR signals Carboxylic acid H (COOH) and 12-9  0 aldehyde H (CHO) Aromatic H   9-6.2 1.49 Olefin H 6.2-4.5 11.79 Alifatic alcohol H, —CHOH or 4.5-3.3 1.16 alifatic ether —CHOR Alifatic H 3.3-0   85.57

(20) TABLE-US-00006 TABLE 6 Elemental compositions of raw materials and oil derivatives Comment/ Sample % C % H % N % S % O description Wood oil as 52.98 7.06 1.37 0.17 38.42 Wood oil as delivered delivered Example 1 75.48 10.59 1.11 <0.01 12.82 Homogeneous, Product RTD-esterified wood oil Example 2 76.40 10.40 0.64 0.06 12.5 Homogeneous, Product RTD-esterified wood oil Example 3 71.80 10.80 0.62 0.00 16.78 Homogeneous, Product oleic acid- esterified wood oil Example 4 70.60 9.10 0.78 0.17 19.35 Solid material Solid 13 g from Fisher esterification Example 4 76.10 10.66 0.96 0.25 12.03 Oil 120 g from Liquid Fisher esterification Example 4 75.56 10.50 0.94 0.24 12.75 Combined Weighted material from Fisher esterification Example 5 69.00 8.49 0.18 0.34 21.99 Solid material Solid 30 g from acid catalyzed transesterification Example 5 76.79 11.72 0.36 <0.01 11.13 Oil 97 g from Liquid acid catalyzed transesterification Example 5 74.95 10.96 0.31 0.08 13.70 Acid catalyzed Weighted transesterification

REFERENCES

(21) [1] M. B. Smith and J. March, Advanced Organic Chemistry, Reactions, Mechanisms and Structure, 6th Edition, John Wiley & Sons, 2007, ISBN 13: 978-0-471-72091-1, ISBN 10: 0-471-72091-7, pages 1414-1416 and references therein. [2] M. B. Smith and J. March, Advanced Organic Chemistry, Reactions, Mechanisms and Structure, 6th Edition, John Wiley & Sons, 2007, ISBN 13: 978-0-471-72091-1, ISBN 10: 0-471-72091-7, pages 1419-1421 and references therein. [3] M. B. Smith and J. March, Advanced Organic Chemistry, Reactions, Mechanisms and Structure, 6th Edition, John Wiley & Sons, 2007, ISBN 13: 978-0-471-72091-1, ISBN 10: 0-471-72091-7, pages 1412-1414 and references therein. [4] Trost and Fleming, Comprehensive Organic Synthesis, Volume 6 Heteroatom Manipulation, Pergamon Press Ltd, 1991, Chapter 2.2 Synthesis of Esters, Activated Esters and Lactones, ISBN 0-08-040597-5, pages 323-380. [5] a) μl-Otaibi et al., Energy Fuels 2005, 19, 2526 and in Perreira et al. “Crude Oil Desalting Process” http://dx.doi.org/10.5772/61274.
b) U.S. Pat. No. 5,114,566. [6] Mhatre et al., Chemical Engineering Research and Design 2015, 9, 177-195. [7] Rinaldi et al., Catalytic Hydrogenation for Biomass Valorisation, ISBN 978-1-84973-801-9 and references therein.

ITEMIZED LIST OF EMBODIMENTS

(22) 1. A process for obtaining an oil derivative, the process comprising the following steps: providing a thermochemical oil comprising a compound having a hydroxyl group; additionally providing a compound having an acyl group; and reacting the compound having a hydroxyl group with the compound having an acyl group, thereby forming an ester between said compounds.

(23) 2. The process according to item 1, wherein the thermochemical oil is a pyrolysis oil, preferably a pyrolysis bio oil, a hydrothermal liquefaction oil, preferably a hydrothermal liquefaction bio oil, or a blend thereof, more preferably a pyrolysis oil, most preferably a pyrolysis bio oil.

(24) 3. The process according to item 1 or 2, wherein the compound having a hydroxyl group is an alcohol or a phenol.

(25) 4. The process according to any one of the preceding items, wherein the compound having an acyl group is a carboxylic acid, an ester or a carboxylic acid anhydride.

(26) 5. The process according to any one of the preceding items, wherein the compound having an acyl group is provided by conversion of a carboxylic acid to a symmetrical or unsymmetrical carboxylic acid anhydride.

(27) 6. The process according to any one of the preceding items, wherein the acyl group has a straight or branched, saturated or unsaturated, preferably saturated, carbon chain with at least 2 carbons, such as 2 to 24 carbons, preferably at least 4 carbons, such as 4 to 18 carbons, more preferably 6 to 18 carbons.

(28) 7. The process according to any one of items 4 to 6, wherein the carboxylic acid or the carboxylic acid anhydride is a fatty acid or a fatty acid anhydride, respectively.

(29) 8. The process according to any one of items 4 to 7, wherein the ester is a triglyceride or a fatty acid ester.

(30) 9. The process according to any one of items 4 to 8, wherein the carboxylic acid is provided as renewable feedstock, preferably as raw tall diesel, tall oil fatty acids, palm fatty acid distillate, algae oil fatty acids or volatile fatty acids having 3 to 6 carbons, or a blend thereof; and/or the ester is provided as renewable feedstock, preferably as vegetable oil, such as rapeseed oil or technical corn oil, animal fat, marine oil, algae oil, used cooking oil or fatty acid methyl esters, or a blend thereof.

(31) 10. The process according to any one of the preceding items, wherein water and/or volatile compounds are removed, preferably by vacuum or ambient pressure distillation, from the thermochemical oil or the oil derivative before, during and/or after, preferably before and/or after, more preferably after, reacting the compound having a hydroxyl group with the compound having an acyl group.

(32) 11. A process for obtaining an intermediate composition, the process comprising the following steps: obtaining an oil derivative by the process according to any one of items 1 to 10; and blending the oil derivative with a refinery feedstock being more lipophilic than the thermochemical oil, such as a fossil feedstock, preferably light gas oil or vacuum gas oil, or a renewable feedstock, preferably a renewable feedstock comprising fatty acids or triglycerides.

(33) 12. An oil derivative obtainable by the process according to any one of items 1 to 10 or an intermediate composition obtainable by the process according to item 11.

(34) 13. A process for obtaining a fuel component, such as a gasoline, kerosene or diesel fuel component, the process comprising the following steps: obtaining an oil derivative by the process according to any one of items 1 to 10 or an intermediate composition by the process according to item 11; and hydrotreating or hydrocracking the oil derivative or intermediate composition.

(35) 14. A process for obtaining a fuel composition, such as a gasoline, kerosene or diesel fuel, the process comprising the following steps: obtaining a fuel component by the process according to item 13; and blending the fuel component with another component of a refinery fuel component pool.

(36) 15. A fuel component obtainable by the process according to item 13 or a fuel composition obtainable by the process according to item 14.