COMPOSITION COMPRISING HEAVY PETROLEUM OIL

Abstract

A composition including a heavy petroleum oil and a lignin oil containing lignin oligomers and methylated sugars.

Claims

1. A composition, comprising: a heavy petroleum oil, and a lignin oil containing lignin oligomers and methylated sugars.

2. The composition according to claim 1, wherein the amount of the lignin oil is 0.1 wt. % to 30 wt. % with respect to the composition, preferably between 10 and 25 wt. %.

3. The composition according to claim 1, wherein the heavy petroleum oil is selected from heavy fuel oil, vacuum gas oil, lubrication oil and mixtures thereof.

4. The composition according to claim 1, wherein the methylated sugars comprise methylated C5 sugars and optionally methylated C6 sugars, and wherein the amount of methylated C5 sugars is at least 50 wt. % of the methylated sugars.

5. The composition according to claim 1, wherein the methylated sugar is selected from the group consisting of methyl-pentopyranoside, methyl-D-glucopyranoside, methyl-D-xylopyranoside, methyl 3-O-acetylpentopyranoside, dimethyl-4-O-methyl-hexanopyroside and mixtures thereof.

6. The composition according to claim 1, wherein the lignin oligomer has a number average molecular mass between 400 and 1000 g/mol.

7. The composition according to claim 1, wherein the composition comprises little or no amount of alcohols selected from methanol, ethanol and butanol, preferably the total amount of said alcohols is at most 1 wt. % with respect to the composition.

8. The composition according to claim 1, wherein the total amount of the heavy petroleum oil and the lignin oil is at least 95 wt. %, at least 98 wt. %, at least 99 wt. %, at least 99.5 wt. %, at least 99.9 wt. % or 100 wt. % of the composition.

9. A process for preparing the composition according to claim 1, comprising the steps of: i) preparing a crude liquid lignin oil comprising the lignin oligomer, the methylated sugar and an alcohol selected from methanol, ethanol and butanol and combinations thereof, ii) obtaining a substantially alcohol free fraction from the crude liquid lignin oil and iii) blending the substantially alcohol free fraction with the heavy petroleum oil.

10. The process according to claim 9, wherein step ii) involves extracting the methylated sugar from the crude liquid lignin oil and step iii) involves blending the extracted methylated sugar with the heavy petroleum oil and the lignin oligomer.

11. The process according to claim 9, wherein step ii) involves removing the alcohol from the crude liquid lignin oil to obtain the substantially alcohol free fraction.

12. The process according to claim 9, wherein step ii) involves separating the crude liquid lignin oil to obtain a first fraction comprising the lignin oligomer and a second fraction comprising the methylated C5/C6 sugar and the alcohol and removing the alcohol from the second fraction to obtain a third fraction and step iii) involves blending the first fraction and the third fraction with the heavy petroleum oil.

13. The process according to claim 9, wherein step i) comprises treating a lignocellulosic feedstock with the alcohol in the presence of an inorganic acid and an added gas.

14. The process according to claim 13, wherein the treatment is conducted at an operating temperature between 100? C. and 210? C., at an operating pressure lower than 200 bar and at least 1 bar above the vapour pressure of the alcohol at the operating temperature, a residence time up to 240 minutes, wherein the amount of water in the process is less than 10 wt. %, and wherein the ratio (w/w) of lignin (in lignocellulosic feedstock) to the alcohol ranges between 1:1.5 and 1:9.

15. Use of a methylated C5 sugar for increasing dispersion of a blend of a heavy petroleum oil and lignin oligomers.

16. The composition according to claim 2, wherein the heavy petroleum oil is selected from heavy fuel oil, vacuum gas oil, lubrication oil and mixtures thereof, and wherein the methylated sugars comprise methylated C5 sugars and optionally methylated C6 sugars, and wherein the amount of methylated C5 sugars is at least 50 wt. % of the methylated sugars.

17. The composition according to claim 16, wherein the methylated sugar is selected from the group consisting of methyl-pentopyranoside, methyl-D-glucopyranoside, methyl-D-xylopyranoside, methyl 3-O-acetylpentopyranoside, dimethyl-4-O-methyl-hexanopyroside and mixtures thereof, and wherein the lignin oligomer has a number average molecular mass between 400 and 1000 g/mol.

18. The composition according to claim 17, wherein the composition comprises little or no amount of alcohols selected from methanol, ethanol and butanol, preferably the total amount of said alcohols is at most 1 wt. % with respect to the composition, and wherein the total amount of the heavy petroleum oil and the lignin oil is at least 95 wt. %, at least 98 wt. %, at least 99 wt. %, at least 99.5 wt. %, at least 99.9 wt. % or 100 wt. % of the composition.

19. A process for preparing the composition according to claim 18, comprising the steps of: i) preparing a crude liquid lignin oil comprising the lignin oligomer, the methylated sugar and an alcohol selected from methanol, ethanol and butanol and combinations thereof, ii) obtaining a substantially alcohol free fraction from the crude liquid lignin oil and iii) blending the substantially alcohol free fraction with the heavy petroleum oil.

20. The process according to claim 19, wherein step i) comprises treating a lignocellulosic feedstock with the alcohol in the presence of an inorganic acid and an added gas, and wherein the treatment is conducted at an operating temperature between 100? C. and 210? C., at an operating pressure lower than 200 bar and at least 1 bar above the vapour pressure of the alcohol at the operating temperature, a residence time up to 240 minutes, wherein the amount of water in the process is less than 10 wt. %, and wherein the ratio (w/w) of lignin (in lignocellulosic feedstock) to the alcohol ranges between 1:1.5 and 1:9.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0056] FIG. 1 Dispersion of particles prepared in Comp Exp 1

[0057] FIG. 2 Dispersion of particles prepared in Comp Exp 2

[0058] FIG. 3 Dispersion of particles prepared in Comp Exp 3

[0059] FIG. 4 Dispersion of particles prepared in Exp 4

[0060] FIG. 5 GPC of the methylated C5 sugar fraction of the lignin oil used in example 4.

DETAILED DESCRIPTION OF THE INVENTION

[0061] The invention is now elucidated by way of the following examples, without however being limited thereto.

Comparative Experiment 1

[0062] 4 g of technical lignin PB1000 were added in a round bottom flask, together with 16 g of heavy fuel oil (HFO). The PB1000 lignin has number average (Mn) molecular weight>1000 g/mol and weight average molecular weight>4000 g/mol. The particle size of the lignin was approx. 210 micron. The flask was transferred to an oil bath of 60? C. and was mixed rigorously for 15 minutes. Then, a representative sample was taken and added onto a glass plate for visual observation on the amount and nature of solid particles in the mixture composition. It is visually obvious that a dispersion with high number of large particles is present. A photo of the representative sample is shown in FIG. 1.

Comparative Experiment 2

[0063] 4 g of technical lignin PB1000 were added in a round bottom flask, together with 16 g of vacuum gas oil (VGO). The flask was transferred to an oil bath of 60? C. and was mixed rigorously for 15 minutes. The PB1000 lignin has number average (Mn) molecular weight>1000 g/mol and weight average molecular weight>4000 g/mol. The particle size of the lignin was approx. 210 micron. Then, a representative sample was taken and added onto a glass plate for visual observation on the amount and nature of solid particles in the mixture composition. It is visually obvious that a dispersion with high number of large particles is present. A photo of the representative sample is shown in FIG. 2.

Comparative Experiment 3

[0064] Lignin oligomers were produced after solvolysis of PB1000 in methanol according to the process described in WO 2019053287A1. The lignin oligomers were produced after mild depolymerization of PB1000 in methanol, 200? C., 30 minutes reaction time and lignin:methanol ratio of 1:10 w/w. After reaction the product mixture was subjected to solid/liquid separation step (such as filtration) or centrifugation to separate insoluble solids. Then the liquid mixture of methanol and soluble lignin oligomers was subjected to vacuum distillation to isolate the solid fraction of lignin oligomers and remove all the solvent. The lignin oligomers have Mn of 1342 g/mol, and dispersity of 1.48. The Glass transition temperature of these lignin oligomers is 82.9?1? C. 4 gr of the solid lignin oligomers were added in a round bottom flask, together with 16 g of vacuum gas oil (VGO). The flask was transferred to an oil bath of 60? C. and was mixed rigorously for 15 minutes. Then, a representative sample was taken and added onto a glass plate for visual observation on the amount and nature of solid particles in the mixture composition. It is visually obvious that a dispersion with larger agglomerates is present in the fuel composition. A photo of the representative sample is shown in FIG. 3.

Example 4

[0065] The product obtained according to the process of WO 2021/064047 was subjected to vacuum distillation in order to remove all the alcohol solvent. The product is a viscous lignin oil composition. 4 g of the lignin oil (comprising lignin oligomers and methylated C5 sugars (no solvent)) were added together with 16 g of HFO into a round bottom flask. The flask was transferred to an oil bath of 60? C. and was mixed rigorously for 15 minutes. Then, a representative samples was taken and added onto a glass plate for visual observation on the amount and nature of solid particles in the mixture composition. It is visually obvious that less or smaller particles were present in the fuel mixture composition. A photo of the representative sample is shown in FIG. 4.

[0066] The methylated C5 sugars present in the lignin oil were analysed with GPC and NMR.

[0067] Table 1 shows the sugars present in the methylated C5 sugar fraction. FIG. 5 shows the GPC of the methylated C5 fraction.

TABLE-US-00001 TABLE 1 Compositional Analysis Sugars Component Concentration (% dm) Mannitol (total by NREL method) (% dm) 0.56 Fucose (total by NREL method) (% dm) 0.37 Rhamnose (total by NREL method) (% dm) 1.10 Arabinose (total by NREL method) (% dm) 2.84 Galactose (total by NREL method) (% dm) 4.43 Glucose (total by NREL method) (% dm) 20.8 Xylose (total by NREL method) (% dm) 32.2 Fructose (total by NREL method) (% dm) <0.44 Ribose (total by NREL method) (% dm) <0.22 Galacturonic acid (total by NREL method) (% dm) 2.25 Guluronic acid (total by NREL method) (% dm) <0.11 Glucuronic acid (total by NREL method) (% dm) <0.11 Mannuronic acid (total by NREL method) (% dm) <0.05 Iduronic acid (total by NREL method) (% dm) <0.21