SLURRY HYDROCRACKING OF PYROLYSIS OIL AND HYDROCARBON FEEDSTOCK, SUCH AS PETROLEUM DERIVED FEEDSTOCK

Abstract

A process of producing a hydrocracking product in a slurry hydrocracking reactor. A pyrolysis oil, a hydrocarbon feedstock, and a hydrocracking catalyst is provided. The pyrolysis oil is combined with the hydrocarbon feedstock and the hydrocracking catalyst, the pyrolysis oil being maintained at a temperature of less than 100° C. until the pyrolysis oil contacts both the hydrocarbon feedstock and the hydrocracking catalyst. The hydrocarbon feedstock and the pyrolysis oil are hydrocracked in the slurry hydrocracking reactor in the presence of the hydrocracking catalyst and hydrogen gas. A fuel precursor obtainable by the process.

Claims

1. A process of producing a hydrocracking product in a slurry hydrocracking reactor, in which process a pyrolysis oil, a hydrocarbon feedstock, and a hydrocracking catalyst is provided; the pyrolysis oil is combined with the hydrocarbon feedstock and the hydrocracking catalyst, the pyrolysis oil being maintained at a temperature of less than 100° C. until the pyrolysis oil contacts both the hydrocarbon feedstock and the hydrocracking catalyst; the hydrocarbon feedstock and the pyrolysis oil are hydrocracked in the slurry hydrocracking reactor in the presence of the hydrocracking catalyst and hydrogen gas.

2. The process according to claim 1, wherein the pyrolysis oil is maintained at a temperature of less than 100° C. until the pyrolysis oil contacts both the hydrocarbon feedstock and the hydrocracking catalyst in the presence of hydrogen gas.

3. The process according to claim 1, wherein the pyrolysis oil and the hydrocarbon feedstock is introduced to the slurry hydrocracking reactor through separate feed lines.

4. The process according to claim 1, wherein the pyrolysis oil is combined with the hydrocarbon feedstock upstream the slurry hydrocracking reactor to form a combined feed; the combined feed subsequently being introduced to the slurry hydrocracking reactor.

5. The process according to claim 1, wherein the hydrocracking catalyst is present in the hydrocarbon feedstock.

6. The process according to claim 1, wherein the hydrocracking catalyst is present in the pyrolysis oil.

7. The process according to claim 1, wherein the pyrolysis oil is combined with the hydrocarbon feedstock under agitation, such as under stirring or under pumping.

8. The process according to claim 1, wherein the slurry hydrocracking reactor is provided with a pump or a stirrer.

9. The process according to claim 1, wherein the slurry hydrocracking reactor is a continuous stirred-tank reactor.

10. The process according to claim 1, wherein the pyrolysis oil is maintained at a temperature in the range of 10-90° C., preferably in the range of 10-60° C., more preferably in the in the range of 10-50° C., until the pyrolysis oil contacts both the hydrocarbon feedstock and the hydrocracking catalyst, optionally in the presence of hydrogen gas.

11. The process according to claim 1, wherein the hydrocarbon feedstock is a petroleum derived feedstock, a biologically derived feedstock and/or a recycled feedstock, and optionally wherein the petroleum derived feedstock comprises vacuum residue (VR) and/or vacuum gas oil (VGO).

12. The process according to claim 1, wherein the pyrolysis oil is a biomass derived pyrolysis oil.

13. The process according to claim 1, wherein the hydrocracking also forms C1-C3 hydrocarbons, and wherein the process further comprises upgrading the C1-C3 hydrocarbons to form hydrogen gas, and recirculating the hydrogen gas from the upgrading to the slurry hydrocracking reactor.

14. The process according to claim 1, wherein the amount of hydrocracking catalyst in the process is less than 10% by weight of the combined weight of the hydrocarbon feedstock and the pyrolysis oil.

15. The process according to claim 1, wherein the liquid hourly space velocity (LHSV) in the reactor is in the range of from 0.25 to 5 h.sup.−1, such as in the range of from 0.5 to 2 h.sup.−1.

16. A fuel precursor obtainable by the process as defined in claim 1.

Description

EXAMPLES

Process Equipment

[0055] The tests below were run in a slurry hydrocracking (SHC) pilot plant provided with a continuous stirred-tank reactor (CSTR). Vacuum gas oil, pyrolysis oil and catalyst feedstock were continuously mixed in the slurry tank by a stirrer and then fed to a SHC reactor by a syringe pump being equipped with a stirrer to ensure a homogenous feed. Vacuum residue was fed separately to the reactor by a gear pump.

Materials

[0056] A first feed comprising 50 wt. % vacuum residue (VR) and 50 wt. % vacuum gas oil (VGO) was provided.

[0057] A second feed comprising 50 wt. % VR, 30 wt. % VGO and 20 wt. % fast pyrolysis bio oil (FPBO) from BTG BV was provided.

[0058] The properties of the feedstocks are presented in Table 1. Molybdenum 2-ethylhexanoate was chosen as catalyst for the trials at a Mo concentration of 0.1 wt. % of the total feed.

TABLE-US-00001 TABLE 1 Properties of raw materials used in this study. All numbers are given as wt. % unless otherwise stated. Method Method Component VR VGO FPBO VR/VGO FPBO C (%) 85.0 85.3 49.2 Dumas ASTM D Combustion 1744 H (%) 10.5 12.1 7.3 Dumas ASTM D Combustion 1744 N (%) 0.8 0.2 0.3 Dumas ASTM D Combustion 1744 S (%) 3.3 1.2 0.0 Dumas ASTM D Combustion 1552 O (%) 0.7 0.4 43.2 Unterzaucher Calculated Pyrolysis by difference Water (%) — — 28 — ASTM D203 TAN — — 87.2 — ASTM (mg KOH/g) D664-11a Asphaltene 6.3 — — ASTM D — (%) 6560 Residue 85.8 1.0 — ASTM D — (% >524° C.) 7169 VGO 14.2 77.9 — ASTM D — (% 343-524° C.) 7169 Distillates 0 20.6 — ASTM D — (% 177-343° C.) 7169 Naphtha 0 0.5 — ASTM D — (% IBP-177° C.) 7169

[0059] Continuous Trials

[0060] Corresponding trials were performed for both the first feed and for the second feed. “Continuous” refer to that the trials were carried out with a continuous feed of reactants, catalyst and hydrogen to the CSTR reactor and a continuous withdrawal of reaction products (solid, liquid and gas) as opposed to typical laboratory experiments using autoclaves in which experiments are carried out in batch mode.

[0061] A first trial with the first feed was performed. In the reactor VGO and catalyst was filled to a liquid level of approximately 80%. To leak test the system it was pressurized with nitrogen to 150 bar and then left overnight. Stirring was maintained at 670 rpm from when the reactor lid was closed until the experiment was initiated. Once the system was determined leak tight, nitrogen was gently released until the system was unpressurized.

[0062] A heating phase followed. During the heating phase the reactor contained only the VGO and catalyst filled prior to closing the reactor. Once liquid temperature in the reactor reached 450° C., feeding of VR through a dip tube and; feeding of a slurry of VGO and catalyst was initiated, with the total flow rate corresponding to a residence time in the reactor of about 1.5 h. Reaction pressure was maintained at 150 bar, hydrogen flow at 800 NL/h, stirring at 1340 rpm throughout the trial from initial heating to shut down. The catalyst slurry was fed through the bottom inlet and VR through the dip tube. Liquid products were collected, and the outlet gas monitored and analysed.

[0063] After feeding raw material to the reactor for about 7.5 h (5 replacements of the reactor volume), the product tanks were emptied in order to start collecting product at stable conditions for the remainder of the trial. The process was maintained at stable conditions for another 13 hours after this and samples of the liquid product were collected every third hour by redirecting the product flow from the product tanks to sample bottles.

[0064] A second trial with the second feed was also performed. This trial differed from the reference trial in that the catalyst slurry comprised catalyst, VGO and pyrolysis oil. The temperature of the catalyst slurry feed tank and feed line was maintained at about 45° C.

[0065] The experimental parameters are summarized in Table 2 (first trial) and Table 3 (second trial).

TABLE-US-00002 TABLE 2 Summarized experimental parameters for the first trial. Parameter Value Wt. % VR in feed 50 Wt. % VGO in feed 50 Wt. % FPBO infeed 0 LHSV (h.sup.−1) 0.71 Catalyst Molybdenum 2-etylhexanoate Catalyst Loading (% Mo) 0.1 Temperature (° C.) 450 Pressure (bar) 150 Hydrogen flow (Ndm.sup.3/h) 800

TABLE-US-00003 TABLE 3 Summarized experimental parameters for second trial. Parameter Value Wt. % VR in feed 50 Wt. % VGO in feed 30 Wt. % FPBO in feed 20 LHSV (h.sup.−1) 0.64 Catalyst Molybdenum 2-etylhexanoate Catalyst Loading (% Mo) 0.1 Temperature (° C.) 450 Pressure (bar) 150 Hydrogen flow (Ndm.sup.3/h) 800

[0066] The liquid products were then analysed using the methods of Table 4.

TABLE-US-00004 TABLE 4 Analysis methods used for characterization of products. Property Analysis Method Elemental Composition Dumas Combustion (Elemental (CHN) Microanalysis, UK) Elemental Composition Mitsubishi NSX-2100V with automatic (S) liquid injector (ASC-250L), vertical furnace (VF-210) and UV-fluorescence detector (SD-210) Elemental Composition Unterzaucher Pyrolysis (Elemental (O) Microanalysis, UK) Total acid number ASTM D664-11a (TAN) Boiling point ASTM 7169 (Heavy oil product) and distribution ASTM 2887 (Light oil product) Asphaltene in heavy ASTM D6560 (Uniper, Sweden) oil product .sup.14C content ISO 13822: 2013 (Tandem Laboratory, Sweden) Water content ASTM E203-16 (Only analyzed in water fraction)

[0067] The results of the analysis are presented in Table 5.

TABLE-US-00005 TABLE 5 Summary of the continuous test trials. VR/VGO/FPBO 50:50:0 50:30:20 Wt. % VR in feed (%) 50.6 48.9 LHSV (h.sup.−1) 0.71 0.64 Total mass balance (%) 94.6 96.9 H.sub.2 Consumption (g/kg feed) 6.5 14.8 Total oil product yield (%) 90.1 76.8 UCO (>524° C.) (%) 10.1 6.4 VGO (343-524° C.) (%) 38.4 24.8 Distillates (177-343° C.) (%) 26.8 26.4 Naphtha (IBP-177° C.) (%) 14.8 19.2 Water (%) — 7.8 Total Sediment yield (%) 1.62 1.38 Coke (%) 0.95 0.86 Asphaltene Sediment (%) 0.67 0.52 Total gas yield (%) 8.2 14.0 CH.sub.4 (%) 2.4 3.7 C.sub.2H.sub.6 (%) 1.5 2.6 C.sub.3H.sub.8 (%) 2.5 3.6 H.sub.2S (%) 1.9 1.9 CO.sub.2 (%) — 1.8 CO (%) — 0.5 VR Conversion (%) 76.0 84.3 Asphaltene Conversion (%) 46.5 45.2 HDS (%) 43.2 58.3 HDO (%) 33.1 91.7 H/C mass ratio 0.134 0.131 O (%) 0.39 0.99 S (%) 1.44 1.05 N (%) 0.63 0.73 TAN (mg KOH/g) 0.057 0.23 Proportion C14 (%) — 8.6

Itemized List of Embodiments

[0068] 1. A process of producing a hydrocracking product in a slurry hydrocracking reactor, in which process [0069] a pyrolysis oil, a petroleum derived feedstock, and a hydrocracking catalyst is provided; [0070] the pyrolysis oil is combined with the petroleum derived feedstock and the hydrocracking catalyst, the pyrolysis oil being maintained at a temperature of less than 100° C. until the pyrolysis oil contacts both the petroleum derived feedstock and the hydrocracking catalyst; [0071] the petroleum derived feedstock and the pyrolysis oil are hydrocracked in the slurry hydrocracking reactor in the presence of the hydrocracking catalyst and hydrogen gas. [0072] 2. The process according to item 1, wherein the pyrolysis oil is maintained at a temperature of less than 100° C. until the pyrolysis oil contacts both the petroleum derived feedstock and the hydrocracking catalyst in the presence of hydrogen gas. [0073] 3. The process according to any one of items 1-2, wherein the pyrolysis oil and the petroleum derived feedstock is introduced to the slurry hydrocracking reactor through separate feed lines. [0074] 4. The process according to any one of items 1-2, wherein the pyrolysis oil is combined with the petroleum derived feedstock upstream the slurry hydrocracking reactor to form a combined feed; the combined feed subsequently being introduced to the slurry hydrocracking reactor. [0075] 5. The process according to any one of the preceding items, wherein the hydrocracking catalyst is present in the petroleum based feedstock. [0076] 6. The process according to any one the preceding items, wherein the hydrocracking catalyst is present in the pyrolysis oil. [0077] 7. The process according to any one of the preceding items, wherein the pyrolysis oil is combined with the petroleum derived feedstock under agitation, such as under stirring or under pumping. [0078] 8. The process according to any one of the preceding items, wherein the slurry hydrocracking reactor is provided with a pump or a stirrer. [0079] 9. The process according to any one of the preceding items, wherein the slurry hydrocracking reactor is a continuous stirred-tank reactor. [0080] 10. The process according to any one of the preceding items, wherein the pyrolysis oil is maintained at a temperature in the range of 10-90° C., preferably in the range of 10-60° C., more preferably in the in the range of 10-50° C., until the pyrolysis oil contacts both the petroleum derived feedstock and the hydrocracking catalyst, optionally in the presence of hydrogen gas. [0081] 11. The process according to any one of the preceding items, wherein the petroleum derived feedstock comprises vacuum residue (VR) and/or vacuum gas oil (VGO). [0082] 12. The process according to any one of the preceding items, wherein the pyrolysis oil is a biomass derived pyrolysis oil. [0083] 13. The process according to any one of the preceding items, wherein the hydrocracking also forms C1-C3 hydrocarbons, and wherein the process further comprises upgrading the C1-C3 hydrocarbons to form hydrogen gas, and recirculating the hydrogen gas from the upgrading to the slurry hydrocracking reactor. [0084] 14. A fuel precursor obtainable by the process as defined in any one of items 1-13.