PROCESS FOR REDUCTION OF ASPHALTENES FROM MARINE FUELS

Abstract

A process dissolves or disperses asphaltenes from marine fuels by using at least one quaternary ammonium compound. A weight ratio of saturates to asphaltenes in the marine fuel is at least 4.0. A marine fuel is produced that includes saturates, aromatics, and asphaltenes in addition to at least one quaternary ammonium compound. Another process reduces or prevents fouling caused by asphaltenes in a marine fuel.

Claims

1. A process, comprising: dissolving or dispersing asphaltenes in a marine fuel by adding at least one quaternary ammonium compound, the marine fuel comprising 5 to 70 wt % saturates (determined according to SARA analysis using TLC-FID, IP 469), 10 to 85 wt % aromatics (determined according to SARA analysis using TLC-FID, IP 469), and 1 to 30 wt % asphaltenes (determined according to ASTM D3279), with the proviso that a sum of the saturates, the aromatics, and the asphaltenes is less than 100 wt %, wherein a weight ratio of the saturates to the asphaltenes is at least 4.0.

2. A marine fuel composition, comprising: 5 to 70 wt % saturates (determined according to SARA analysis using TLC-FID, IP 469), 10 to 85 wt % aromatics (determined according to SARA analysis using TLC-FID, IP 469), 1 to 30 wt % asphaltenes (determined according to ASTM D3279), and 50 to 2000 ppm by weight of at least one quaternary ammonium compound, wherein a weight ratio of the saturates to the asphaltenes is at least 4.0.

3. A process for reducing or preventing fouling caused by asphaltenes in a marine fuel, the marine fuel comprising: 5 to 70 wt % saturates (determined according to SARA analysis using TLC-FID, IP 469), 10 to 85 wt % aromatics (determined according to SARA analysis using TLC-FID, IP 469), 1 to 30 wt % asphaltenes (determined according to ASTM D3279), and wherein a weight ratio of the saturates to the asphaltenes is at least 4.0, wherein the process comprises adding 50 to 2000 ppm by weight of at least one quaternary ammonium compound to the said marine fuel.

4. The process according to claim 3, wherein a potential total sediment (TSP) value, determined according to ISO 10307-2:2009(E), procedure A, of an unadditised marine fuel is reduced by at least 25% by adding the indicated amounts of the at least one quaternary ammonium compound to the said marine fuel.

5. The process according to claim 1, wherein the marine fuel is selected from the group consisting of ISO-F-DMX, DMA, DFA, DMZ, DFZ, and DFB, and ISO-F RMA, RMB, RMD, RME, RMG, and RMK according to DIN ISO 8217.

6. The process according to claim 1, wherein the marine fuel is selected from the group consisting of MOO (Marine gas oil), MDO (Marine diesel oil), IFO (Intermediate fuel oil), MFO (Marine fuel oil), HFO (Heavy fuel oil), IFO 380 (<3.5% sulphur)), IFO 180 (<3.5% sulphur)), LS 380 (<1.0% sulphur), LS 180 (<1.0% sulphur), LSMGO (<0.1% sulphur, and ULSMGO (sulphur 0.0015% max).

7. The process according to claim 1 wherein the at least one quaternary ammonium compound is of a formula
.sup.+NR.sup.1R.sup.2R.sup.3R.sup.4A.sup. in which A.sup. stands for an anion, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are an organic residue with from 1 to 100 carbon atoms, substituted or unsubstituted, linear or branched alkyl, alkenyl or hydroxyalkyl residue with 1 to 100 carbon atoms, R.sup.5 additionally may be substituted or unsubstituted cycloalkyl or aryl residues bearing 5 to 20 carbon atoms.

8. The process according to claim 1, wherein the at least one quaternary ammonium compound is of formula ##STR00010## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, R stands for a C.sub.1- to C.sub.4-alkyl or hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

9. The process according to claim 1, wherein the at least one quaternary ammonium compound is of formula ##STR00011## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, and R stands for a hydroxy-C.sub.1- to C.sub.4-alkyl.

10. The process according to claim 1, wherein the at least one quaternary ammonium compound is of formula ##STR00012## wherein in this formula PIB stands for a polyisobutenyl residue having a number average molecular weight M.sub.n of from 550 to 2300 g/mol, R stands for an C.sub.1- to C.sub.4-alkyl or hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

11. The process according to claim 1, wherein the at least one quaternary ammonium compound is of formula ##STR00013## wherein in this formula R.sup.a stands for C.sub.1-C.sub.20-alkyl, R.sup.b stands for a hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

12. The process according to claim 1, wherein the at least one quaternary ammonium compound is of formula ##STR00014## wherein in this formula X.sub.i for i=1 to n and 1 to m are independently of another selected from the group consisting of CH.sub.2CH.sub.2O, CH.sub.2CH(CH.sub.3)O, CH(CH.sub.3)CH.sub.2O, CH.sub.2C(CH.sub.3).sub.2O, C(CH.sub.3).sub.2CH.sub.2O, CH.sub.2CH(C.sub.2H.sub.5)O, CH(C.sub.2H.sub.5)CH.sub.2O and CH(CH.sub.3)CH(CH.sub.3)O, m and n independently of another are positive integers, with the proviso that a sum (m+n) is from 2 to 50, R stands for an C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

13. The process according to claim 1, wherein the at least one quaternary ammonium compound is of formula ##STR00015## wherein in this formula R.sup.a and R.sup.b independently of another stand for C.sub.1-C.sub.20-alkyl or hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup. stands for an anion.

14. The process according to claim 7, wherein the marine fuel has a content of saturates according to IP 469 of at least 15 wt %.

15. The process according to claim 1, wherein the at least one quaternary ammonium compound is used in the marine fuel in amounts of from 20 to 5000 ppm by weight.

16. The process according to claim 1, wherein the marine fuel comprises: 10 to 50 wt % saturates, 30 to 70 wt % aromatics, and 5 to 20 wt % asphaltenes, and wherein the weight ratio of the saturates to the asphaltenes is at least 5.0.

17. The marine fuel composition according to claim 2, comprising: 10 to 50 wt % saturates, 30 to 70 wt % aromatics, 5 to 20 wt % asphaltenes, and 70 to 1000 ppm by weight of the at least one quaternary ammonium compound, and wherein the weight ratio of the saturates to the asphaltenes is at least 5.0.

18. The process according to claim 3, wherein the marine fuel comprises: 10 to 50 wt % saturates, 30 to 70 wt % aromatics, and 5 to 20 wt % asphaltenes, and wherein the weight ratio of the saturates to the asphaltenes is at least 5.0, and wherein the process comprises adding 70 to 1000 ppm by weight of the at least one quaternary ammonium compound to the said marine fuel.

19. The process according to claim 3, wherein the TSP value, determined according to ISO 10307-2:2009(E), procedure A, of the unadditised marine fuel is reduced by at least 40% by adding the indicated amounts of the at least one quaternary ammonium compound to the said marine fuel.

Description

EXAMPLES

Analytical Methods

[0131] SARA analyses were performed on the components according to IP 469 via TLC-FID using a Latroscan MK 6 from company NTS America, Inc.

[0132] In addition, asphaltene contents according to ASTM D3279 and sulfur contents via EN ISO 8754:2003-12 were determined. Values are given in weight %, unless stated otherwise.

[0133] Total sediment (TSE) was determined according to ISO 10307-1:2009(E).

[0134] Potential total sediment (TSP) was determined according to ISO 10307-2:2009(E), procedure A. Accelerated total sediment (TSA) was determined according to ISO 10307-2:2009(E), procedure B.

Materials

[0135] 4-Dodecylbenzenesulfonic acid (DBSA, CAS 121-65-3) was obtained from Aldrich.

[0136] N-Vinylpyrrolidone-Hexadecen-Copolymer Ganex V-216 (see WO 2012/039900) was obtained from company Ashland.

[0137] The inventive quaternary ammonium compound Quat1 was prepared from polyisobutene-substituted succinic anhydride (from polyisobutene with a molecular weight of 1000), 3-dimethylamino-propane-1-amine and propylene oxide (PO) in analogy to Herstellungsbeispiel 1 from WO 2012/004300 by replacing styrene oxide by PO.

[0138] Fuel components 1 to 4 were used for blending of Marine fuels:

TABLE-US-00001 Compo- Compo- Compo- Compo- nent 1 nent 2 nent 3 nent 4 Saturates(1) [%] 6.38 6.45 42.67 11.14 Aromatics and 34.23 82.78 17.87 85.24 Polyaromatics(1) [%] Resins(1) [%] 47.6 9.94 18.84 3.07 Asphaltenes [%] 8.7 1.5 1.1 0.1 (ASTM D3279) Sulfur content [%] 0.77 0.94 0.03 0.066 TSE [%] 0.06 0.04 0.01 0.01 TSP [%] 0.06 0.04 0.01 0.01 TSA [%] 0.06 0.04 0.01 0.01 (1)Measured according to IP 469

[0139] Marine fuels 1-3 were blended according to the following tale (wt %):

TABLE-US-00002 Compo- Compo- Compo- Compo- nent 1 nent 2 nent 3 nent 4 Marine fuel 1 45% 10% 35% 10% Marine fuel 2 32% 20% 38% 10% Marine fuel 3 35% 20% 18% 27%

[0140] For Marine fuels 1-3 the following properties were calculated from their compositions:

TABLE-US-00003 Marine fuel 1 Marine fuel 2 Marine fuel 3 Saturates(1) [%] 19.56 20.66 14.21 Aromatics and 38.46 42.83 54.77 Polyaromatics(1) [%] Resins(1) [%] 29.32 24.69 22.87 Asphaltenes [%] 4.5 3.5 3.6 (ASTM D3279) Sulfur content [%] 0.46 0.45 0.48 Wt Ratio 4.3 5.9 3.9 Saturates:Asphaltenes (1)Measured according to IP 469

[0141] The components were blended in the order 2, 4, 1, 3. In the case of dispersant additization, the respective additive was dissolved in component 2 and then blended in the other components were added in the order 4, 1, 3.

TABLE-US-00004 Additive TSP dosage active improvement Marine compound TSP over Type fuel Additive [ppm] [%] reference Reference 1 None 0.16 Inventive 1 Quat1 250 0.11 34% Example 1 Comparative 1 DBSA 562 0.17 +5% Example 1 Comparative 1 Ganex 511 0.12 25% Example 2 V-216 Reference 2 None 0.10 Inventive 2 Quat1 250 0.06 40% Example 2 Reference 3 None 0.03 Inventive 3 Quat1 250 0.02 26% Example 3

[0142] The potential total sediment (TSP value, total sediment aged) is the total amount of sediment that can be formed under normal storage conditions, excluding external influences. If the potential total sediment aged of the heavy fuel oil markedly exceeds the specification value (0.10% m/m maximum) for all grades of intermediate (IFOs) and heavy fuel oils (HFOs)), problems with the fuel cleaning system can occur, fuel filters can get plugged and combustion can become erratic.

TABLE-US-00005 Marine fuel 1 Marine fuel 2 Marine fuel 3 Saturates(1) [%] 19.56 20.66 14.21 Aromatics and 38.46 42.83 54.77 Polyaromatics(1) [%] Resins(1) [%] 29.32 24.69 22.87 Asphaltenes [%] 4.5 3.5 3.6 (ASTM D3279) Wt Ratio 4.3 5.9 3.9 Saturates:Asphaltenes TSP Improvement 34% 40% 26% (1)Measured according to IP 469

[0143] It can easily be seen that the quaternary compound according to the invention reduces the potential total sediment more than compounds known from the prior art. This effect is more pronounced the higher the weight ratio of saturates to asphaltenes is.

[0144] Marine fuels 4 and 5 were commercially available with compositions as follows:

TABLE-US-00006 Marine fuel 4 Marine fuel 5 Saturates(1) [%] 67.85 63.90 Aromatics and 14.38 12.73 Polyaromatics(1) [%] Resins(1) [%] 11.20 17.03 Asphaltenes [%] 3.93 4.29 (ASTM D3279) Sulfur content [%] 0.47 0.47 Wt Ratio Saturates 17.26 14.90 (1):Asphaltenes (ASTM D3279) (1)Measured according to IP 469

TABLE-US-00007 Additive TSP dosage active improvement Marine compound TSP over Type fuel Additive [ppm] [%] reference Reference 4 None 0.22 Inventive 4 Quat1 250 0.09 55% Example 4 Reference 5 None 0.10 Inventive 5 Quat1 250 0.07 30% Example 5