Mixtures for improving or boosting the separation of water from fuels

Abstract

Mixtures of certain olefin-carboxylic acid copolymers (A) with at least one additive with detergent action, preferably at least one quaternary nitrogen compound (B), and optionally further fuel additives, are useful for improving or boosting the separation of water from fuel oils and gasoline fuels.

Claims

1. A process for improving or boosting the separation of water from fuel oils and gasoline fuels, the process comprising: applying mixtures of olefin-carboxylic acid copolymers (A) with a number-average molecular weight Mn of from 0.5 to 10 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard), obtainable by in a first reaction (I), copolymerizing (Aa) at least one ethylenically unsaturated mono- or dicarboxylic acid or derivative thereof, (Ab) at least one ?-olefin having from at least 12 up to and including 30 carbon atoms, (Ac) optionally, at least one further aliphatic or cycloaliphatic olefin which has at least 4 carbon atoms and is different than (Ab), and (Ad) optionally one or more further copolymerizable monomers other than monomers (Aa), (Ab), and (Ac), selected from the group consisting of (Ada) vinyl esters, (Adb) vinyl ethers, (Adc) (meth)acrylic esters of alcohols having at least 5 carbon atoms, (Add) allyl alcohols or ethers thereof, (Ade) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides, and N-vinyllactams, (Adf) ethylenically unsaturated aromatics, (Adg) ?,?-ethylenically unsaturated nitriles, (Adh) (meth)acrylamides, and (Adi) allylamines, followed by in a second optional reaction (II) partly or fully hydrolyzing and/or saponifying anhydride or carboxylic ester functionalities present in a copolymer obtained from (I), the second reaction being run at least when the copolymer obtained from reaction (I) does not comprise any free carboxylic functionalities; with at least one additive with detergent action selected from the group consisting of quaternary nitrogen compounds (B), and polyisobutenylsuccinimides (G), to the water containing fuel oils and gasoline fuels, and allowing an organic phase and aqueous phase to separate.

2. The process according to claim 1, wherein monomer (Aa) is maleic acid anhydride.

3. The process according to claim 1, wherein monomer (Ab) is one or more linear or branched 1-alkene.

4. The process according to claim 1, wherein no (Ac) and (Ad) are present in the copolymer.

5. The process according to claim 1, wherein compound (B) is of the formula
.sup.+NR.sup.1R.sup.2R.sup.3R.sup.4A.sup.? in which A.sup.? stands for an anion comprising a carboxylate or carbonate, 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, R.sup.5 additionally may be a substituted or unsubstituted cycloalkyl or aryl residue bearing 5 to 20 carbon atoms.

6. The process according to claim 1, wherein nitrogen compounds (B) are obtainable by addition of a compound which comprises at least one oxygen- or nitrogen-containing group reactive with an anhydride and additionally at least one quaternizable amino group onto a polycarboxylic anhydride compound and subsequent quaternization in the presence of an acid or in an acid-free manner, in the absence of free acid, or with a carboxylic ester.

7. The process according to claim 1, wherein the nitrogen compound (B) is of formula ##STR00008## 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 comprising a carboxylate or carbonate.

8. The process according to claim 1, wherein the nitrogen compound (B) is of formula ##STR00009## 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.

9. The process according to claim 1, wherein the nitrogen compound (B) 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 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 comprising a carboxylate or carbonate.

10. The process according to claim 1, wherein the nitrogen compound (B) is of formula ##STR00011## 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 comprising a carboxylate or carbonate.

11. The process according to claim 1, wherein the nitrogen compound (B) is of formula ##STR00012## 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 the 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 comprising a carboxylate or carbonate.

12. The process according to claim 1, wherein the nitrogen compound (B) is of formula ##STR00013## 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 comprising a carboxylate or carbonate.

13. The process according to claim 1, wherein the polyisobutenylsuccinimide (G) is of formula ##STR00014## 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 n stands for a positive integer of from 2 to 6.

14. The process according to claim 1, wherein the mixture of (A) and (B) or (G) is applied together with at least one dehazer as additive component (C) selected from the group consisting of (C1) alkoxylation copolymers of ethylene oxide, propylene oxide, butylene oxide, styrene oxide and/or other oxides; and (C2) alkoxylated phenol formaldehyde resins.

15. The process according to claim 1, wherein the mixture of (A) and (B) or (G) is applied together with at least one organic nitrate as additive cetane number improver (D).

16. The process according to claim 1, wherein (Aa) is at least one ethylenically unsaturated dicarboxylic acid.

17. The process according to claim 5, wherein A.sup.? is a carboxylate R.sup.5COO.sup.? or a carbonate R.sup.5OCOO.sup.?; R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are an unsubstituted, linear or branched alkyl, alkenyl, or hydroxyalkyl residue with 1 to 100 carbon atoms; and R.sup.5 additionally may be a substituted or unsubstituted cycloalkyl or aryl residue bearing 5 to 12 carbon atoms.

18. The process according to claim 7, wherein PIB is a polyisobutenyl residue having a number average molecular weight M.sub.n of from 750 to 1300 g/mol, R is methyl or 2-hydroxypropyl, and A.sup.? is acetate, salicylate or methyloxalate.

19. The process according to claim 9, wherein PIB is a polyisobutenyl residue having a number average molecular weight M.sub.n of from 750 to 1300 g/mol, R is methyl, and A.sup.? is salicylate or methyloxalate.

20. The process according to claim 12, wherein R.sup.a is a C.sub.1-C.sub.20-alkyl, R.sup.b is a hydroxy-C.sub.1- to C.sub.4-alkyl, and A.sup.? is a C.sub.12-C.sub.100-alkyl- and -alkenyl succinic acid.

Description

EXAMPLES

(1) Detergent 1: Reaction product of polyisobutenyl succinic acid anhydride (based upon polyisobutene with a molecular weight of 1000 g/mol) with 3-(N,N-dimethylamino) propane-1-amine (DMAPA) with consecutive quaternization with propylene oxide in an analogous matter as described in WO 2012/004300 A1, Synthetic Example 1 (applied as 50 wt % solution in 2-ethylhexanol).

(2) Detergent 2: reaction product of n-hexadecyldimethylamine with propylene oxide, with hydrolyzed polyisobutenyl succinic acid as counterion as described in EP 3004294 B1, Synthetic Example 6 (applied as 50 wt % solution in 2-ethylhexanol).

(3) Detergent 3: In the table, the conventional succinimide detergent is a reaction product of polyisobutenyl succinic acid anhydride (based upon polyisobutene with a molecular weight M.sub.w of 1000 g/mol) and tetraethylene pentamine (TEPA) in a mole ratio of about 1.6 to 1 as generally disclosed in U.S. Pat. No. 8,475,541 (applied as 50 wt % solution in 2-ethylhexanol).

(4) Detergent 4: Amide of oleic acid and DMAPA quaternized with propylene oxide with oleic acid as counterion as described in EP 2796534 A1, Inventive Example 3 (applied as 50 wt % solution in 2-ethylhexanol).

(5) Detergent 5: Condensation product of polyisobutenyl succinic acid anhydride (based upon polyisobutene with a molecular weight of 1000 g/mol) with 3-aminopropyl imidazol, quarternized with methyl salicylate in an analogous matter as described in WO 2013/000997, Synthetic Example 2 (applied as 50 wt % solution in 2-ethylhexanol).

(6) Dehazing Booster (Compound (A)): Hydrolyzed copolymer of a mixture of C.sub.20 to C.sub.24 alpha-olefins with maleic acid anhydride, Mn: 1500 g/mol, Mw: 3200 g/mol, 40% solution in Solvesso, as described in EP 3099720 B1, Synthetic Example 2.

(7) Comparative Dehazing Booster according to WO 2015/003961: Hydrolyzed polyisobutenyl succinic acid anhydride (based upon polyisobutene with a molecular weight of 1000 g/mol). 50 wt % solution in Solvesso.

(8) As commercially available dehazers Dehazer 1 (TOLAD 2898 by Baker Hughes) and Dehazer 2 (Kerocom 3821 by BASF SE) were optionally used, furthermore a commercially available antifoam additive TP 645 by Momentive.

(9) Fuels:

(10) Fuel 1: German B7 fuel: according to EN590 with 7% (v/v) fatty acid methyl ester FAME Fuel 2: Haltermann Reference Fuel RF 79-07 Fuel 3: B10 Diesel: Haltermann RF 79-07+10% palm oil methyl ester (POME)

(11) For evaluating the capability of separating water from diesel fuels and gasoline fuels containing of the respective mixtures of additives, the corresponding standard test method according to ASTM D 1094 was applied. For this test, a glass cylinder was filled with 20 ml of water buffer and 80 ml of the diesel fuel and then shaken for 2 minutes. After the emulsion generated has been allowed to settle the quantities (volumes) of the water loss and the time for 15 ml and 20 ml of water separation were determined in minutes.

(12) The dehazing formulation was prepared in a solvent (Solvent Naphtha) and the formulation added to the respective fuel in the amounts given in the tables. All amounts are given in ppm by weight (mg additive per kg fuel).

Example 1: Dehazing Examples with Detergent 1 (Components Applied as Solutions as Pointed Out Above

(13) TABLE-US-00001 Base Inv Comp Comp Inv Inv Comp Comp Fuel Entry 1 2 3 4 5 6 7 8 Detergent 1 100 100 100 100 100 Dehazing Booster 20 30 10 100 30 Comparative 16 Dehazing Booster Dehazer 1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Antifoam 4 4 4 4 4 4 4 Solvent 153.5 153.5 153.5 153.5 153.5 153.5 223.5 Total 280 276 260 290 270 260 260 Fuel 1 Time to 15 ml 08:30 09:50 12:00 07:10 10:00 >30:00 >30:00 >30:00 Time to 20 ml 16:00 20:20 32:20 16:00 31:20 >30:00 >30:00 >30:00 Fuel 2 Time to 15 ml 02:50 08:50 >30:00 03:30 00:50 Time to 20 ml 04:30 13:30 >30:00 7:30 >30:00

(14) It can be seen from entries 3, 6, and 7 that Detergent 1 and compound (A) alone yield long times for phase separation, compound (A) alone even leads to longer separation times.

(15) Mixtures of Detergent 1 and compound (A) significantly shorten the times for phase separation, even more than a combination of Detergent 1 with the Comparative Dehazing Booster (polyisobutene succinic acid according to WO 2015/003961), see entries 1 vs 2. Since the Dehazing Booster is used as a 40% solution and Comparative Dehazing Booster as a 50% solution, Entries 1 and 2 are directly comparable and demonstrate the advantage of the Dehazing Booster over Comparative Dehazing Booster (polyisobutene succinic acid according to WO 2015/003961).

Example 2: Dehazing Examples with Detergent 2 (Components Applied as Solutions as Pointed Out Above

(16) TABLE-US-00002 Entry Inv Comp Comp 1 2 3 Detergent 2 100 100 100 Dehazing Booster 20 Comparative 16 Dehazing Booster Dehazer 1 2.5 2.5 2.5 Antifoam 4 4 4 Solvent 153.5 153.5 153.5 Total 280 276 260 Fuel 1 Time to 15 ml 04:00 05:50 04:30 Time to 20 ml 08:20 10:50 10:40 Fuel 2 Time to 15 ml 04:10 05:30 Time to 20 ml 08:00 12:40

(17) It can be seen from entry 2 vs entry 3 that the presence of dehazers does not necessarily shorten the time for phase separation.

(18) Mixtures of Detergent 2 and compound (A) significantly shorten the times for phase separation, even more than a combination of Detergent 2 with the Comparative Dehazing Booster (polyisobutene succinic acid according to WO 2015/003961), see entries 1 vs 2.

Example 3: Dehazing Examples with Detergent 3 (Components Applied as Solutions as Pointed Out Above

(19) TABLE-US-00003 Entry 1 2 Detergent 3 100 100 Dehazing Booster 20 0 Comparative Dehazing Booster Dehazer 1 2.5 2.5 Antifoam 4 4 Solvent 153.5 153.5 Total 280 260 Fuel 1 Time to 15 ml 04:35 06:10 Time to 20 ml 07:50 12:00 Fuel 2 Time to 15 ml 02:43 03:00 Time to 20 ml 04:45 07:20

Example 4: Dehazing Examples with Detergent 4 (Components Applied as Solutions as Pointed Out Above

(20) TABLE-US-00004 Entry Inv Comp 1 2 Detergent 4 100 100 Dehazing Booster 20 0 Comparative Dehazing Booster Dehazer 1 2.5 2.5 Antifoam 4 4 Solvent 153.5 153.5 Total 280 260 Fuel 1 Time to 15 ml 04:20 08:00 Time to 20 ml 06:45 11:10

Example 5: Dehazing Examples with Detergent 5 (Components Applied as Solutions as Pointed Out Above

(21) TABLE-US-00005 Entry Inv Comp 1 2 Detergent 5 100 100 Dehazing Booster 20 0 Comparative Dehazing Booster Dehazer 1 2.5 2.5 Antifoam 4 4 Solvent 153.5 153.5 Total 280 260 Fuel 1 Time to 15 ml 04:20 06:10 Time to 20 ml 08:30 11:20

Example 6: Dehazing Examples with Detergent 1, Compatibility with Cetane Number Improver 2-Ethylhexyl nitrate (2-EHN) (Components Applied as Solutions as Pointed Out Above

(22) TABLE-US-00006 Entry Inv Comp 1 2 Detergent 1 80 100 Dehazing Booster 20 Dehazer 1 2.5 2.5 Antifoam 4 4 2-EHN 500.5 500.5 Total 607 607 Fuel 3 Time to 15 ml 03:00 10:40 Time to 20 ml 06:50 23:00

Example 7: Dehazing Examples with Detergent 2, Compatibility with Cetane Number Improver 2-Ethylhexyl nitrate (2-EHN) (Components Applied as Solutions as Pointed Out Above

(23) TABLE-US-00007 Entry Inv Comp 1 2 Detergent 2 80 100 Dehazing Booster 20 Dehazer 1 2.5 2.5 Antifoam 4 4 2-EHN 500.5 500.5 Total 607 607 Fuel 3 Time to 15 ml 03:40 06:40 Time to 20 ml 08:55 17:30

Example 8: Dehazing Examples with Detergent 2 as Co Detergent on Gasoline (Haltermann Reference Gasoline RF 12-09) (Components Applied as Solutions as Pointed Out Above

(24) TABLE-US-00008 Entry 1 2 3 4 Polyisobutylenamine .sup.1) 300 300 300 300 Detergent 2 50 50 50 50 Dehazing Booster (A) 5 10 20 Dehazer (Tolad? 286) 1 1 1 1 Treat rate 351 356 361 371 Time to 20 ml/min:sec >30:00 05:05 04:30 04:00 .sup.1) Polyisobutene amine, molecular weight approx. 1000 g/mol, commercially available as KEROCOM? PIBA 03 from BASF