AU619957B2

AU619957B2 - Middle distillate fuel having improved storage stability

Info

Publication number: AU619957B2
Application number: AU50603/90A
Authority: AU
Inventors: John Gray Bostick; Larry John Cunningham; John Vincent Hanlon
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 1989-03-02
Filing date: 1990-03-01
Publication date: 1992-02-06
Anticipated expiration: 2010-03-01
Also published as: EP0385633A1; CA2010183A1; AU5060390A; JPH02292392A; DE69001269T2; EP0408087A1; DE69001269D1; EP0385633B1

Description

Ili___ciii__i 61995 7 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1932 COMPLETE SPECIFICATION NAME ADDRESS OF APPLICANT: Ethyl Petroleum Additives, Inc.

South Fourth Street St.Louis Missouri 63102-1886 United States of America NAME(S) OF INVENTOR(S): John Gray BOSTICK ,Larry John CUNNINGHAM V John Vincent HANLON SADDRESS FOR SERVICE: DAVIES COLLISON Patent Attorneys I 1 Little Collins Street, Melbourne, 3000.

r i 0 S I ;COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: Middle Distillate Fuel Having Improved Storage Stability j The following statement is a full description of this invention, including the best method of performing it known to me/us:la= This invention relates generally to improving the stability of middle distillate fuels and more particularly to stabilized middle distillate fuel compositions which contain a combination of N,N-dimethylcyclohexyl amine and a Mannich Base.

'00 Middle distillate fuels such as diesel oil, fuel o oe So.oo° oil, jet fuel and kerosene when stored for long periods of i00c, S°o. time are subject to the formation of color and solid depos- 0*00 "10 its. The deposits accumulate on filters causing the fil- 0 00 0 ters to become plugged. Various additives and combinations of additives have been employed to reduce color and Ideposit formation. For example: U.S. Patent 2,984,550 0 discloses the use of Mannich bases derived from phenols, formaldehyde and polyamines for stabilization; U.S. Patent 00 S 3,490,882 discloses stabilized petroleum distillate fuel I oils containing N,N-dimethylcyclohexylamine antioxidant and a N,N'-di(ortho-hydroxyarylidene)-1,2-alkylenediamine I metal deactivator such as N,N'-disalicylidene-l,2propylenediamine; U.S. Patent 4,166,726 discloses a fuel additive which is a mixture of a polyalkylene amine and a Mannich Base; and U.S. Patents 4,501,595 and 4,533,361 disclose diesel oil which contains a condensate of tetraethylene pentamine, paraformaldehyde, a hindered phenol

I

r 2 such as 2,6-di-t-butylphenol and polyisobutenyl succinic anhydride.

The effectiveness of any particular type of additive combination can vary with different fuel stocks and combinations which are more effective at the same total additive concentration reduce treatment cost. We have now discovered novel, synergistic additive combinations which include certain Mannich Bases and provide middle distillate fuels having generally improved storage stability i compared to fuels containing the same total concentrations 0000 i 0 of either N,N-dimethylcyclohexylamine antioxidant alone or 0 00 ii N,N-dimethylcyclohexylamine in combination with an N,N'-di- 0000 o 0 (ortho-hydroxyarylidene)-1,2-alkylenediamine metal deacti- 0 0 0 a 00oo 0 I vator.

0046 ~s 0141 0* 0. 6 In accordance with this invention, there is provided a fuel additive concentrate comprising a mixture of N,N-dimethylcyclohexylamine and a Mannich Base which is the reaction product of an aldehyde, an amine and an alkyl phenol selected from hindered phenol having the formula:

OH

R1I R2

R

3 where R 1

R

2

R

3 are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl, provided 3 that at least one of R 1

R

2 and R 3 is hydrogen and at least one of R1 and R2 is t-butyl, t-amyl or isopropyl; and p-alkyl phenol having the formula:

OH

R

4 0 where R4 is C9 to C30 alkyl.

0000 i 0 00 o o o 0 0 The concentrate can also contain a N,N'-di(ortho-hydroxy- 000 0S arylidene)-1,2-alkylenediamine metal deactivator such as O 0 0 00 N,N'-disalicylidene-l,2-propylenediamine. Also provided is a stabilized fuel containing from 1 to 1400 mgs/liter 0000 of N,N-dimethylcyclohexylamine, from 0.5 to 1100 mgs/liter 0oo 0 0 e. of Mannich Base and from 0 to 400 mgs/liter of an N,N'oo o a di(ortho-hydroxyarylidene)-1,2-alkylenediamine.

o° o, S* The N,N-dimethylcyclohexylamine component of the compositions of the invention is a commercially available fuel antioxidant.

The N,N'-di(ortho-hydroxyarylidene)-1,2-alkylenediamine component, in which, typically, the arylidene radical contains 6-7 carbon atoms and the alkylene radical contains 2-3 carbon atoms, is a metal deactivator whose presence in combination with the other components provides a 4 fuel compositions of the invention having the most improved stability. The preferred metal deactivator is N,N'-disalicylidene-1,2-propylenediamine which is commercially available.

The Mannich Base component of the invention is produced by the Mannich condensation reaction of a hindered or p-alkyl phenol, an aldehyde, such as formaldehyde, ethanal, propanal, and butanal (preferably iormaldehyde in its monomeric form or paraformaldehyde) and primary and Ci°e secondary amines.

oo o 0000 oooo The hindered phenols which are useful in preparing 0000 oooo the Mannich Base component of the invention are phenols oooo 0 0 0000 which are characterized by the presence of at least one 0 0 0 0000 and preferably two ortho-t-butyl, t-amyl, and/or isopropyl groups. Specific examples of such hindered phenols include: 2,4-di-t-butylphenol, 2,4-diisopropylphenol, 2,6- 0 0 000oo0 diisopropylphenol, 2-t-butylphenol, and 2-t--amylphenol 9 0 40 with 2,6-di-t-butylphenol being most preferred.

t The p-alkyl phenols which are useful in preparing the Mannich Base component of the invention are those which contain from 9 to 30 carbons which can be arranged in either a straight or a branched chain. Preferred phenols are C 9 to C 12 p-alkylphenols such as, for example, p-nonylphenol and p-dodecylphenol.

The amines which are useful in preparing the Mannich Base component of the invention are primary and P_ -L-F MI 1CI i_ 00 00 0 0 a o0 0000 0 0 0000 0000 0 a 0000 0 00 0 0 1 O 0 5 secondary amines which can be selected from one or more of: A. alkyl monoamines of the formula;

R

HN

where R 5 is selected from H and C 1 to C alkyl, and R6 is selected from C 1 to C 14 alkyl and the group -(CH 2 )n-OR 7 where n 1 to 10 and R7 is

C

1 to C 20 alkyl, B. alkyl diamines of the formula;

A

HN-R -N

B

where R 5 is selected from H and C 1 to C alkyl, Rg is C 1 to C 6 alkylene and A and B are independently selected from H, C 1 to C 5 alkyl, monohydroxysubstituted C 1 to C 5 alkyl, and the group

(CH

2 )n-OR 7 where n 1 to 10 and R7 is C 1 to

C

20 alkyl, C. ethylene polyamines of the formula;

H

2

N((CH

2 2 NH)-nH where n =2 to 10, and D. cyclic amines of the formula; S 5

(CH

2 )n HN X

(CH

2 )m 00 where n and m are independently integers from 1 to o o0 0 3, X is selected from CH 2 O, S and NR 9 where R 9 is 0 00 H, C 1 to C 10 alkyl, or the group (CH 2 )n-NH 2 0 0 00 where n is 1 to 10. The alkyl groups can have a branched 0 0 00 0 .0 chain.

Specific examples of such amines include 1,3-diaminopropane, 1,2 diaminopropane, dimethylamine, diethyl- S amine, dipropylamine, dibutylamine, N,N-dimethyl-l,3diaminopropane, 1,1-dimethyldodecylamine, mixed C 12 00 I C 14 t-alkyl amines, ethylenediamine; cyclic amines such as piperazine, i tt.^ aminoethylpiperazine, morpholine and thiomorpholine; and 0 0 ethylene polyamines such as diethylene triamine and Striethylene tetraamine.

The Mannich Base can be formed by reacting from 1 to 5 moles of aldehyde, from about 1 to 2 moles of amine and from 1 to 4 moles of phenol at a temperature of from 0°C to 150°C for 0.5 to 10 hours. An inert solvent such 7 as isopropanol can be used which is distilled from the product along with water formed in the reaction.

The Mannich Base product is usually a mixture of materials which may contain unreacted ingredients, especially the phenol. The Mannich Bases can be isolated from the product mixture but the product mixture itself can conveniently be used in forming the compositions of the invention. Examples of Mannich reactions and products are illustrated below: 00 0o 0 0 o o 0000 0o 0006 0 00 000 0 00 000 ctc e 0 0 00 0 i t 0 r 0 0 0ee -8

OH

R4 R5 ~OH

R

HCHO +HN- CH 2 R6 R4IR HCHO NH 2 4(CH 2 3

-NH

2 09 00 0 0 9 0 0 0000 o 0 0000 0 00 000 0000 00000 0 0 0 00 0 000 0 HO CH 2 -NH-f OH 2 3 -NH 2 0000 00 9 00 O H 2

CH

2 N NH

CH

2

//OH

2

OH

2

III

HO 0H /OH 2

OH

2

OH

2

OH

2

R

2

IV

4 9 where R1, R 2

R

4

R

5 and Rg are as defined above.

The additive mixtures of the invention are usually prepared and marketed in the form of concentrates for addition to the fuel by the customer although the individual components could be added directly into the fuel. Suitable proportions of additives in the concentrates of the invention, based on the total weight of concentrate, include from 25 to 95 wt% N,N-dimethylcyclohexylamine, from 0 to 25 wt% N,N'-di(ortho-hydroxyaryli- 0ooz S°oo dene)-1,2-alkylenediamine and, from 5 to 75 wt% Mannich 0 I 0 os Base.

sa4 The concentrates are added to the fuel in effective I o0 amounts to provide improved stability. Suitable amounts of additive concentrate in the fuel are from 1 to 500 pounds per thousand barrels (Ptbs) (3 to 1500 mgs/liter, j tt preferred 2.5 to 100 Ptbs or 8 to 300 mgs/liter). This will provide a stabilized fuel containing from 1 to 1400 mgs/liter (preferred 2 to 250 mgs/liter) N,N-dimethylcyclohexylamine, from 0 to 400 mgs/liter (preferred 0 to 100 c mgs/liter) N,N'-di(ortho-hydroxyarylidene)-1,2-alkylene- Sdiamine metal deactivator and from 1 to 1100 mgs/liter S(preferred 1 to 250 mgs/liter) of Mannich Base. When used, the metal deactivator is present in amounts of to 25 wt% of concentrate or .3 to 400 mgs/liter of fuel.

The concentrates can also contain an inert diluent or

I

i 1 i Pr C o 0 10 a 000 o o o0 0 0000 0000 0 0 0000 0 00 I oO o 0 0 0 000 0 0 t 0000 0 t at C 10 solvent which can be, for example, an aliphatic hydrocarbon such as kerosene or an aromatic hydrocarbon such as xylene.

*The middle distillate fuels whose stability is improved by the invention typically include those boiling within a temperature range of 150'-400"C which may commonly be labeled as kerosene, fuel oil, diesel oil, No.

l-D, or No. 2-D.

The compositions of the invention are further illustrated by, but are not intended to be limited to, the following examples wherein parts are parts by weight unless otherwise indicated.

Example 1 A Mannich Base reaction product of formaldehyde, 1,3-diaminopropane ard 2,6-di-t-butylphenol is prepared by the following process.

Dissolve 103 grams (0.5 mole) of 2,6-di-t-butylphenol in 100 grams of isopropyl alcohol (IPA) in a 500 ml round bottom flask. Add 18.5 grams (0.25 mole) of 1,3-diaminopropane dropwise over 15 minutes while the contents of the flask are stirred. There is an exotherm observed as the amine is added. Cool the contents of the flask to below 30"C and add a 10% excess, (44.6 grams 0.55 mole) of 37% aqueous formaldehyde solution dropwise over 30 minutes while maintaining the temperature below 30*C. Heat the contents of the flask to reflux and continue to reflux for r i i i I s a :i

S

5 0000 o o o o 0 00 0015 0 0000 0 0 0000 0o 0 0 0 0 0 0 0000 o t 11 one hour. Switch from reflux to distillation and distill off IPA/water mixture to 105"C. Apply 28 in. Hg vacuum to remove residual materials. The total product yield is 122.2 or 96% of theory which contains co-mciounds of the Structure III and IV.

Additive blends of the reaction product were prepared and tested in different fuels using both the D 4625 43 0 C (110F) Storage Stability Test, in which the color change (using ASTM D1500) and the total insolubles in the fuel (reported in mg/100 ml) are determined on 400 ml samples stored for 13 weeks in the dark and the F-21-61 149"C (300*F) Accelerated Stability Test in which the color change and insoluble gums are determined on 50 ml samples heated to 149*C for a selected time, which was minutes, allowed to cool in the dark, tested for color (ASTM D1500), and then filtered (using a 4.25 cm Whatman #1 filter paper) and the filtrate discarded. The filter is washed clean of fuel with isooctane and measured for deposits by comparison with a set of reference papers.

The blend compositions and test results in comparison to untreated fuel and blends without the Mannich Base oroduct are reported in Table I below.

TABLEI

Composition in Pounds Per Thousand Barrels #2 Fuel #3 4 5 1 2 3 21 2 Fuel #1 DMCA 0.0 IIDA 20.0 Mannich Base 0.0 Total Additives 0.0 4.75 3.80 0.0 0.25 0.25 0.0 0.00 0.95 0.0 4.75 3.8 0.0 0.25 0.24 TO0 0.0 0.96 0.0 5.0 5.0 5.0 5.0 0.0 5.0 5.0 0.0 10.0 10.0 Test Results 149-C (F-21-61) Fuel #4 1. 2 3 4 0.0 2.38 1.90 4.75 3.80 0.0 0.12 0.12 0.25 0.24 0.0 0.00 0.48 0.00 0.96 0.0 2.5 2.5 5.0 Fuel 44 1 2 3 4 12.5 2 2 2.5 6 4 4 4 4 Fuel #4 1. 2 3. 4 Color 17 Deposit 13 2 3 13.5 2.5 5 4 #2 4 2.1 2 3 Fuel #3 1. 2 3 12.5 2 5 3 43-C (D 4625) Fue l #1 Corprer~nn 2. 1 2 3 4 5 Fuel #2 2. 2 Fuel #3 2. 3 Colior 15 4 Deposit 6.8 3.2 13.5 13.5 13.5 L3.5 13.5 13.5 7.9 4 4.7 6.7 3 2.1 12.5 12.5 12.5 12.5 2 1.6 1.3 1 L =less then 1 N N-dimethytcy,,Lohexytemine 2 N,N'-disallilidoh&e1 ,2-propyLenediamin-i Fuel #1 is Midwest Refinery Fuel #2 is Mid-Continent #2 Diesjtl (Corning Crude) Fuel #3 is Mid-Continent #2 Diesel (ILL. Basin Crude) Fuel #4 is Midwest #2 Diesel (KS/Tx Crude) 0 0 0 0 o 0 0 0 #4 00 0 0 0 000 0 00 0 000 0 00 000 0 0 00 00 V 0000 0 0 13 13 A significant difference in stability at 149'C is indicated by a color difference of about. 1/2 number and/or a deposit difference of 2 numbers and a significant difference in stability at 43°C is indicated by a color difference of about 1/2 number and a deposit difference of 4 20%. The results in Table I show that the blends of the invention which contain Mannich Base in addition to DMCA or DMCA and MDA gave significantly better overall stability when compared to comparable blends which did not con- 1i ;lT, tain the Mannich Base, for example, blend 3 vs blend 2 and i o blend 5 vs blend 4 of Fuel #1.

i Example 2 0 0 b° A Mannich Base reaction product of formaldehyde, dimethylamine, and 2,6-di-t-butylphenol is prepared by the following process.

Dissolve 103 grams (0.5 mole) of 2,6-di-t-butylphenol in 100 grams of IPA in a 500 ml round bctom flask c and add 72 grams (0.64 mole) of a 40% aqueous dimethylamine solution. Cool the mixture to about 30°C and add 2 09, dropwise with stirring 44.6 grams (0.55 mole) of 37% I formaldehyde while keeping the mixture at a temperature below 40'C. Heat the mixture to reflux and reflux for 4 hours. Remove IPA/water by distillation and apply vacuum to remove residual materials. The product yield is 113 grams or 86% of theory which contains t-butyl4-hydroxybenzylamine.

S 14 14 Additive blends of the above reaction product were prepared and tested in different fuels using the test K procedures described in Example 1. The blend compositions i and test results in comparison to untreated fuel and blends which did not contain the Mannich Base product are reported in Table II below.

0 ft so rt 0 0 Oi s 8 C 8 t ta 6 6 r Ii TABLE I I Composition in Pounds Per Thousand Barrels Fuel #1 Fuel #2 Fuel #3 Fuel #4 Coraoents 1 2 3 4 5 1 2 3 1 2 3 1 2 3 4 DMCA 0.0 5.0 4.0 4.75 3.80 0.0 9.5 7.6 0.0 28.5 22.8 0.0 2.38 1.90 4.75 3.80 MDA 0.0 0.0 0.0 0.25 0.25 0.0 0.5 0.5 0.0 1.5 1.5 0.0 0.12 0.12 0.25 0.24 Mannich Base 0.0 0.0 1.0 0.00 0.95 0.0 0.0 1.9 0.0 0.0 5.7 0.0 0.00 0.48 0.00 0.96 Total Additives 0.0 5.0 5.0 5.0 5.0 0.0 10.0 10.0 0.0 30.0 30.0 0.0 2.5 2.5 5.0 Test Results 149'C (F-21-61) Cormponents 1 2 Color L7 L3.5 Deposit 13 5 Fuel #1 Fuel #2 Fuel #3 Fuel #4 3 4 5 1 2 3 1 2 3 1 2 3 4 3 L3 13 8 3 3 4.5 L4 3.5 L2.5 2 L2.5 2.5 6 4 4 17 10 6 5 3 3 6 4 5 4 3 43°C (D 4625) Fuel #1 2 3 Components 1 Fuel #2 Fuel #3 Fuel #4 4 5 1 2 3 1 2 3 1 2 3 4 Color L5 4 4 4 4 L3.5 L3.5 L3.5 2.5 L2.5 L3 L2.5 Deposit 6.8 3.2 2.8 2.5 2 6.7 4 3.9 7, 2 1.9 1.3 0.9 The fuels were the same as in Example 1 except that Fuel #3 is a fuel containing unhydrotreated residual cracked stock.

I, 4. 1 P P 4* ~t4* Ce e ce CeO 4*4* o C C C C CC CC o~C Ce C 0 4.

C SC. C CC it CC 0 CC c *.n k r

.A

16 The results indicated that the blends containing Mannich Base gave fuels having significantly improved stability except in" the case of Fuel #4 where the results were mixed.

Example 3 A Mannich Base reaction product of formaldehyde,

C

12

-C

14 t-alkyl amine mixture (Primene 81R) and 2,6- I di-t-butyl phenol is prepared by the process described in i Exar.le 2 using 95.5 grams (0.5 mole) of Primene 81R in i 0 o place of the dimethylamine. The product yield is 200 I00 grams or 82% of theory which contains N-[3,5-di-t-butyl-4hydroxybenzyl]-mixed C 1 2

-C

1 4 t-alkyl amines.

Additive blends of the above reaction product were prepared and tested in #2 diesel fuel using the test procedures described in Example 1. The blend compositions I and test results are reported in Table III below.

DMCA 0.0 0.0 4.75 19.0 0.0 MDA 0.0 0.5 0.5 0.50 1.0 1.0 'TABLE III I Composition Pounds Per Thousand Barrels ii C Components 1 2 3 4 5 6 7 aj i, 20 CMCA 0.0 9.5 0.0 4.75 19.0 0.0 MDA 0.0 0.5 0.5 0.50 1.0 1.0 Mannich Base 0.0 0.0 9.5 4.75 0.0 19.0 Total Additives 0.0 10.0 10.0 10.0 20.0 20.0 20.0 -17 Test Results 149°C (F-21-61) SComponents 1 2 3 4 5 6 7 Color L5.5 IA.5 L5 L4.5 L4.5 L5 Deposit 8 6 4 3 4 3 2 43"C (D 4625) Components 1 2 3 4 5 6 7 Color L6.5 L6 6 L6 5.5 L6 Deposit 8.3 3.2 5 2.8 3.3 5 3 The results indicate that blends 4 and 7 according °0 to the invention which contain the Mannich Base in addii to i tion to DMCA and MDA have better stability at the same .n i total additive levels compared to blends 2 and 5 containc• S°ing only DMCA and MDA.

Exan-'le 4

C

i A Mannich Base reaction product of formaldehyde, 1,2-diaminopropane, and 2,6-di-t-butyl phenol is prepared S: by the following process.

Dissolve 103 gm (0.5 mole) of 2,6-di-t-butyl phenol S Get, in 100 grams of IPA in a 500 ml roundbottom flask and add 18.5 grams (0.25) moles of 1,2-diaminopropane. Cool this mixture to about 30°C and add dropwise with stirring 44.6 grams (0.55 mole) of 37% formaldehyde while keeping the temperature of the mixture below 40"C. Heat the mixture to reflux and reflux for 1 hour. Remove IPA/w4ater by II 18 distillation and apply vacuum to remove residual materials.

Additive blends of the above reaction product were prepared and tested in Fuel #1 fuel using the test procedures described in Example 1. The blend compositions and results are reported in Table IV below.

TABLE IV Composition Pounds Per Thousand Barrels 00 04 0 o 0 0 00 0 o0 0000 0 0 0 0000o 0 0 0 0000 0 0 0000 oo0 0 0 0 00 00 00 00 0 0 0 0 0 0 0 Components

EMCA

MDA

Mannich Base Total Additives 2 5.0 0.0 0.0 5.0 3 4.75 0.25 0.00 5.0 3.8 0.25 0.95 Components Color Deposit Components Color Deposit 1 L7 13 1 L5 6.8 Test Results 149C (F-21-61) 2 3 L3.5 L3 5 4 3 L4 1.7 43*C (D 4625) 2 4 3.2 3 4 2.5 The results indicate that blend 4 of the invention containing the Mannich Base has improved stability compound to blend 2 which containing DMCA alone. Blend containing the Mannich Base has improved stability over blend 3 which contained DMCA and MDA alone.

Y_ I_ _F_ 19 Example A Mannich Base reaction product of formaldehyde, N,N-dimethyl-l,3-diaminopropane, and p-dodecylphenol was prepared by the following procedure.

Combine 262.4 grams (1.0 mole) of the alkyl (C 1 2 phenol with 102.2 grams (1.0 mole) of N,N-dimethyl-l,3-diamino-propane and add 89.2 grams (1.1 mole) of 37% formaldehyde with stirring while keeping the temperature below Heat the mixture to 100°C for two hours and then :i e' remove water by distillation (100°C 28 in vacuum). The product yield is 176 grams or 93% of theory which contains N,N-dimethyl-N'-[2 hydroxy-5-dodecylbenzyl]-1,3-diamino- I propane.

Additive blends of the above reaction product were prepared and tested in midcontinent #2 diesel fuel using the test procedures described in Example 1. The blend t r compositions and results are reported on Table V below.

4 C I r TABLE V Composition Pounds Per Thousand Barrels i 20 Components 1 2 3 4 DMCA 0.0 4.75 2.05 9.5 MDA 0.0 0.25 0.25 0.5 Mannich Base 0.0 0.00 2.70 0.0 5.4 Total Additives 0.0 5.0 5.0 10.0 10.0

B

"T

20 cmponents Color Deposit Color Deposit Test Results l49*C (F-21-61) 1 2 8 3 1 13 10 43*C (D 4625) 1 2 2 T-3.5 L.3.5 2 6 42 4 12.5 5 1.2.5 M. 2.4 4 M3.5 3 0* Ct :io eq., eq eq C Q 0 @000 *00e 0 C 00CC o eq eq 0 eq. 0 The results indicate that blends 3 and 5 of the invention have over-all improved stability compared to blends at the same total additive level which did not include the Mannich Base.

0010 e C 6*00 Os ~-C 0 C *1 C qe o~

C

Octet O C

Claims

2. The concentrate of claim 1 wherein the concen- trate also contains from 1 to 25 wt% N,N'-di(ortho-hydroxy- arylidene)-1,2-alkylenediamine metal deactivator.
3. The concentrate of claim 1 or 2 wherein the S 5 aldehyde is formaldehyde, and the amine is selected from one or more of: A. alkyl monoamines of the formula; 9 R o" R 6 t where R 5 is selected from H and C 1 to C alkyl, and Rg is selected from C 1 to C 14 alkyl and the group -(CH 2 )n-OR 7 where n 1 to 10 and R 7 is i 99 r C 1 to C 20 alkyl, B. alkyl diamines of the formula; R tI t A Sj N 8WB where Rg is selected from H and C 1 to C alkyl, R 8 is C 1 to C 6 alkylene and A and B are independently selected from H, C 1 to C 5 alkyl,
23- mono-hydroxysubstituted C 1 to C 5 alkyl, and the group (C 2 nO 7 where n 1. to 10 and Ris C 1 to C 0 alkyl, C. ethylene polyamines of the formula; H 2 N-((CH 2 2 NH~-H where n 2 to 10, and D. cyclic amines of the formula; (CH 2 M 'A H C1toC10alyl orth grupHC)m/NH where n anisr needntyitresfo 1 to :::rei 3,e hno is seece fromre phen0,, and th we e R 9 is c 0 :0 -,C 1 to C 1 0 talkyl, ormte group (Cthyl)nNH 2 l4. The coentrlate of conpudof the reedigulaim 24 zCH 2 CH 2 -N NH I I CH 2 ~CH 2 where Rand R2are independently selected from hydrogen, t-butyl, t-amyl and isopropyl provided that at least one of Rand R 2 is t-butyl, t-amyl, or iso- propyl, or a compound of the formula: II I It 4 t 4411 1 *441 4 11 ~L3 4 11 I *61 I CH 2 CH 2 -N N- CH 2 CH 2 .V CH 4< I LI 15 $1 I where Rand R2are independently selected from hydrogen, t-butyl, t-amyl and isopropyl provided that at least one of Rand.R is t-butyl, t-amyl, or iso- propyl. The concentrate of anyofcas1-whri the phenol is a p-alkylphenoi, and the Mannich Base comprises N, N-dimethyl-N' -[2-hydroxy--5-dodecylbenzyl] 1, 3-diaminopropane. I ~l--P4 -e r- I j B i. 4) 25 I C It I It I II L14 SI I~ It I W* 20 6. The concentrate of claim 2 wherein the metal deactivator is N,N'-disalicylidene-l,2-propylenediamine and the Mannich Base is the reaction product of formal- dehyde, 2,6-di-t-butyl phenol and an amine selected from 1,3-diaminopropane, 1,2-diaminopropane, mixed C12-C14 t-alkyl amines, and dimethylamine. 7. The concentrate of -laim 2 wherein the metal deactivator is N,N'-disalicylidene-1,2-propylenediamine and the Mannich Base is the reaction product of formal- dehyde, p-dodecyl phenol, and N,N.-dimethyl-l,3-diamino- propane. 8. A fuel composition comprising middle distillate fuel containing from 3 to 1500 mgs/liter of the concen- one. trate of any of claims 1-7. 9. A fuel composition comprising a middle distil- late fuel and from 1 to 1400 mgs/liter N,N-dimethylcyclo- hexylamine, from 0 to 400 mgs/liter N,N-di(ortho-hydroxy- arylidene)-1,2-alkylenediamine and from 1 to 1100 mgs/ liter of a Mannich Base which is the reaction product of an aldehyde, an amine and an alkyl phenol selected from hindered phenol having the formula: 26 OH R R2 R 3 where RI, F2, R 3 are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl, provided that at least one of R 1 R 2 and R3 is hydrogen and at least one of R1 and R 2 is t-butyl, t-amyl or e isopropyl; and p-alkyl phenol having the formula: OH °°rr R4 o t its, The fuel composition of claim 9 wherein the aldehyde is formaldehyde and the amine is selected from one or more of: 4 1 It A. alkyl monoamines of the formula; HN 4, 4. -27 where R 5 is selected from H and C 1 to C alkyl and R 6 is selected from C 1 to C 4 alkyl and thegrup (H2)n-_Rwhere n 1 ito 10 and Ris C 1 to C 20 alkyl, B. alkyl diamines of the formula; R I A HN-R 8 -N B where is selected from H and C 1 to C alkyl R 8 is C 1 to C 6 alkylene. and A and B are in- dependently selected from H, C 1 tC 5 akl oo hydroxysubstituted C 1 to C 5 alkyl, and the group (CH 2 )n-OR 7 where n =1 to 10 and R7is C 1 to 415 C 20 alkyl, C. ethylene polyamines of the formula; H N* (CH) 2 NH-)nH S sf tt where n =2to 10, and D. cyclic amines of the formula; /(CH 2 n HN X (CH 2 )m p 4. 4 aa 4 0. b 28 where n and m are independently intergers from 1 to 3, X is selected f rom CH 2 0, S and NR9 whcre R 9 is H, C1 to 010 alkyl, or the group (CH 2 )n-IIH 2 where n is 1 to 4*4 a 4* a a a. a. a,. a a a a 29 ,11. Fuel additive concentrate or compositions containing them, substantially as hereinbefore described with reference to the Examples. 1. The e foLus op, ctit Li and c01ou 1U i J disclosed herein or referred to or indi ina-t the specification and/or claim is application, individually e ectively, and any and all combinations of.-a- two or more of said steps or features. OO te 0 0 (9 0 0 Ethyl Petroleum Additives, Inc. o0 SDATED this FIRST day of MARCH 1990 o Pat Ethyl Petroleum Additives, Inc. 0 04 0 0 4 000 0 0000 0 3 o000o a0 0 00 0 0 00 0 0 9 000 90 0 0