U.S. patent application number 11/617005 was filed with the patent office on 2007-07-05 for detergent comprising the reaction product an amino alcohol, a high molecular weight hydroxy aromatic compound, and an aldehydye.
This patent application is currently assigned to SAMSUNG ELECTRONICS CO., LTD.. Invention is credited to William J. Colucci, Peter W. Hou, Dennis J. Malfer.
Application Number | 20070151144 11/617005 |
Document ID | / |
Family ID | 39365485 |
Filed Date | 2007-07-05 |
United States Patent
Application |
20070151144 |
Kind Code |
A1 |
Hou; Peter W. ; et
al. |
July 5, 2007 |
DETERGENT COMPRISING THE REACTION PRODUCT AN AMINO ALCOHOL, A HIGH
MOLECULAR WEIGHT HYDROXY AROMATIC COMPOUND, AND AN ALDEHYDYE
Abstract
There is disclosed a Mannich reaction product and a reaction to
create a Mannich reaction product prepared from an amino alcohol, a
high molecular, weight hydroxy aromatic compound, and an aldehyde.
Compositions comprising a hydrocarbon fuel and the reaction product
are also disclosed.
Inventors: |
Hou; Peter W.;
(Chesterfield, VA) ; Colucci; William J.; (Glen
Allen, VA) ; Malfer; Dennis J.; (Glen Allen,
VA) |
Correspondence
Address: |
Alexander D. Raring;John H. Thomas, P.C.
536 Granite Avenue
Richmond
VA
23226
US
|
Assignee: |
SAMSUNG ELECTRONICS CO.,
LTD.
Suwon-si
KR
|
Family ID: |
39365485 |
Appl. No.: |
11/617005 |
Filed: |
December 28, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10840304 |
May 6, 2004 |
7173676 |
|
|
11617005 |
Dec 28, 2006 |
|
|
|
Current U.S.
Class: |
44/412 |
Current CPC
Class: |
C08G 14/06 20130101;
C10L 1/238 20130101; C08F 8/32 20130101; C10L 10/18 20130101; C08F
8/32 20130101; C08F 110/10 20130101; C10L 1/2387 20130101; C10L
10/04 20130101; C10L 1/221 20130101 |
Class at
Publication: |
044/412 |
International
Class: |
C10L 1/22 20060101
C10L001/22 |
Foreign Application Data
Date |
Code |
Application Number |
May 6, 2003 |
KR |
2003-28650 |
Claims
1. A fuel detergent comprising the reaction product of reacting at
least the components (a) a high molecular weight hydroxyaromatic
compound, (b) an aldehyde and (c) an amino hydroxy compound.
2. The fuel detergent of claim 1, wherein the components are
present in the ratio of 1:1:1, respectively.
3. The fuel detergent of claim 1, wherein the hydroxy aromatic
compound is selected from the group consisting of phenols and
cresols.
4. The fuel detergent of claim 1, wherein the aldehyde is selected
from the group consisting of formaldehyde, acetaldehyde,
propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde,
heptaldehyde, and stearaldehyde, benzaldehyde, salicylalidehyde,
furfural, thiophene aldehyde, and formaldehyde-producing reagents,
where the formaldehyde-producing regent is selected from the group
consisting of paraformaldehyde and formalin.
5. The fuel detergent of claim 1, wherein the amino hydroxy
compound is selected from the group consisting of a compound
containing both (i) at least one primary or secondary amine and
(ii) at least one hydroxyl groups.
6. The fuel detergent of claim 1, wherein the high molecular weight
hydroxy aromatic compound has a molecular weight greater than
500.
7. The fuel detergent of claim 6, wherein the high molecular weight
hydroxy aromatic compound is a PIB-cresol, the PIB-cresol having a
molecular weight of about 700 to about 1100.
8. A fuel comprising the reaction product of claim 1.
9. The fuel of claim 8, wherein the use of the additized fuel
reduces intake valve deposits relative to use of a fuel without the
reaction product.
10. A fuel additive comprising the reaction product of claim 1.
11. A reaction process comprising adding an alklate to a flask;
providing an aromatic solvent to the flask; stirring contents of
flask under a N.sub.2 blanket, the N.sub.2 set to about 0.1 to 0.2
SCFH; adding an amine; adding an aldehyde; wherein the alkylate,
amine and aldehyde are provided in a ratio or about 1:1:1,
respectively and wherein the alkylate is a high molecular weight
ortho alkyl substituted hydroxyl aromatic.
12. The process of claim 11, further comprising the step of
distilling the contents of the flask under a N.sub.2 blanket, the
N.sub.2 blanket set to about 0.5 SCFH.
13. The process of claim 12, further comprising the step of
providing additional solvent following the step of distillation,
the step of adding the additional solvent bringing the resulting
composition to about 25% solvent.
14. The process of claim 11, wherein the amine is an amino alcohol,
the amino alcohol selected from the group comprising
2-arnino-1,3-propanediol, 3-amino-1,2-propanediol, ethanolamine and
diethanolamine.
15. The process of claim 11 herein the aldehyde is selected from
the group consisting of formaldehyde, acetaldehyde,
propionaldehyde, buyraldehyde, valeraldehyde, caproaldehyde,
heptaldehyde, and stearaldehyde, benzaldehyde, salicylaldehyde,
furfural, thiophene aldehyde, and formaldehyde-producing reagents,
where the formaldehyde-producing regent is selected from the group
consisting of paraformaldehyde and formalin
Description
FIELD OF THE DISCLOSURE
[0001] The present disclosure relates to a novel reaction to create
a Mannich reaction product and the Mannich product prepared from
the reaction of an amino alcohol, a high molecular weight hydroxy
aromatic compound, and an aldehyde. Also provided are a fuel
additive and a fuel composition using the Mannich base detergent,
and benefits resulting from the use of the Mannich base detergent
in the same.
BACKGROUND OF THE DISCLOSURE
[0002] The use of Mannich compounds is known Mannich reaction
products have been taught for use as detergents in fuels,
Non-volatile constituents of fuel, such as additives, form deposits
on engine components. Conventional oil/fuel-soluble Mannich
condensation products help to reduce deposits.
[0003] Known Mannich reaction products are made from the
three-component reaction of an amine, an aldehyde and a hydroxy
aromatic compound. It has been disclosed to create a Mannich
condensation product from alkylphenols, aliehydes, and amines.
Mannich condensation products can also be formed by combining a
polyisobutyl-substituted hydroxyaromatic compound, an aldehyde, an
amino acid or ester thereof, and an alkali metal base.
[0004] A lubricity additive, as taught by U.S. Pat. No. 6,176,886,
for use in low sulfur content, middle-distillate fuels, is known to
be a fuel-soluble reaction product obtained by the reaction of a
low molecular weight alkyl-substituted hydroxyaromatic compound, an
aldehyde, and an amino-alcohol. U.S. Pat. No 6,176,886 is hereby
incorporated herein by reference in its entirety. However, a low
molecular weight Mannich product is thought to be a poor detergent.
Therefore, the '886 reference itself suggests combining the
reaction product taught in that reference (a lubricity additive)
with a Mannich condensation product comprising the reaction product
of a high molecular weight alkyl-substituted hydroxyaromatic
compound an aldehyde and a polyamine (a detergent additive). It is
believed that the low molecular weight carbon chains decompose on
intake valves or other engine components. Deposits or material that
were attached to the Mannich product are left behind as a deposit
in fuel injectors or on intake valves. While numerous treatments
for fuels are known, the prior art does not disclose reaction
product of the present invention. There is a need or desire to
create new processes to prepare Mannich products and/or to improve
the performance of such a product as a detergent fuel additive or
additized fuel formulation.
SUMMARY OP THE DISCLOSURE
[0005] In accordance with the disclosure, there is disclosed a
Mannich product formed by reacting or combining the compounds
having the formulas (I), (II), and (III) where the formulas are
defined as follows: ##STR1## [0006] wherein R1=H or C1-C4, [0007]
R2=H or C1-C4 such that at least one of R1 or R2 is H, [0008]
R3=C35-C100 [0009] R4=H [0010] R5=C1-C6, or another amino group, or
a hydroxyl group [0011] R6=C1-C6 or another amino group [0012] R7=H
or another amino group or an alkyl C1-C6 hydroxyl group. [0013]
R8=branched or straight chain, saturated or unsaturated C1-C20
[0014] Further, there is also disclosed an additive package
including the reaction product formed by reacting the compounds of
formulas (I), (II), and (III). The additive package acts as a
detergent in a fuel. Therefore, use of the additive package with a
fuel reduces intake valve deposits, increases or better maintains
injector cleanliness, and the like relative to a fuel without the
additive
[0015] Further, there is disclosed a fuel composition comprising a
major amount of fuel and a minor amount of a Mannich additive or
reaction product prepared by the reaction of compounds having
formulas (I), (II), and (III). The Mannich additive may be present
in the fuel in an amount within the range of from about 10 ppm-1000
ppm w/w treat rate. In one example, a 30 ppm-500 ppm w/w treat rate
for the additive is preferred.
[0016] Further, there are disclosed unexpected performance benefits
of using a fuel additized with the reaction product formed by
reacting the compounds of formulas (I), (II), and (III). This
Mannich additive unexpectedly decreases intake valve deposits and
increases or better maintains fuel injector cleanliness and
performance relative to a fuel that does not contain the reaction
product. A relatively high molecular weight chain was found to
increase the reaction product's detergency characteristics.
[0017] Additional objects and advantages of the disclosure will be
set forth in part in the description which follows, and/or can be
learned by practice of the disclosure. The objects and advantages
of the disclosure will be realized and attained by means of the
elements and combinations particularly pointed out in the appended
claims.
[0018] It is to be understood that both the foregoing general
description and the following detailed description are exemplary
and explanatory only and are not restrictive of the disclosure, as
claimed.
DESCRIPTION OF THE EMBODIMENTS
[0019] The Mannich reaction product taught herein is operable with
a fuel or fuel additive package to increase the performance of a
combustion engine and/or associated components (intake valves, fuel
injectors, and the like). The Mannich reaction product is obtained
by the reaction of an amino alcohol, a high molecular, weight
hydroxyaromatic compound, and an aldehyde. As opposed to (or
alternatively in addition to) the COOH groups typically found on
the amine compound, the present invention contains an OH group on
the amine.
[0020] The reaction product is intended for use as a detergent that
operates to decrease intake valve deposits (IVDs) and to increase
fuel injector cleanliness and performance. The high molecular
weight hydroxyaromatic compound provides detergency characteristics
to the reaction product. The long chain/high molecular weight of
the hydroxcyaromatic compound in the reaction product helps the
reaction product resist decomposition on intake valves. Therefore,
any material attached to the polar end of the reaction product is
"washed off" the intake valve as the reaction product moves through
the valve. The increased detergency characteristics also provide
improved injector cleanliness.
[0021] More specifically, the Mannich product is formed by reacting
or combining compounds of the formulas (I), (II), and (III) where
the formulas are defined as follows: ##STR2## [0022] wherein R1=H
or C1-C4, [0023] R2=H or C1-C4, such that at least one of R1 or R2
is H, [0024] R3=C35-C100 [0025] R4=H [0026] R5=C1-C6, or another
amino group, or a hydroxyl group [0027] R6=C1-C6 or another amino
group [0028] R7=H or another amino group or an alkyl C1-C6 hydroxyl
group. [0029] R8=branched or straight chain, saturated or
unsaturated C1-C20.
[0030] The hydroxy aromatic compound for use with the present
invention has a molecular weight of at least about 500. This
relatively high molecular weight provides detergency
characteristics to the resulting reaction product, as discussed
herein. In one example, the molecular weight is between about 550
and about 1500. For example, in yet another embodiment, the hydroxy
aromatic compound might be a PIB-cresol with a molecular weight
ranging from about 700 to about 1100. The detergency
characteristics include, but are not limited to, the reduction of
intake valve deposits and improved injector cleanliness relative to
a fuel that does not contain the reaction product.
[0031] The reaction is conducted, in one preferred embodiment, by
first adding an alkylate to a flask. An aromatic solvent, such as
Aromatic 100, is added to the container holding the components.
Other suitable solvents are available (eg., toluene). Approximately
75% of the total calculated aromatic solvent is added to the
components at this point. The components are stirred under a
N.sub.2 blanket. N.sub.2 is set to approximately 0.1 to 0.2
SCFH.
[0032] When homogenous, the specified amine is added. Temperature
will normally be in the 40 to 45 degrees Celsius range. The
aldehyde is then added and the temperature rises to bout 45 to 50
degrees Celsius. The alkylate, the amine, and an aldehyde can be
combined at different quantities that are pre-determined based upon
requested mole rations. In one example, the ratio is 1:1:1 of
alkylate:amine:aldehyde. The alkylate, in one example, is an ortho
alkyl substituted hydroxyl aromatic.
[0033] Once combined, the temperature set point is increased to
about 80 degrees Celsius where it is held for about 30 to 60
minutes. At that point, the temperature is set to 145 degrees
Celsius in preparation of the start of distillation, which
generally takes place about 30 minutes later. Distillation occurs
at 95-105 degrees Celsius, and, for distillation, the N.sub.2 is
set to approximately 0.5 SCFH.
[0034] The temperature is maintained at 145 degrees Celsius for
another 2 to 2.5 hours. After distillation, the total weight of the
product in the container determines the amount of additional
solvent needed to bring the final package composition to 25%
solvent.
[0035] The alkylate can comprise other suitable high molecular
weight components such as, and without limitation, a PIB-cresol,
PIB-phenol, or the like. There are also numerous suitable
amino-alcohols. The amino-alcohol may be, for example,
2-arnino-1,3-propanediol, 3-amino-1,2-propanediol, ethanolamine and
diethanolamine.
[0036] The aldehyde is, in the example discussed above,
formaldehyde. Other representative aldehydes for use in the
preparation of the high molecular weight Mannich product include
other aliphatic aldehydes such as acetaldehyde, propionaldehyde,
butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, and
stearaldehyde. Aromatic aldehydes are suitable as well, including,
for example, benzaldehyde and salicylaldehyde. Illustrative
heteroqyclic aldehydes for use herein are furfural and thiophene
aldehyde, and the like. Formaldehyde-producing reagents such as
paraformaldehyde or aqueous formaldehyde solutions such as formalin
could be used.
[0037] When formulating the additized fuel or fuel composition, the
Mannich additive, with or without other additives, is employed in
an amount effective to decrease IVDs or to increase or better
maintain fuel injector cleanliness relative to a fuel that does not
contain the additive. Generally speaking, an additized fuel would
include the Mannich additive in an amount within the range of from
about 10 ppm-1000 ppm w/w. In one example, a 30 ppm-500 ppm w/w
treat rate for the additive may be used.
[0038] The fuel composition with the reaction product of the
present invention may contain or be joined with supplemental
additives, such as lubricity additives, dispersants, cetane
improves, other detergents, antioxidants, carrier fluids, and the
like. The reaction product of the present invention should not
adversely impact upon the activity of these other additives.
Further, a fuel or additive package containing the reaction product
should not detrimentally impact the combustion properties of a
fuel.
[0039] As used herein, the term "amino alcohol" or "amino hydroxy
compound", unless expressly stated otherwise, means a compound
containing both (i) at least one primary or secondary amine and
(ii) at least one hydroxyl group. It is therefore contemplated and
included herein that one, two or more amine groups can be present
on the structure (II) in addition to the one or more hydroxyl
groups. The structure (II) can be an aminated glycol or animated
polyol.
[0040] Prepared samples have been analyzed and submitted to engine
testing:
1. IVD Bench Test.
[0041] This test is to qualify additive effectiveness on reducing
intake valve deposit. The additive is added to a base fuel
(European reference fuel) at a specified dosage rate. The test is
to simulate the IVD deposition (IVD Simulator, Model L-2. Chinese
Patent No. ZL03261710.0). 300 ml of additized fuel is used for the
test. The fuel and air flow are metered through a flow meter to an
injector. The mixture of air and fuel is spraying against a heated
metal plate at around 174.degree. C. The metal plate is weighted
before and after the test. Each test lasts about 70 minutes.
TABLE-US-00001 TABLE 1 Dosage Base Additive rate Deposit Test #
Plate # fuel Fuel code Additive code (PPMV) (mg) 236 20 Europe
R06005192 none none none 15.0 Ref 252 16 Europe R06005192
Methylaminoethanol Mannich/A-100 #281879-B 300 1.1 Ref 253 11
Europe R06005192 Methylaminoethanol Mannich/A-100 #281879-B 200 2.3
Ref 255 29 Europe R06005192 Methylaminoethanol Mannich/AC-
#281885-A 300 0.2 Ref 2400 261 18 Europe R06005192
Methylaminoethanol Mannich/AC- GAR115L01 200 3.7 Ref 2400/A-100
[0042] As demonstrated in Table 1 above, a Mannich detergent or
dispersant in accordance with the teachings herein showed
substantial IVD reduction as compared with the unadditized
fuel.
2. PFI Rig Test
[0043] This test is to determine the effectiveness of additives
keeping fuel injector clean. It follows a modified standard test
procedure ASTM D-6421. Instead of Chrysler injectors required by
the method, New Honda injectors are used in this case.
TABLE-US-00002 TABLE 2 Test Additive Treat # Fuel Code Additive
Code rate 1 2 3 4 Avg. 176 R05005977 Base fuel none none 9.8 16.2
5.2 47.5 19.7 191 R06005977 2-Methylaminoethanol Mannich in 50%
A-100 #281879-B 80 19.3 5.7 1.9 6.7 8.4 ptb 195 R06005977
Methylaminoethanol Mannich/AC-2400/A-100/ GAR115L01 80 15.4 4.4 22
8.4 12.6 #230162-1 ptb 201 R06005977 Methylaminoethanol
Mannich/AC-2400/A-100/ GAR115L01 200 10.9 9.9 16.7 9.1 11.7
#230162-1 ppmv
[0044] As is evident from the results shown in Table 2, a Mannich
reaction products in accordance with the present invention are
effective fuel injector cleaners.
3. Ford 2.3 L Engine Test
[0045] This is a standard test (ASTM D-6201) to determine fuel
additive on IVD deposit. TABLE-US-00003 TABLE 3 Test # Fuel Code
Additive Code Dosage IVD, mg DA115-241 00002192L01 none none none
850.6 DA115-260 00002192L01 2-methylaminoethanol Mannich/AC-
219931-2 93.7 196.2 2400 ptb DA115-261 00002192L01 H-6410/AC-2400
211987 93.7 145 ptb DA115-228 99000206L01 none none none 514.1
DA115-238 99000206L01 2-methylaminoethanol Mannich/AC- 211956-2
93.7 39.7 2400 ptb DA115-240 99000206L01 H-6410/AC-2400 211940 93.7
56.6 ptb
[0046] As demonstrated in Table 3, a Mannich reaction product in
accordance with the teaching herein showed substantial IVD
reduction as compared with the unadditized fuel.
4. Intrepid Vehicle Test
[0047] Vehicle test on additive IVD reduction effectiveness.
Mileage accumulation is generated by a four-cycle test performed at
an average speed of 45.7 MPH with a cycle length of 76 miles) using
a standard 1997 Dodge Intrepid, 3.3 L, V-6. TABLE-US-00004 TABLE 4
Vehicle IVD, Test # ID Fuel Code Additive Code Dosage mg 69 7D12
R04004651 none none none 648.0 82 7D12 R04006588
2-methylaminoethanol GAR115L01 28.8 ptb solids 5.8 Mannich/AC-2400
78 7D12 R04006588 HR-6410/AC-2400 GAR115J01 28.8 ptb solids 1.8
[0048] Table 4 demonstrates that a Mannich product as taught in one
embodiment of the present invention provides excellent IVD
performance.
[0049] In examining the tables, fuel codes R04004651 and R04006588
are identical fuels taken from different fuel batches. AC-2400 is a
commercial product "ACTACLEAR".TM. 2400 from Bayers. A-100 is
aromatic 100 solvent. H-6410 is a commercial product from Afton
Chemical
[0050] The ratio ranges of (I), (II) and (III) might be, in one
embodiment, 1:2.5:2.5. In another example, the compounds of (I),
(II), and (III) are supplied in the ratios of 1:2:2. In yet another
example, the ratio of the three components is 1:1:1. Therefore,
examples of preferred ratios range from 1:1-2.5:1-2.5 for the
components (I), (II), and (III).
[0051] This invention is susceptible to considerable variation in
its practice. Therefore the foregoing description is not intended
to limit, and should not be construed as limiting, the invention to
the particular exemplifications presented hereinabove. Rather, what
is intended to be covered is as set forth in the ensuing claims and
the equivalents thereof permitted as a matter of law.
* * * * *