Technique for emulsifying highly saturated hydroisomerized...

Details Technique for emulsifying highly saturated hydroisomerized... Technique for emulsifying highly saturated hydroisomerized...

2003-01-29

2004-01-06

Metzmaier, Daniel S. (Department: 1712)

Drug, bio-affecting and body treating compositions

Preparations characterized by special physical form

Biocides; animal or insect repellents or attractants

C514S546000, C514S668000, C514S762000, C514S786000, C514S941000, C504S363000, C516S073000

Reexamination Certificate

active

06673360

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates emulsifiers for highly saturated, hydrocracked and/or hydroisomerized fluids. More particularly, the present invention relates to compositions containing emulsified, highly saturated hydrocracked, and/or hydroisomerized oils particular useful when applied to crops.
BACKGROUND OF THE INVENTION
Petroleum oils have long been sprayed on agricultural crops as a means of pest control. Properly processed petroleum oils are generally less phytotoxic than many synthetic pesticides, with the resulting oil cover affecting the target mites, flies, bugs, scales, aphids and the like but having little deleterious effect on the target tree, plant or crop.
Conventional spray oils are manufactured from crude oil and petroleum fractions using conventional solvent refining techniques or using hydro-treated base oils. Typically, the higher the paraffinic content (i.e., the proportion of saturated straight or branched hydrocarbon chains) in the oil, the more effective the oil is against pests and the less phytotoxic it is to plants. Oils containing high normal paraffinic contents can lead to an elevated pour temperature, which can cause problems when the oil is applied as a spray oil in colder climates.
Finished spray oils typically include 1 to 3 weight percent (wt %) of an emulsifier to allow the oil to remain emulsified in a water carrier during spraying. Conventional emulsifiers for this purpose include alkyl phenol ethoxylates.
Although such alkyl phenol ethoxylates perform satisfactorily under most conditions, their emulsification capability decreases substantially under hard water conditions. When conventional spray oils emulsified with alkyl phenol ethoxylates and hard water, separation can occur during or shortly after spraying, in which case the non-emulsified oil or other composition constituents separate out on the plant leaf, causing phytotoxicity which may be evidenced by leaf browning.
Severely hydrocracked and/or severely hydrocracked hydroisomerized oils, having a saturate content of ≧99% and/or exhibiting a high degree of branching of the paraffin molecules, are now available. Exemplary severely hydrocracked and hydroisomerized oils include the Spray Oil 10, Spray Oil 13, Spray Oil 15 and Spray Oil 22 hydrocracked and hyroisomerized oils available from Petro-Canada Lubricants of Mississauga, Ontario L5K 1A8, Canada, characteristics of which are summarized below:
Spray
Spray
Spray Oil
Oil
Spray Oil
Oil
Quality
Test Method
1
13
15
22
Appearance
Visual
clear
clear
clear
clear
bright
bright
bright
bright
Color
ASTM D1500
<0.5
<0.5
<0.5
<0.5
Density @
ASTM D1298
0.83
0.84
0.84
0.84
15° C.
kg/l
kg/l
kg/l
kg/l
Viscosity @
ASTM D445 
9.5 cSt
20.0 cSt
20.0 cSt
20.0 cSt
40° C.
Analine
ASTM D611 
103
113
113
113
Point
Nitrogen
ASTM D4629
<1 ppm
<1 ppm
<1 ppm
<1 ppm
Sulphur
ASTM D5453
<1 ppm
<1 ppm
<1 ppm
<1 ppm
Saturates
PCM 528
>99.9
>99.9
>99.9
>99.9
wt %
wt %
wt %
wt %
Aromatics
PCM 528
<0.1 wt %
0.1
0.1 wt %
0.1
wt %
wt %
Polynuclear
HRMS
<1 ppm
<1 ppm
<1 ppm
<1 ppm
aromatics
The hydrotreating or hydrocracking step can be carried out in the presence of a catalyst based group VIB and VIII metals, or alternatively, in the presence of a catalyst based on a crystalline silicoaluminophosphate molecular sieve. Typical hydrocracking or hydrotreating conditions include temperatures of from 200 to 450° C., hydrogen pressures of from 400 to 5,000 psig, a hydrogen circulation rate of 400 to 15,000 SCF/B and space velocities of from 0.1 to 20 hr-1. Hydroisomerization is typically carried out after the hydrocracking or hydrotreating step using a crystalline silico-aluminophosphate molecular sieve catalyst, which optionally contains group VIII and IIA metals. The process is carried out at a temperature of from 250 to 450° C., at hydrogen pressures of from 100 to 5000 psig, a hydrogen circulation rate of 400 to 15,000 SCF/B and liquid hourly space velocity of 0.1 to 20 hr-1. The hydroisomerized fluid is hydrofinished at temperatures of from 190 to 340° C. and pressures of from 400 to 500 psig, a hydrogen circulation rate of 400 to 15,000 SCF/B, in the presence of a solid metal hydrogenation catalyst. The initial hydrotreating or hydrocracking step can be carried out in the presence of a catalyst based group VIB and VIII metals, or alternatively, in the presence of a catalyst based on a crystalline silicoaluminophosphate molecular sieve. Typical hydrocracking or hydrotreating conditions include temperatures of from 200 to 450° C., hydrogen pressures of from 400 to 5,000 psig, a hydrogen circulation rate of 400 to 15,000 SCF/B and space velocities of from 0.1 to 20 hr-1. Typically, the finished product has a natural pour point of from −30 to −60° C., and below, with a preferred pour point of below −50° C.
While the above techniques are used to produce severely hydrocracked and hydroisomerized fluids, issues of adequate emulsification performance under hard water conditions present with such fluids can also be present with fluids which are not hydroisomerized but are hydrocracked or obtained through solvent extraction and contain 80-95 wt % or more saturates. As used herein the phrase hydrocracked and/or hydroisomerized fluids includes organic fluids which are either hydrocracked or hydroisomerized or both and contain a saturate content of >80%. Examples of such fluids available from suppliers other than Petro-Canada are described below:
Chevron
SunSpray
Quality
Test Method
Exxon 100N
100R
11N
Appearance
Visual
clear/bright
clear/
clear/
bright
bright
Color
ASTM
<0.5
<0.5
<0.5
D1500
Density @
ASTM
0.8639
0.8551
0.857
15° C.
D1298
Viscosity @
ASTM
20.24
20.52
19.28
40° C.
D445 
Analine Point
ASTM
97.6
106.4
101.9
D611 
Saturates
PCM 528
81.2
95.6
93.0
Aromatics
PCM 528
18.8
4.4
7.0
Polynuclear
HRMS
5.8
1.2
1.7
aromatics
Unfortunately, hydrocracked and/or hydroisomerized fluids are not readily usable as spray oils because they are often less soluble then conventional oils. As a result of this poorer solubility, the otherwise conventional alkyl phenol emulsifiers tend to drop out of solution upon standing. Conventionally used emulsifiers do not seem to perform adequately and do not have the required storage stability when added to hydrocracking and/or hydroisomerized oils.
The emulsification capability of a potential emulsifier may be evaluated by considering its hydrophile/lipophile balance (hereinafter HLB value). The HLB value, which is an approximate measure of polarity, usually ranges from 2-18. The higher the number, the more polar the subject molecule—the lower the number, the less polar the subject molecule. The more polar molecules are generally more soluble in water and the less polar molecules generally more soluble in oil. However, in evaluating potential emulsifiers for use with hydroisomerized fluids, the HLB values have proven to have poor predictive value, with no single emulsifier performing satisfactorily.
Below is a list of commercially available emulsifiers, which were tested for emulsification ability with hydrocracking and hydroisomerized fluids, including emulsifier class, source, product name, HLB value, average number of ethoxylate or alcohol groups per molecule, and carbon chain numbers, if known.
emulsifier
# EO/
class
source
product name
HLB
OH
C Chain
ethoxylated
De-
Delonic LF-EP-18
6.0
alcohol
forest
1
Delonic LF-EP-20
6.2
Delonic LF-EP-25
7.0
Delonic LF-EP-30
8.0
ethoxylated
Shell
2
Neodol 23-3
7.9
  2.9
C12-C13
alcohol
Neodol-23-1
3.7
1
C12-C13
Neodol 25-3
7.5
  
2.8
C12-C13;
C14-C15
Neodol 1-3
8.7
3
C11
sorbitan
ICI
3
SPAN 80
4.3
monooleate
ethoxylated
Synperonic A4
9.1
4
C13-C15
alcohol
Synperonic A3
7.9
3
C13-C15
polyoxy-
Brij 30
9.7
4
C16-C18
ethylene
Brij 93
4.9
2
lauryl ether
emulsifier
# EO/
class
source
product name
HLB
OH
C Chain
ethoxylated
De-
Delonic LF-EP-18
6.0
alcohol
forest
1
Delonic LF-EP-20
6.2
Delonic LF-EP-25
7.0
Delonic LF-EP-30

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