U.S. patent application number 14/598966 was filed with the patent office on 2015-05-14 for bio-based synthetic fluids.
The applicant listed for this patent is REG Synthetic Fuels, LLC. Invention is credited to Ramin Abhari, Peter Z. Havlik, E. Gary Roth, H. Lynn Tomlinson.
Application Number | 20150133355 14/598966 |
Document ID | / |
Family ID | 51654861 |
Filed Date | 2015-05-14 |
United States Patent
Application |
20150133355 |
Kind Code |
A1 |
Abhari; Ramin ; et
al. |
May 14, 2015 |
BIO-BASED SYNTHETIC FLUIDS
Abstract
A method is provided involving altering the viscosity of
bio-derived paraffins to produce a paraffinic fluid, where the
altering step includes chlorinating the bio-derived paraffins; the
bio-derived paraffins include a hydrodeoxygenated product produced
by hydrodeoxygenating a bio-based feed where the bio-based feed
includes bio-derived fatty acids, fatty acid esters, or a
combination thereof; the bio-derived paraffins include n-paraffins;
and the n-paraffins have a biodegradability of at least 40% after
about 23 days of exposure to microorganisms. Also provided are
methods of protecting and/or cleaning a substance by applying the
paraffinic fluid.
Inventors: |
Abhari; Ramin; (Bixby,
OK) ; Roth; E. Gary; (Bristow, OK) ; Havlik;
Peter Z.; (Tulsa, OK) ; Tomlinson; H. Lynn;
(Tulsa, OK) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
REG Synthetic Fuels, LLC |
Ames |
IA |
US |
|
|
Family ID: |
51654861 |
Appl. No.: |
14/598966 |
Filed: |
January 16, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13871972 |
Apr 26, 2013 |
8969259 |
|
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14598966 |
|
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|
61809183 |
Apr 5, 2013 |
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Current U.S.
Class: |
508/589 ;
252/364; 252/601; 507/103; 507/203; 510/461 |
Current CPC
Class: |
C10G 50/00 20130101;
A01N 25/02 20130101; C10G 2300/1014 20130101; C10M 105/52 20130101;
C09K 21/08 20130101; C10N 2040/20 20130101; Y02P 30/20 20151101;
C10G 50/02 20130101; C10M 105/04 20130101; C09K 8/34 20130101; C11D
7/241 20130101; E21B 43/26 20130101; C09K 8/64 20130101; C10G 3/50
20130101; C10G 49/02 20130101; C10G 2300/1018 20130101; C09K 8/32
20130101; C10G 3/00 20130101; C10G 49/00 20130101; C10G 2300/1011
20130101 |
Class at
Publication: |
508/589 ;
507/103; 507/203; 252/601; 252/364; 510/461 |
International
Class: |
C10G 3/00 20060101
C10G003/00; C09K 8/64 20060101 C09K008/64; C11D 7/24 20060101
C11D007/24; C09K 21/08 20060101 C09K021/08; C10G 49/00 20060101
C10G049/00; C09K 8/32 20060101 C09K008/32; C10M 105/52 20060101
C10M105/52 |
Claims
1. A method comprising altering the viscosity of bio-derived
paraffins to produce a paraffinic fluid, wherein the altering step
comprises chlorinating the bio-derived paraffins to produce a
chlorinated product, where the chlorinated product comprises
haloalkanes and has a kinematic viscosity of greater than about 10
cSt at 40.degree. C.; the paraffinic fluid comprises the
chlorinated product; the bio-derived paraffins comprise a
hydrodeoxygenated product produced by hydrodeoxygenating a
bio-based feed where the bio-based feed comprises bio-derived fatty
acids, fatty acid esters, or a combination thereof; and the
bio-derived paraffins comprise n-paraffins where the n-paraffins
have a kinematic viscosity of less than about 10 cSt at 40.degree.
C.; and have a biodegradability of at least about 40% after about
23 days of exposure to microorganisms.
2. The method of claim 1, wherein chlorinating the bio-derived
paraffins comprises contacting the bio-derived paraffins with
chlorine gas at a temperature between about 60.degree. C. and about
150.degree. C. to produce the chlorinated product.
3. The method of claim 2, wherein the chlorinated product is about
30 wt % to about 70 wt % chlorine.
4. The method of claim 2, wherein the chlorinated product has less
than about 1 wt % aromatics.
5. The method of claim 2, wherein the chlorinated product is free
of benzene.
6. The method of claim 2, wherein the hydrodeoxygenated product has
less than about 1 wt % aromatics; the chlorinated product has less
than about 1 wt % aromatics; and the paraffinic fluid has less than
about 1 wt % aromatics.
7. The method of claim 2, wherein the hydrodeoxygenated product has
less than about 0.1 wt % aromatics; the chlorinated product has
less than about 0.1 wt % aromatics; and the paraffinic fluid has
less than about 0.1 wt % aromatics.
8. The method of claim 2, wherein the temperature for contacting
the bio-derived paraffins with chlorine gas is about 80.degree. C.
to about 120.degree. C.
9. The method of claim 2, wherein contacting the bio-derived
paraffins with chlorine gas does not involve a catalyst.
10. The method of claim 2, wherein contacting the bio-derived
paraffins with chlorine gas further comprises UV light.
11. The method of claim 2, further comprising purging the
chlorinated product with air or nitrogen.
12. The method of claim 2, wherein the paraffinic fluid comprises
bio-derived paraffins within the C.sub.16-C.sub.36 range.
13. The method of claim 1, wherein the bio-derived paraffins are
produced by at least partially hydroisomerizing the
hydrodeoxygenated product to produce a hydroisomerized product;
wherein the bio-derived paraffins comprise the hydrodeoxygenated
product and the hydroisomerized product; the hydrodeoxygenated
product comprises n-paraffins; the hydroisomerized product
comprises isoparaffins where at least about 80 wt % of the
isoparaffins are mono-methyl branched paraffins and the mono-methyl
branched paraffins comprise less than about 30 wt % terminal
branched isoparaffins; and the isoparaffins have a kinematic
viscosity of greater than about 10 cSt at 40.degree. C.; and have a
biodegradability of at least about 40% after about 23 days of
exposure to microorganisms.
14. The method of claim 13, wherein the hydrodeoxygenated product
comprises n-paraffins in the range of about 80 wt % to about 100 wt
%; cycloparaffins in the range of about 0 wt % to about 10 wt %;
and less than about 1 wt % total aromatics.
15. The method of claim 13, wherein the hydrodeoxygenated product
comprises n-paraffins in the range of about 90 wt % to about 100 wt
%; cycloparaffins in the range of about 0 wt % to about 10 wt %;
and less than about 0.1 wt % total aromatics.
16. The method of claim 2, wherein the bio-derived paraffins are
produced by hydrodeoxygenating the bio-based feed to produce a
hydrodeoxygenated product; and at least partially hydroisomerizing
the hydrodeoxygenated product to produce a hydroisomerized product;
wherein the bio-derived paraffins comprise the hydrodeoxygenated
product and the hydroisomerized product; the hydrodeoxygenated
product comprises n-paraffins; the hydroisomerized product
comprises isoparaffins where at least about 80 wt % of the
isoparaffins are mono-methyl branched paraffins and the mono-methyl
branched paraffins comprise less than about 30 wt % terminal
branched isoparaffins; and the isoparaffins have a kinematic
viscosity of greater than about 10 cSt at 40.degree. C.; and have a
biodegradability of at least about 40% after about 23 days of
exposure to microorganisms.
17. The method of claim 16, wherein contacting the bio-derived
paraffins with chlorine gas does not involve a catalyst.
18. The method of claim 16, wherein contacting the bio-derived
paraffins with chlorine gas further comprises UV light.
19. The method of claim 16, further comprising purging the
chlorinated product with air or nitrogen.
20. The method of claim 16, wherein paraffinic fluid comprises
bio-derived paraffins within the C.sub.16-C.sub.36 range.
21. The method of claim 16, wherein the hydrodeoxygenated product
comprises n-paraffins in the range of about 80 wt % to about 100 wt
%; cycloparaffins in the range of about 0 wt % to about 10 wt %;
and less than about 1 wt % total aromatics.
22. The method of claim 16, wherein the hydrodeoxygenated product
comprises n-paraffins in the range of about 90 wt % to about 100 wt
%; cycloparaffins in the range of about 0 wt % to about 10 wt %;
and less than about 0.1 wt % total aromatics.
23. The method of claim 1, wherein the bio-derived fatty acids,
fatty acid esters, or a combination thereof comprises algae oils,
beef tallow, camelina oil, canola oil, rapeseed oil, castor oil,
choice white grease, coconut oil, coffee bean oil, corn oil,
cottonseed oil, fish oils, hemp oil, Jatropha oil, linseed oil,
mustard oil, palm oil, palm kernel oil, poultry fat, soybean oil,
sunflower oil, tall oil, tall oil fatty acid, Tung oil, used
cooking oils, yellow grease, products of the food industry, or
combinations of any two or more thereof.
24. The method of claim 1, wherein the bio-derived fatty acids,
fatty acid esters, or a combination thereof comprise soybean oil,
corn oil, cottonseed oil, canola oil, coconut oil, sunflower oil,
palm oil, palm kernel oil, rapeseed oil, or a combination of any
two or more thereof.
25. The method of claim 1, wherein the paraffinic fluid is free of
benzene.
26. The paraffinic fluid produced by the method of claim 1.
27. The paraffinic fluid of claim 26, wherein the paraffinic fluid
is used as a protecting agent, a cleaning agent, or a combination
of both.
28. The paraffinic fluid of claim 26, wherein the paraffinic fluid
acts as a flame retardant.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser.
No. 13/871,972, filed Apr. 26, 2013, which claims the benefit of
priority from U.S. Provisional Application No. 61/809,183, filed on
Apr. 5, 2013, each of which is incorporated herein by reference in
its entirety for any and all purposes.
FIELD
[0002] The technology relates to production of synthetic fluids
from bio-derived feeds. More particularly, this technology relates
to methods for conversion of animal fat, vegetable oils, and other
sources of bio-based fatty acid/esters into paraffinic fluids
suitable for use as solvents, industrial process fluids, and
lubricating base oils.
BACKGROUND
[0003] Low aromatic hydrocarbon fluids, i.e. typically containing
less than 1 wt % total aromatics, are used in a diverse range of
applications where chemical inertness, thermal/oxidative stability,
low toxicity, and low odor are desired. These hydrocarbons are
characterized by their paraffinic nature, a carbon number
distribution in the C.sub.5-C.sub.40 range, preferably in the
C.sub.15-C.sub.40 range. For most applications, the preferred
fluids have a flash point greater than about 100.degree. C. Other
properties specified for hydrocarbon fluids include viscosity
(specification range dictated by application), and pour point
(typically <-10.degree. C.). Mineral oil is an example of a low
aromatic hydrocarbon fluid.
[0004] As a result of a number of industry trends, such as
increased demand for drilling and hydraulic fracturing fluids and
tightening environmental standards concerning eco-toxicity,
biodegradability, and work place safety/health, demand for such
paraffinic fluids has experienced rapid growth. This has coincided
with an increased demand for middle distillate fuels
(C.sub.10-C.sub.20 hydrocarbons) that compete for much of the same
petroleum molecules. Furthermore, with high aromatic feeds such as
tar sands finding their way into the North American petroleum pool,
more extensive upgrading (such as aromatic hydrogenation) is
required in order to meet fluid product specifications. Use of
mineral oils in cosmetics and food preparation is banned in the
European Union due to concerns about presence of trace amounts of
carcinogenic polyaromatic hydrocarbons--thus providing the need for
synthetic products that are inherently free of these aromatic
components.
[0005] Synthetic hydrocarbon products have been used for some
industrial fluid applications. For example C.sub.16/C.sub.18 linear
alpha olefins (LAOs) from oligomerization of ethylene, are used as
drilling base fluids. However, this synthetic route is
non-selective, producing a wide distribution of even carbon number
LAOs, mostly in the C.sub.4 to C.sub.10 range, such that further
expensive processing and separation steps are required to achieve
the desired LAO product. Moreover, these even carbon number LAOs in
the C.sub.4 to C.sub.10 range are chemical intermediates and not
end-products suitable for use in industrial fluid applications.
[0006] Use of the Fischer-Tropsch process for producing synthetic
hydrocarbons suitable for certain hydrocarbon fluid applications
has also been reported. However, the FT process is very capital
intensive and most of the FT manufacturing is dedicated to fuel
production. Because the hydrocarbon range of interest for synthetic
hydrocarbon fluids comprises a small percentage of the wide
distribution of FT hydrocarbons (C1-C50+), it is more economical to
hydrocrack and hydrotreat the FT wax and light oil fractions into
complex compositions for fuel use.
[0007] There is thus a need for new processes for producing
hydrocarbon fluids from alternative feeds. More specifically, there
is a need for hydrocarbon fluid products that, based on their
feedstocks and conversion processes, are substantially free of
aromatics without further processing such as by aromatic
hydrogenation conditions.
SUMMARY
[0008] In an aspect, a method is provided involving altering the
viscosity of bio-derived paraffins to produce a paraffinic fluid,
where the altering step includes oligomerizing bio-derived
paraffins, unsaturating bio-derived paraffins, chlorinating
bio-derived paraffins, or a combination of any two or more thereof;
the bio-derived paraffins are produced by hydrodeoxygenating a
bio-based feed; the bio-based feed comprises bio-derived fatty
acids, fatty acid esters, or a combination thereof; the bio-derived
paraffins comprise n-paraffins; and the n-paraffins have a
kinematic viscosity of less than about 10 cSt at 40.degree. C. and
have a biodegradability of at least 40% after about 23 days of
exposure to microorganisms.
[0009] In some embodiments, oligomerizing bio-derived paraffins
includes contacting the bio-derived paraffins with an organic
peroxide to produce an oligomerized product, where the oligomerized
product has a kinematic viscosity of at least about 10 cSt at
40.degree. C. In some embodiments, the oligomerized product has a
biodegradability of at least about 40% after about 23 days of
exposure to microorganisms. In some embodiments, the oligomerized
product is a dimer, trimer, tetramer, or a mixture of any two or
more thereof. In some embodiments, the organic peroxide is present
in an amount between about 2 wt % and about 40 wt % based on the
total weight of paraffins and organic peroxide. In some
embodiments, the organic peroxide comprises di-tert butyl peroxide
(DTBP), 2,5-dimethyl 2,5-di(t-butylperoxy)hexane, dicumyl peroxide,
dibenzoyl peroxide, dipropyl peroxide, ethyl propyl peroxide, or
tert-butyl tert-amyl peroxide. In some embodiments, the contacting
is performed at a temperature between about 50.degree. C. and about
250.degree. C. In some embodiments, the oligomerized product is
used as a drilling fluid, a hydraulic fracturing fluid, a metal
working fluid, a protecting agent, or a combination of any two or
more thereof.
[0010] In some embodiments, chlorinating the bio-derived paraffins
includes contacting the bio-derived paraffins with chlorine gas at
a temperature between about 60.degree. C. and about 150.degree. C.
to produce a chlorinated product, where the chlorinated product
comprises haloalkanes; and the chlorinated product has a kinematic
viscosity of greater than about 10 cSt at 40.degree. C. In some
embodiments, the chlorinated product is used as a protecting agent,
a cleaning agent, or a combination of both. In some embodiments,
the chlorinated product acts as a flame retardant. In some
embodiments, the chlorinated product is used to clean fabric,
metal, or plastic.
[0011] In some embodiments, unsaturating the bio-derived paraffins
comprises dehydrogenation of the bio-derived paraffins by
contacting the bio-derived paraffins with a dehydrogenation
catalyst at a temperature from about 360.degree. C. to about
660.degree. C. to produce an olefinic fluid, where the olefinic
fluid comprises at least about 10 wt % internal olefins in the
C.sub.15 to C.sub.18 range; and the olefinic fluids have a
kinematic viscosity of less than about 10 cSt at 40.degree. C. In
some embodiments, the olefinic fluid comprises at least about 20 wt
% internal olefins in the C.sub.15 to C.sub.18 range. In some
embodiments, the method further involves oligomerizing the olefinic
fluid to produce dimers, trimers, tetramers, or a mixture of any
two or more thereof. In some embodiments, the olefinic fluid is
used as a hydraulic fracturing fluid, as a drilling fluid, or a
combination of the two.
[0012] In some embodiments, the bio-derived paraffins are produced
by hydrodeoxygenating the bio-based feed to produce a
hydrodeoxygenated product; and at least partially hydroisomerizing
the hydrodeoxygenated product to produce a hydroisomerized product;
where the bio-derived paraffins comprise the hydrodeoxygenated
product and the hydroisomerized product; the hydrodeoxygenated
product comprises n-paraffins; the hydroisomerized product
comprises isoparaffins where at least about 80 wt % of the
isoparaffins are mono-methyl branched paraffins; the mono-methyl
branched paraffins comprise less than about 30 wt % terminal
branched isoparaffins; and the isoparaffins have a kinematic
viscosity of less than about 10 cSt at 40.degree. C. and have a
biodegradability of at least about 40% after about 23 days of
exposure to microorganisms. In some embodiments, the
hydrodeoxygenated product includes n-paraffins in the range of
about 80 wt % to about 100 wt %; cycloparaffins in the range of
about 1 wt % to about 10 wt %; and less than about 1 wt % total
aromatics.
[0013] In some embodiments, the bio-derived fatty acids, fatty acid
esters, or a combination thereof comprises algae oils, beef tallow,
camelina oil, canola oil, rapeseed oil, castor oil, choice white
grease, coconut oil, coffee bean oil, corn oil, cottonseed oil,
fish oils, hemp oil, Jatropha oil, linseed oil, mustard oil, palm
oil, palm kernel oil, poultry fat, soybean oil, sunflower oil, tall
oil, tall oil fatty acid, Tung oil, used cooking oils, yellow
grease, products of the food industry, or combinations of any two
or more thereof. In some embodiments, the bio-derived fatty acids,
fatty acid esters, or a combination thereof comprise soybean oil,
corn oil, cottonseed oil, canola oil, coconut oil, sunflower oil,
palm oil, palm kernel oil, rapeseed oil, or a combination of any
two or more thereof.
[0014] In an aspect, a method is provided involving producing an
orifice in a substrate by at least injecting a viscosity-altered
paraffinic fluid into the substrate, wherein the paraffinic fluid
includes a hydrodeoxygenated product and a hydroisomerized product;
the hydrodeoxygenated product is produced by hydrodeoxygenating a
bio-derived feed; the hydroisomerized product is produced by at
least partially hydroisomerizing the hydrodeoxygenated product; the
bio-derived feed includes bio-derived fatty acids, fatty acid
esters, or a combination thereof; the hydrodeoxygenated product
includes n-paraffins; the hydroisomerized product includes
isoparaffins; the paraffinic fluid contains less than about 1 wt %
aromatics; and the n-paraffins have a kinematic viscosity of less
than about 10 cSt at 40.degree. C. and have a biodegradability of
at least about 40% after about 23 days of exposure to
microorganisms; the isoparaffins are at least about 80 wt %
mono-methyl branched paraffins where the mono-methyl branched
paraffins comprise less than about 30 wt % terminal branched
isoparaffins, have a kinematic viscosity of less than about 10 cSt
at 40.degree. C., and have a biodegradability of at least about 40%
after about 23 days of exposure to microorganisms. In some
embodiments, the substrate includes a soil substrate, a topsoil
substrate, a subsoil substrate, a clay substrate, a sand substrate,
a rock substrate, or a stone substrate. In some embodiments, the
step of producing an orifice includes hydraulic fracturing of the
substrate with the paraffinic fluid.
[0015] In another aspect, a method is provided involving protecting
a substance by applying a paraffinic fluid. In the method, the
paraffinic fluid includes a hydrodeoxygenated product; where the
hydrodeoxygenated product is produced by hydrodeoxygenating a
bio-derived feed; the bio-derived feed comprises bio-derived fatty
acids, fatty acid esters, or a combination thereof; the
hydrodeoxygenated product comprises n-paraffins; the paraffinic
fluid contains less than 1 wt % aromatics; and the n-paraffins have
a kinematic viscosity of less than about 10 cSt at 40.degree. C.
and have a biodegradability of at least 40% after about 23 days of
exposure to microorganisms. In some embodiments, the
hydrodeoxygenated product includes n-paraffins in the range of
about 80 wt % to about 100 wt %; cycloparaffins in the range of
about 1 wt % to about 10 wt %; less than about 1 wt % total
aromatics. In some embodiments, the paraffinic fluid further
comprises a hydroisomerized product produced by at least partially
hydroisomerizing the hydrodeoxygenated product; where the
hydroisomerized product comprises isoparaffins where at least about
80 wt % of the isoparaffins are mono-methyl branched paraffins; the
mono-methyl branched paraffins comprise less than about 30 wt %
terminal branched isoparaffins; and the isoparaffins have a
kinematic viscosity of less than about 10 cSt at 40.degree. C. and
have a biodegradability of at least about 40% after about 23 days
of exposure to microorganisms.
[0016] In some embodiments, the substance is a food crop, a metal,
or wood. In some embodiments, protecting involves solvating the
substance. In such embodiments, the substance includes pesticides,
herbicides, paints, inks, or coatings. In some embodiments,
protecting involves cleaning the substance with the paraffinic
fluid In such embodiments, the substance comprises fabric, metal,
or plastic. In some embodiments, protecting involves lubricating
the substance where the substance is metal.
[0017] In an aspect, a method is provided which involves producing
an orifice in a substrate by at least injecting a paraffinic fluid
into the substrate, wherein the paraffinic fluid comprises a
hydrodeoxygenated product; the hydrodeoxygenated product is
produced by hydrodeoxygenating a bio-derived feed; the bio-derived
feed comprising bio-derived fatty acids, fatty acid esters, or a
combination thereof; the hydrodeoxygenated product comprises
n-paraffins; the paraffinic fluid contains less than about 1 wt %
aromatics; and the n-paraffins have a kinematic viscosity of less
than about 10 cSt at 40.degree. C. and have a biodegradability of
at least about 40% after about 23 days of exposure to
microorganisms. In some embodiments, the hydrodeoxygenated product
includes n-paraffins in the range of about 80 wt % to about 100 wt
%; cycloparaffins in the range of about 1 wt % to about 10 wt %;
and less than about 1 wt % total aromatics. In some embodiments,
the paraffinic fluid further includes a hydroisomerized product
produced by at least partially hydroisomerizing the
hydrodeoxygenated product; wherein the hydroisomerized product
comprises isoparaffins where at least about 80 wt % of the
isoparaffins are mono-methyl branched paraffins; the mono-methyl
branched paraffins comprise less than about 30 wt % terminal
branched isoparaffins; and the isoparaffins have a kinematic
viscosity of less than about 10 cSt at 40.degree. C. and have a
biodegradability of at least about 40% after about 23 days of
exposure to microorganisms.
[0018] In some embodiments, the substrate comprises a soil
substrate, a topsoil substrate, a subsoil substrate, a clay
substrate, a sand substrate, a rock substrate, or a stone
substrate. In some embodiments, the bio-derived fatty acids, fatty
acid esters, or a combination thereof comprises algae oils, beef
tallow, camelina oil, canola oil, rapeseed oil, castor oil, choice
white grease, coconut oil, coffee bean oil, corn oil, cottonseed
oil, fish oils, hemp oil, Jatropha oil, linseed oil, mustard oil,
palm oil, palm kernel oil, poultry fat, soybean oil, sunflower oil,
tall oil, tall oil fatty acid, Tung oil, used cooking oils, yellow
grease, products of the food industry, or combinations of any two
or more thereof. In some embodiments, the bio-derived fatty acids,
fatty acid esters, or a combination thereof comprise soybean oil,
corn oil, cottonseed oil, canola oil, coconut oil, sunflower oil,
palm oil, palm kernel oil, rapeseed oil, or a combination of any
two or more thereof. In some embodiments, the step of producing an
orifice comprises hydraulic fracturing of the substrate with the
paraffinic fluid.
BRIEF DESCRIPTION OF THE DRAWING
[0019] FIG. 1 depicts a process for conversion of a bio-derived
feed to industrial fluids, the process comprising
hydrodeoxygenation, hydroisomerization, peroxide-initiated
oligomerization, and fractionation
DETAILED DESCRIPTION
[0020] Various embodiments are described hereinafter. It should be
noted that the specific embodiments are not intended as an
exhaustive description or as a limitation to the broader aspects
discussed herein. One aspect described in conjunction with a
particular embodiment is not necessarily limited to that embodiment
and can be practiced with any other embodiment(s).
[0021] As used herein, "about" will be understood by persons of
ordinary skill in the art and will vary to some extent depending
upon the context in which it is used. If there are uses of the term
which are not clear to persons of ordinary skill in the art, given
the context in which it is used, "about" will mean up to plus or
minus 10% of the particular term.
[0022] The use of the terms "a" and "an" and "the" and similar
referents in the context of describing the elements (especially in
the context of the following claims) are to be construed to cover
both the singular and the plural, unless otherwise indicated herein
or clearly contradicted by context. Recitation of ranges of values
herein are merely intended to serve as a shorthand method of
referring individually to each separate value falling within the
range, unless otherwise indicated herein, and each separate value
is incorporated into the specification as if it were individually
recited herein. All methods described herein can be performed in
any suitable order unless otherwise indicated herein or otherwise
clearly contradicted by context. The use of any and all examples,
or exemplary language (e.g., "such as") provided herein, is
intended merely to better illuminate the embodiments and does not
pose a limitation on the scope of the claims unless otherwise
stated. No language in the specification should be construed as
indicating any non-claimed element as essential.
[0023] In general, "substituted" refers to an alkyl or aryl group
as defined below (e.g., an alkyl group) in which one or more bonds
to a hydrogen atom contained therein are replaced by a bond to
non-hydrogen or non-carbon atoms. Substituted groups also include
groups in which one or more bonds to a carbon(s) or hydrogen(s)
atom are replaced by one or more bonds, including double or triple
bonds, to a heteroatom. Thus, a substituted group will be
substituted with one or more substituents, unless otherwise
specified. In some embodiments, a substituted group is substituted
with 1, 2, 3, 4, 5, or 6 substituents. Examples of substituent
groups include: halogens (i.e., F, Cl, Br, and I); hydroxyls;
alkoxy, alkylperoxy, alkenoxy, alkynoxy, aryloxy, arylperoxy,
aralkyloxy; carbonyls (oxo); carboxyls; esters; urethanes; oximes;
hydroxylamines; alkoxyamines; aralkoxyamines; thiols; sulfides;
sulfoxides; sulfones; sulfonyls; sulfonamides; amines; N-oxides;
hydrazines; hydrazides; hydrazones; azides; amides; ureas;
amidines; guanidines; enamines; imides; isocyanates;
isothiocyanates; cyanates; thiocyanates; imines; nitro groups;
nitriles (i.e., CN); and the like.
[0024] As used herein, "alkyl" groups include straight chain and
branched alkyl groups having from 1 to about 20 carbon atoms, and
typically from 1 to 12 carbons or, in some embodiments, from 1 to 8
carbon atoms. As employed herein, "alkyl groups" include cycloalkyl
groups as defined below. Alkyl groups may be substituted or
unsubstituted. Examples of straight chain alkyl groups include
methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and
n-octyl groups. Examples of branched alkyl groups include, but are
not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, and
isopentyl groups. Representative substituted alkyl groups may be
substituted one or more times with, for example, amino, thio,
hydroxy, cyano (i.e. CN), alkoxy, and/or halo groups such as F, Cl,
Br, and I groups.
[0025] Cycloalkyl groups are cyclic alkyl groups such as, but not
limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, and cyclooctyl groups. In some embodiments, the
cycloalkyl group has 3 to 8 ring members, whereas in other
embodiments the number of ring carbon atoms range from 3 to 5, 6,
or 7. Cycloalkyl groups may be substituted or unsubstituted.
Cycloalkyl groups further include polycyclic cycloalkyl groups such
as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl,
isocamphenyl, and carenyl groups, and fused rings such as, but not
limited to, decalinyl, and the like. Cycloalkyl groups also include
rings that are substituted with straight or branched chain alkyl
groups as defined above. Representative substituted cycloalkyl
groups may be mono-substituted or substituted more than once, such
as, but not limited to: 2,2-; 2,3-; 2,4-; 2,5-; or
2,6-disubstituted cyclohexyl groups or mono-, di-, or
tri-substituted norbornyl or cycloheptyl groups, which may be
substituted with, for example, alkyl, alkoxy, amino, thio, hydroxy,
cyano, and/or halo groups.
[0026] As used herein, "aryl" groups are cyclic aromatic
hydrocarbons that do not contain heteroatoms. Aryl groups include
monocyclic, bicyclic and polycyclic ring systems. Thus, aryl groups
include, but are not limited to, phenyl, azulenyl, heptalenyl,
biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl,
pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl,
indanyl, pentalenyl, and naphthyl groups. In some embodiments, aryl
groups contain 6-14 carbons, and in others from 6 to 12 or even
6-10 carbon atoms in the ring portions of the groups. The phrase
"aryl groups" includes groups containing fused rings, such as fused
aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl,
and the like). Aryl groups may be substituted or unsubstituted.
[0027] The term "microorganisms" as used herein refers to microbes
capable of degrading hydrocarbons.
[0028] The term "paraffins" as used herein means branched or
unbranched hydrocarbon alkanes. An unbranched paraffin is an
n-paraffin; a branched paraffin is an isoparaffin.
[0029] The term "paraffinic" as used herein means both paraffins as
defined above as well as predominantly hydrocarbon chains
possessing regions that are alkane, either branched or unbranched,
with mono- or di-unsaturation (i.e. one or two double bonds),
halogenation from about 30 wt % to about 70 wt %, or where the
hydrocarbon is both unsaturated and halogenated. However, the term
does not describe a halogen on a carbon involved in a double
bond.
[0030] The phrase "C.sub.2+ chain branching" as used herein means
alkyl branches wherein the alkyl group has two or more carbons;
e.g. ethyl or isopropyl branches.
[0031] "Protecting" as used herein includes, but is not limited to,
solvating, coating, cleaning, lubricating, or preserving a
substance, surface, or composition.
[0032] "Orifice" as used herein encompasses holes, channels,
fractures, and fissure; in other words, the term encompasses spaces
of any three-dimensional length, width, and diameter that are not
filled with solid material.
[0033] The present technology provides bio-based synthetic fluids
as well as methods for making the fluids and methods that utilize
the advantageous properties of the bio-based synthetic fluids, as
discussed herein.
[0034] In an aspect, a method is provided involving altering the
viscosity of bio-derived paraffins to produce a paraffinic fluid,
where the altering step includes oligomerizing bio-derived
paraffins, unsaturating bio-derived paraffins, chlorinating
bio-derived paraffins, or a combination of any two or more thereof;
the bio-derived paraffins are produced by hydrodeoxygenating a
bio-based feed; the bio-based feed comprises bio-derived fatty
acids, fatty acid esters, or a combination thereof; the bio-derived
paraffins comprise n-paraffins; and the n-paraffins have a
biodegradability of at least about 40% after about 23 days of
exposure to microorganisms. The biodegradability may be about 42%,
about 44%, about 46%, about 48%, about 50%, about 52%, about 54%,
about 56%, about 58%, about 60%, about 62%, about 64%, about 66%,
about 68%, about 70%, about 72%, about 74%, about 76%, about 78%,
about 80%, and ranges between any two of these values or greater
than any one of these values. In some embodiments, the paraffinic
fluid contains below about 1 wt % total aromatics. The paraffinic
fluid may contain aromatics in the amount of about 0.9 wt %, about
0.8 wt %, about 0.7 wt %, about 0.6 wt %, about 0.5 wt %, about 0.4
wt %, about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, and ranges
between any two of these values or below any one of these values.
In some embodiments, the paraffinic fluid contain less than 0.1 wt
% total aromatics. In some embodiments, the paraffinic fluid is
free of benzene.
[0035] In some embodiments, the paraffinic fluid has a kinematic
viscosity less than about 10 cSt at 40.degree. C. In such
embodiments, the paraffinic fluid may have a kinematic viscosity at
40.degree. C. of about 9 cSt, about 8 cSt, about 7 cSt, about 6
cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2 cSt, about 1
cSt, and ranges in between any two of these values or below any one
of these values. In some embodiments, the paraffinic fluid has a
kinematic viscosity greater than about 10 cSt at 40.degree. C. In
such embodiments, the paraffinic fluid may have a kinematic
viscosity at 40.degree. C. of about 12 cSt, about 14 cSt, about 16
cSt, about 18 cSt, about 20 cSt, about 22 cSt, about 24 cSt, about
26 cSt, about 28 cSt, about 30 cSt, and ranges in between any two
of these values or greater than any one of these values. In some
embodiments, the paraffinic fluid has a kinematic viscosity greater
than about 20 cSt at 40.degree. C.
Bio-Based Feed:
[0036] Bio-derived fatty acids, fatty acid esters, or combinations
thereof, are utilized as the bio-based feed for making the fluids
described throughout this application. The bio-derived fatty acids,
fatty acid esters, or combinations thereof include algae oils, beef
tallow, camelina oil, canola/rapeseed oil, castor oil, choice white
grease, coconut oil, coffee bean oil, corn oil, fish oils, hemp
oil, Jatropha oil, linseed oil, mustard oil, palm oil, poultry fat,
soybean oil, sunflower oil, tall oil, tall oil fatty acid, Tung
oil, used cooking oils, yellow grease, products of the food
industry, or combinations of any two or more thereof. In some
embodiments, the bio-derived fatty acids, fatty acid esters, or
combinations thereof include soybean oil, corn oil, cottonseed oil,
canola oil, coconut oil, sunflower oil, palm oil, palm kernel oil,
rapeseed oil, or a combination of any two or more thereof.
[0037] In their natural form, most of these fats and oils contain
phosphorus as well as metals such as calcium, magnesium, sodium,
potassium, iron, and copper. Additionally, most also contain
nitrogen compounds such as chlorophyll or amino acids. When the
level of phosphorus is greater than about 40 wppm, and total metals
greater than about 30 wppm, the fats and oils may be subjected to
treatment steps including, but not limited to, acid degumming,
neutralization, bleaching, or a combination of any two or more
thereof. Acid degumming involves contacting the fat/oil with
concentrated aqueous acids. Exemplary acids are phosphoric, citric,
and maleic acids. This pretreatment step removes metals such as
calcium and magnesium in addition to phosphorus. Neutralization is
typically performed by adding a caustic (referring to any base,
such as aqueous NaOH) to the acid-degummed fat/oil. The process
equipment used for acid degumming and neutralization includes high
shear mixers and disk stack centrifuges.
[0038] Bleaching typically involves contacting the degummed fat/oil
with adsorbent clay and filtering the spent clay through a pressure
leaf filter. Use of synthetic silica instead of clay is reported to
provide improved adsorption. The bleaching step removes chlorophyll
and much of the residual metals and phosphorus. Any soaps that may
have been formed during the caustic neutralization step (i.e. by
reaction with free fatty acids) are also removed during the
bleaching step. The aforementioned treatment processes are known in
the art and described in the patent literature, including but not
limited to U.S. Pat. Nos. 4,049,686, 4,698,185, 4,734,226, and
5,239,096. It should be recognized by those skilled in the art that
other fat/oil treatment methods, including those involving
alternate physical, thermal, and chemical processes, may be adapted
to pretreatment of a bio-based feed.
Hydrodeoxygenation:
[0039] The bio-based feed is subjected to hydrodeoxygenation (HDO)
in a catalytic reactor wherein the fatty acids and/or fatty acid
esters are converted to straight-chain paraffins. In
hydrodeoxygenation, the oxygen atoms of the fatty acid/ester are
removed through hydrogenolysis to form water, while the unsaturated
carbon-carbon double bonds of the fatty acid chains are
simultaneously hydrogenated. HDO may be accompanied by
decarbonylation and decarboxylation reactions (wherein the oxygen
atom is removed as CO and CO.sub.2 respectively). The HDO reaction
takes place at temperatures from about 200.degree. C. to about
400.degree. C., and hydrogen partial pressure between about 20 bar
to about 160 bar. The HDO reaction may occur at a temperature of
about 220.degree. C., 240.degree. C., 260.degree. C., 280.degree.
C., 300.degree. C., 320.degree. C., 340.degree. C., 360.degree. C.,
380.degree. C., and ranges between any two of these values or above
any one of these values. In some embodiments, temperature range is
from about 260.degree. C. to about 370.degree. C. The HDO reaction
may occur at a hydrogen partial pressure of about 30 bar, 40 bar,
50 bar, 60 bar, 70 bar, 80 bar, 90 bar, 100 bar, 110 bar, 120 bar,
130 bar, 140 bar, 150 bar, and ranges between any two of these
values or above any one of these values. In some embodiments, the
pressure range is from about 30 bar to about 130 bar. Suitable
catalysts for the HDO process include sulfided forms of
hydrogenation metals from Group VIB and Group VIII of the periodic
table. Examples of suitable mono-metallic, bi-metallic, and
tri-metallic catalysts include Mo, Ni, Co, W, CoMo, NiMo, NiW,
NiCoMo. These catalysts may be supported on alumina, or alumina
modified with oxides of silicon and/or phosphorus. These catalysts
may be purchased in the reduced sulfide form, or more commonly
purchased as metal oxides and sulfided during startup. To ensure
these catalysts remain in the reduced sulfide form required for
desired activity/selectivity balance, use of a "sulfur spike"
compound such as dimethyl disulfide may be utilized. Fixed-bed
and/or slurry reactor systems and operating conditions may be used.
In some embodiments, continuous reactor systems are used. In some
embodiments, continuous fixed-bed reactors are used. In continuous
fixed-bed reactor systems, the liquid hourly space velocity (LHSV)
is between about 0.2 h.sup.-1 and about 10 h.sup.-1, and the
hydrogen gas-to-oil ratio (GOR at standard conditions) is between
about 200 NL/L and about 1600 NL/L. The LHSV may be about 0.3
h.sup.-1, about 0.4 h.sup.-1, about 0.5 h.sup.-1, about 0.6
h.sup.-1, about 0.7 h.sup.-1, about 0.8 h.sup.-1, about 0.9
h.sup.-1, about 1.0 h.sup.-1, about 1.2 h.sup.-1, about 1.4
h.sup.-1, about 1.6 h.sup.-1, about 1.8 h.sup.-1, about 2.0
h.sup.-1, about 2.2 h.sup.-1, about 2.4 h.sup.-1, about 2.6
h.sup.-1, about 2.8 h.sup.-1, about 3.0 h.sup.-1, about 3.0
h.sup.-1, about 3.2 h.sup.-1, about 3.4 h.sup.-1, about 3.6
h.sup.-1, about 3.8 h.sup.-1, about 4.0 h.sup.-1, about 4.2
h.sup.-1, about 4.4 h.sup.-1, about 4.6 h.sup.-1, about 4.8
h.sup.-1, about 5.0 h.sup.-1, about 5.2 h.sup.-1, about 5.4
h.sup.-1, about 5.6 h.sup.-1, about 5.8 h.sup.-1, about 6.0
h.sup.-1, about 6.2 h.sup.-1, about 6.4 h.sup.-1, about 6.6
h.sup.-1, about 6.8 h.sup.-1, about 7.0 h.sup.-1, about 7.2
h.sup.-1, about 7.4 h.sup.-1, about 7.6 h.sup.-1, about 7.8
h.sup.-1, about 8.0 h.sup.-1, about 8.2 h.sup.-1, about 8.4
h.sup.-1, about 8.6 h.sup.-1, about 8.8 h.sup.-1, about 9.0
h.sup.-1, about 9.2 h.sup.-1, about 9.4 h.sup.-1, about 9.6
h.sup.-1, about 9.8 h.sup.-1, and ranges between any two of these
values or above any one of these values. In some embodiments with
continuous fixed-bed reactor systems, the LHSV is from about 0.5
h.sup.-1 to about 5.0 h.sup.-1. The GOR may be about 250 NL/L, 300
NL/L, 350 NL/L, 400 NL/L, 450 NL/L, 500 NL/L, 550 NL/L, 600 NL/L,
650 NL/L, 700 NL/L, 750 NL/L, 800 NL/L, 850 NL/L, 900 NL/L, 950
NL/L, 1000 NL/L, 1050 NL/L, 1100 NL/L, 1150 NL/L, 1200 NL/L, 1250
NL/L, 1300 NL/L, 1350 NL/L, 1400 NL/L, 1450 NL/L, 1500 NL/L, 1550
NL/L, and ranges between any two of these values or above any one
of these values. In some embodiments with continuous fixed-bed
reactor systems, GOR is from about 400 NL/L to about 1400 NL/L.
[0040] The reactor effluent is directed to a high pressure
separator for separating the gas stream containing unreacted
hydrogen and gas phase byproducts such as water, CO, CO.sub.2,
H.sub.2S, NH.sub.3, and propane from the liquid HDO products. The
gas is then cooled and directed to a three-phase cold separator
drum. There a water stream with dissolved carbonate, bisulfide, and
ammonium salts, a hydrocarbon stream containing light hydrocarbons,
and a hydrogen rich gas stream are separated. The hydrogen rich gas
is optionally scrubbed to remove the gas phase byproducts and
recycled to the reactor. The liquid HDO product from the high
pressure separator may also be partially recycled to the reactor to
dilute the reactive bio-based feed to the exothermic HDO
reactor.
[0041] Those skilled in the art recognize that variations to these
operating conditions may be made based on purity of available
hydrogen gas and to ensure proper three-phase (H.sub.2 gas/liquid
feed/solid catalyst) contacting regime within the reactor. The
liquid paraffin product composition obtained from subjecting most
fatty acid/ester bio-based feeds to HDO is a hydrocarbon
composition rich in n-paraffins in the C.sub.11 to C.sub.22 range.
The HDO product contains between about 80 wt % and 100 wt %
n-paraffins, between about 0 wt % and about 20 wt % isoparaffins,
between about 0 wt % and about 10 wt % cycloparaffins (also called
naphthenes or naphthenics), between about 0 wt % and about 10% wt %
olefins, and below about 1 wt % total aromatics. It is important to
note that the method does not involve more severe aromatic
hydrogenation conditions. The HDO product may contain n-paraffins
in the amount of about 82 wt %, about 84 wt %, about 86 wt %, about
88 wt %, about 90 wt %, about 92 wt %, about 94 wt %, about 96 wt
%, about 98 wt %, and ranges between any two of these values or
above any one of these values. The n-paraffins have a
biodegradability of at least about 40% after about 23 days of
exposure to microorganisms. The biodegradability may be about 42%,
about 44%, about 46%, about 48%, about 50%, about 52%, about 54%,
about 56%, about 58%, about 60%, about 62%, about 64%, about 66%,
about 68%, about 70%, about 72%, about 74%, about 76%, about 78%,
about 80%, and ranges between any two of these values or greater
than any one of these values. The n-paraffins have a kinematic
viscosity of less than about 10 cSt at 40.degree. C. The
n-paraffins may have a kinematic viscosity at 40.degree. C. of
about 9 cSt, about 8 cSt, about 7 cSt, about 6 cSt, about 5 cSt,
about 4 cSt, about 3 cSt, about 2 cSt, about 1 cSt, and ranges in
between any two of these values or below any one of these
values.
[0042] The HDO product may contain cycloparaffins in the amount of
about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt
%, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, and
ranges between any two of these values or below any one of these
values. The HDO product may contain aromatics in the amount of
about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about 0.6 wt %,
about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt %,
about 0.1 wt %, and ranges between any two of these values or below
any one of these values. In some embodiments, the HDO product
contains less than 0.1 wt % total aromatics. In some embodiments,
the HDO product is free of benzene. The HDO product has a kinematic
viscosity of less than about 10 cSt at 40.degree. C. The HDO
product may have a kinematic viscosity at 40.degree. C. of about 9
cSt, about 8 cSt, about 7 cSt, about 6 cSt, about 5 cSt, about 4
cSt, about 3 cSt, about 2 cSt, about 1 cSt, and ranges in between
any two of these values or below any one of these values.
[0043] The HDO product may be distilled to yield a synthetic
renewable drilling base fluid in the C.sub.16-C.sub.18 range. This
fluid has a flash point greater than about 100.degree. C., a
kinematic viscosity in the range of about 3 cSt to about 4 cSt at
40.degree. C., a pour point of about 16.degree. C. to about
20.degree. C., high thermal and oxidative stability due to
paraffinic structure (i.e. having a total insoluble content of 0.2
mg/100 mL or less according to the ASTM D2274 accelerated oxidative
aging method when 20 wppm or more anti-oxidant is added to the
fluid), low aquatic toxicity and ecotoxicity (i.e. having an
LC.sub.50 value of 3.5 mg/L or higher where LC.sub.50 is the
concentration at which half a population of the organism dies of
ingesting the fluid, and is typically the average of 24 hour, 48
hour, and 72 hour exposure tests on Daphia magna, Pimephales
promelas, or Rainbow Trout), and a biodegradability greater than
about 40% according to ASTM D5864-05, incorporated herein by
reference. ASTM D5864-05 measures how much of a material breaks
down into CO.sub.2 by microorganisms over a period of 23 days. In
contrast to the paraffins of this application, typical
petroleum-based mineral oils have biodegradability in the 15-35%
range, while synthetic oils like poly alpha-olefins (PAOs) have
biodegradability in the 5-30% range. Organic compounds with low
biodegradability (i.e. less than about 40% biodegradability) are
said to bioaccumulate. Bioaccumulation tends to magnify the toxic
effect of chemicals on the environment.
Hydroisomerization of Bio-Based Paraffins:
[0044] The HDO paraffins may be subjected to hydroisomerization to
provide a hydroisomerized product. The hydroisomerized product
includes methyl-branched paraffins in the C.sub.16-C.sub.18 range
with low pour point, high thermal/oxidative stability, and low
ecotoxicity. Hydroisomerization is conducted over a bifunctional
catalyst at temperatures in the range of about 200.degree. C. to
about 500.degree. C. The hydroisomerization may be conducted at a
temperature of about 220.degree. C., about 240.degree. C., about
260.degree. C., about 280.degree. C., about 300.degree. C., about
320.degree. C., about 340.degree. C., about 360.degree. C., about
380.degree. C., about 400.degree. C., about 420.degree. C., about
440.degree. C., about 460.degree. C., about 480.degree. C., and
ranges between any two of these values or above any one of these
values. Bifunctional catalysts are those having a
hydrogenation-dehydrogenation activity from a Group VIB and/or
Group VIII metal, and acidic activity from an amorphous or
crystalline support such as amorphous silica-alumina (ASA),
silicon-aluminum-phosphate (SAPO) molecular sieve, or aluminum
silicate zeolite (ZSM). In some embodiments, the hydroisomerization
catalysts include Pt/Pd-on-ASA, and Pt-on-SAPO-11.
[0045] In some embodiments, hydroisomerization is conducted in
continuous fixed-bed reactors. In such embodiments, the hydrogen
partial pressure for hydroisomerization is in the range between
about 30 bar and about 160 bar, GORs are in the range of about 100
NL/L to about 1,000 NL/L, and LHSV in the range from about 0.2
hr.sup.-1 to about 5 hr.sup.-1. In some embodiments, the hydrogen
partial pressure for hydroisomerization is about 40 bar, about 50
bar, about 60 bar, about 70 bar, about 80 bar, about 90 bar, about
100 bar, about 110 bar, about 120 bar, about 130 bar, about 140
bar, about 150 bar, and ranges between any two of these values or
above any one of these values. In some embodiments, the GOR may be
about 150 NL/L, about 200 NL/L, about 250 NL/L, 300 NL/L, 350 NL/L,
400 NL/L, 450 NL/L, 500 NL/L, 550 NL/L, 600 NL/L, 650 NL/L, 700
NL/L, 750 NL/L, 800 NL/L, 850 NL/L, 900 NL/L, 950 NL/L, and ranges
between any two of these values or above any one of these values.
The LHSV may be about 0.3 h.sup.-1, about 0.4 h.sup.-1, about 0.5
h.sup.-1, about 0.6 h.sup.-1, about 0.7 h.sup.-1, about 0.8
h.sup.-1, about 0.9 h.sup.-1, about 1.0 h.sup.-1, about 1.2
h.sup.-1, about 1.4 h.sup.-1, about 1.6 h.sup.-1, about 1.8
h.sup.-1, about 2.0 h.sup.-1, about 2.2 h.sup.-1, about 2.4
h.sup.-1, about 2.6 h.sup.-1, about 2.8 h.sup.-1, about 3.0
h.sup.-1, about 3.0 h.sup.-1, about 3.2 h.sup.-1, about 3.4
h.sup.-1, about 3.6 h.sup.-1, about 3.8 h.sup.-1, about 4.0
h.sup.-1, about 4.2 h.sup.-1, about 4.4 h.sup.-1, about 4.6
h.sup.-1, about 4.8 h.sup.-1, and ranges between any two of these
values or above any one of these values.
[0046] In an embodiment, the HDO product is hydroisomerized
according to the conditions described herein using Pt/SAPO-11
catalyst. The hydroisomerizate is preferably stripped of light
hydrocarbons in order to raise the flash point above 60.degree. C.
The flash point may be above 70.degree. C., above 80.degree. C.,
above 90.degree. C., or above 100.degree. C. The hydroisomerized
product has a ratio of isoparaffins-to-normal paraffins in the
range of about 1:1 to about 30:1. The ratio of
isoparaffins-to-normal paraffins may be about 2:1, about 3:1, about
4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, about
10:1, about 11:1, about 12:1, about 13:1, about 14:1, about 15:1,
about 16:1, about 17:1, about 18:1, about 19:1, about 20:1, about
21:1, about 22:1, about 23:1, about 24:1, about 25:1, about 26:1,
about 27:1, about 28:1, about 29:1, and ranges between any two of
these values or above any one of these values. In some embodiments,
the ratio of isoparaffins-to-normal paraffins is between about 5:1
and about 20:1. In the hydroisomerized product at least 80 wt % of
the isoparaffins are mono-methyl branched paraffins. The
mono-methyl branched paraffins may be about 81 wt %, about 82 wt %,
about 83 wt %, about 84 wt %, about 85 wt %, about 86 wt %, about
87 wt %, about 88 wt %, about 89 wt %, about 90 wt %, about 91 wt
%, about 92 wt %, about 93 wt %, about 94 wt %, about 95 wt %,
about 96 wt %, about 97 wt %, about 98 wt %, about 99 wt %, and
ranges between any two of these values or above any one of these
values. Examples of the mono-methyl branched paraffins in the
hydroisomerized HDO product include 4-methyl heptadecane, 3-methyl
hexadecane, and 2-methyl pentadecane. Of the mono-methyl branched
isoparaffins, less than 30 wt % are terminal branched (i.e.
2-methyl branched). In some embodiments, less than 20 wt % of the
mono-methyl branched isoparaffins are terminal branched. In some
embodiments, less than 15 wt % of the mono-methyl branched
isoparaffins are terminal branched. In some embodiments, less than
10 wt % of the mono-methyl branched isoparaffins are terminal
branched. In some embodiments, less than 5 wt % of the mono-methyl
branched isoparaffins are terminal branched. It is important to
note that the method does not involve more severe aromatic
hydrogenation conditions.
[0047] The isoparaffins have a biodegradability of at least about
40% after about 23 days of exposure to microorganisms. The
biodegradability may be about 42%, about 44%, about 46%, about 48%,
about 50%, about 52%, about 54%, about 56%, about 58%, about 60%,
about 62%, about 64%, about 66%, about 68%, about 70%, about 72%,
about 74%, about 76%, about 78%, about 80%, and ranges between any
two of these values or greater than any one of these values. The
isoparaffins have a kinematic viscosity of less than about 10 cSt
at 40.degree. C. The isoparaffins may have a kinematic viscosity at
40.degree. C. of about 9 cSt, about 8 cSt, about 7 cSt, about 6
cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2 cSt, about 1
cSt, and ranges in between any two of these values or below any one
of these values.
[0048] The hydroisomerized product may contain aromatics in the
amount of about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about 0.6
wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt
%, about 0.1 wt %, and ranges between any two of these values or
below any one of these values. In some embodiments, the
hydroisomerized product contains less than 0.1 wt % total
aromatics. In some embodiments, the hydroisomerized product is free
of benzene. The hydroisomerized product has a kinematic viscosity
of less than about 10 cSt at 40.degree. C. The hydroisomerized
product has a kinematic viscosity of less than about 10 cSt at 40
.degree. C. The hydroisomerized product may have a kinematic
viscosity at 40.degree. C. of about 9 cSt, about 8 cSt, about 7
cSt, about 6 cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2
cSt, about 1 cSt, and ranges in between any two of these values or
below any one of these values.
[0049] Due the presence of mostly internal mono-methyl branched
paraffins, the hydroisomerized HDO product of this technology has
an excellent balance of properties for use as drilling and/or
hydraulic fracturing fluids. The pour point of the hydroisomerized
fluid of this embodiment is at most -10.degree. C. The pour point
may be at most about -15.degree. C., at least about -20.degree. C.,
at most about -25.degree. C., at most about -30.degree. C., at most
about -35.degree. C., at most about -40.degree. C., or at most
about -45.degree. C. The thermo-oxidative stability of the fluid
may be measured by amount of insolubles formed upon heating and
reported as mg/100 mL according to ASTM D2274. For example, the
stability thus measured can be as high as 20 mg/100 mL for fluids
with inferior oxidative stability properties, such as fatty acid
esters. The lower the concentration of insolubles formed, the
higher the thermo-oxidative stability of the fluid. The ASTM D2274
oxidative stability of the fluid produced by hydroisomerization of
the HDO product as described herein is between about 0 mg/100 mL
and about 2 mg/100 mL upon addition of up to 20 wppm anti-oxidant.
Preferred anti-oxidants for the bio-based hydrocarbon fluids of
this technology are hindered phenols, such as butyrated hydroxy
toluene (BHT). Other examples of suitable anti-oxidants for the
bio-based synthetic hydrocarbon fluids of this invention include
2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2- and
3-t-butyl-4-hydroxyanisol (BHA), 2,6-distyrenated p-cresol,
2,6-di-t-butylphenol, 2,6-di-t-butyl-4-sec-butylphenol,
2,6-di-t-butyl-4-nonylphenol,
2,4-bis-(n-octylthio)-6-(4-hydroxy-3',5'-di-t-butylanilino)-1,3,5-triazin-
e, 2,4-bis-(octylthiomethyl)-6-methylphenol,
2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, the
butylated reaction product of p-cresol and dicylcopentadiene, the
mixed methylenic bridged adducts of alkylated phenol and dodecane
thiol, tetrakis methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)
methane, 1,3,5-trimethyl-2,4,6-tris
(3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris
(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, and mixtures of any
two or more thereof of the recited anti-oxidants.
Chlorinating Bio-Based Paraffins:
[0050] Paraffin chlorination according to the present technology is
one way of increasing the viscosity of a paraffinic fluid while
reducing crystallinity and hence lowering the paraffin pour point.
For example, the HDO product does not have the required viscosity
and pour point for use, by itself, in such industrial processing
fluid applications as metal-working.
[0051] The HDO product and/or the hydroisomerized product may be
chlorinated in a batch reactor by sparging pure chlorine gas into
the liquid at a temperature in the range between about 60.degree.
C. and about 150.degree. C. The temperature of the chlorination
reaction may be about 65.degree. C., about 70.degree. C., about
80.degree. C., about 85.degree. C., about 90.degree. C., about
95.degree. C., about 100.degree. C., about 105.degree. C., about
110.degree. C., about 115.degree. C., about 120.degree. C., about
125.degree. C., about 130.degree. C., about 140.degree. C., about
145.degree. C., and ranges in between any two of these values or
greater than any one of these values. In some embodiments, the
temperature is in the range between about 80.degree. C. and about
120.degree. C. Chlorination is an exothermic reaction and cooling
is necessary. Generally catalysts are not necessary at these
temperatures, but in some embodiments UV light is used to
accelerate the reaction. Once the desired degree of chlorination,
typically between about 30 wt % and about 70 wt %, and viscosity
has been achieved, the chlorine supply is discontinued and the
reactor purged with air or nitrogen to remove excess chlorine and
hydrochloric acid gas. Hydrochloric acid is a co-product of the
paraffin chlorination process.
[0052] The chlorinated paraffins, i.e. the chlorinated product, can
be used as an industrial process fluid for metal-working
lubricants, as plasticizers, flame-retardants, and fat liquors for
leather. Plasticizers are generally used to make rigid polymers
like PVC soft and rubbery. Addition of chlorinated paraffins also
imparts flame-retardancy to the polymer compound. Fat liquors are
fluids that are used to improve the life and appearance of articles
made of leather, such as jackets, handbags, and shoes. In some
embodiments, the chlorinated product is used as a protecting agent,
a cleaning agent, or a combination of both. In some embodiments,
the chlorinated product acts as a flame retardant. In some
embodiments, the chlorinated product is used to clean fabric,
metal, or plastic.
[0053] The chlorinated product has a kinematic viscosity of greater
than about 10 cSt at 40.degree. C. The chlorinated product may have
a kinematic viscosity at 40.degree. C. of about 12 cSt, about 14
cSt, about 16 cSt, about 18 cSt, about 20 cSt, about 22 cSt, about
24 cSt, about 26 cSt, about 28 cSt, about 30 cSt, and ranges in
between any two of these values or greater than any one of these
values. The chlorinated product is between about 30 wt % and about
70 wt % chlorine in the form of chlorine covalently bound to
carbon. The amount of covalently bonded chlorine in the chlorinated
product may be about 35 wt %, about 40 wt %, about 45 wt %, about
50 wt %, about 55 wt %, about 60 wt %, about 65 wt %, and ranges
between any two of these values or greater than any one of these
values. The chlorinated product has less than about 1 wt %
aromatics. The chlorinated product may contain aromatics in the
amount of about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about 0.6
wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt
%, about 0.1 wt %, and ranges between any two of these values or
below any one of these values. In some embodiments, the chlorinated
product contains less than 0.1 wt % total aromatics. In some
embodiments, the chlorinated product is free of benzene. In some
embodiments, the chlorinated product is used as a protecting agent,
a cleaning agent, or a combination of both. In some embodiments,
the chlorinated product acts as a flame retardant. In some
embodiments, the chlorinated product is used to clean fabric,
metal, or plastic.
Dehydrochlorinadon of Bio-Derived Paraffins:
[0054] The chlorinated products may optionally be subjected to
dehydrochlorination, wherein the chlorine is removed as
hydrochloric acid. As an example, in embodiments where the
chlorinated product is exclusively made from the HDO product,
dehydrochlorination yields a linear olefin composition having a
carbon number range similar to the HDO paraffin. The
dehydrochlorination reaction takes place over silica or bauxite at
temperatures in the 360.degree. C.-700.degree. C. range. The
reaction may take place at a temperature of about 380.degree. C.,
about 400.degree. C., about 420.degree. C., about 440.degree. C.,
about 460.degree. C., about 480.degree. C., about 500.degree. C.,
about 550.degree. C., about 600.degree. C., about 650.degree. C.,
and ranges in between any two of these values or above any one of
these values. In some embodiments, the reaction takes place at
temperature in the range from about 400.degree. C. to about
600.degree. C. Dehydrochlorination may proceed in the range from
about 68% conversion to about 100% conversion. Dehydrochlorination
can proceed to about 70% conversion, about 75% conversion, about
80% conversion, about 85% conversion, about 90% conversion, about
95% conversion, about 98% conversion, about 99% conversion, and
ranges in between any two of these values or above any one of these
values. As such, the dehydrochlorination reactor product from
dehydrochlorination of the HDO product is a C.sub.16/C.sub.18
linear hydrocarbon composition comprising up to 100% internal
olefins, characterized by higher biodegradability than saturated
hydrocarbons. This olefinic composition has a lower pour point and
higher lubricity than the equivalent paraffin composition, making
it particularly well-suited for drilling and hydraulic fracturing
fluid formulations.
[0055] The olefinic composition has a biodegradability of at least
about 40% after about 23 days of exposure to microorganisms. The
biodegradability may be about 42%, about 44%, about 46%, about 48%,
about 50%, about 52%, about 54%, about 56%, about 58%, about 60%,
about 62%, about 64%, about 66%, about 68%, about 70%, about 72%,
about 74%, about 76%, about 78%, about 80%, and ranges between any
two of these values or greater than any one of these values. The
olefinic composition has a kinematic viscosity of less than about
10 cSt at 40.degree. C. The olefinic composition may have a
kinematic viscosity at 40.degree. C. of about 9 cSt, about 8 cSt,
about 7 cSt, about 6 cSt, about 5 cSt, about 4 cSt, about 3 cSt,
about 2 cSt, about 1 cSt, and ranges in between any two of these
values or below any one of these values. The olefinic composition
may contain aromatics in the amount of about 0.9 wt %, about 0.8 wt
%, about 0.7 wt %, about 0.6 wt %, about 0.5 wt %, about 0.4 wt %,
about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, and ranges between
any two of these values or below any one of these values. In some
embodiments, the olefinic composition contains less than 0.1 wt %
total aromatics. In some embodiments, the olefinic composition is
free of benzene. In some embodiments, the olefinic composition is
used as a hydraulic fracturing fluid, as a drilling fluid, or a
combination of the two.
Dehydrogenation of Bio-Derived Paraffins:
[0056] The paraffinic fluid, for example the HDO product and/or the
hydroisomerization product, may be subjected to dehydrogenation to
produce a olefinic fluid with an improved balance of
biodegradability, lubricity, thermo-oxidative stability,
ecotoxicity, and pour point, for drilling base fluids. The reaction
takes place at a temperature in the range from about 360.degree. C.
to about 660.degree. C. The reaction may take place at about
380.degree. C., about 400.degree. C., about 420.degree. C., about
440.degree. C., about 460.degree. C., about 480.degree. C., about
500.degree. C., about 520.degree. C., about 540.degree. C., about
560.degree. C., about 580.degree. C., about 600.degree. C., about
620.degree. C., about 640.degree. C., and ranges between any two of
these values or above any one of these values. In some embodiments,
the reaction takes place in a temperature in the range from about
440.degree. C. to about 580.degree. C. The reaction is endothermic
and is favored at low pressures. Typical operating pressures are in
the range from about 1 bar to about 20 bar. The operating pressure
may be about 2 bar, about 3 bar, about 4 bar, about 5 bar, about 6
bar, about 7 bar, about 8 bar, about 9 bar, about 10 bar, about 11
bar, about 12 bar, about 13 bar, about 14 bar, about 15 bar, about
16 bar, about 17 bar, about 18 bar, about 19 bar, and ranges
between any two of these values or above any one of these values.
In some embodiments, the operating pressure is from about 2 bar to
about 12 bar. At these conditions, the hydrocarbons are in vapor
phase. Generally base metals and noble metal catalysts from Groups
VIB and VIII that have hydrogenation-dehydrogenation activity
provide a low activation energy mechanism for paraffin
dehydrogenation. Such metals include Pt, Pd, Rh, Ru, Ir, Os, and
Re. The reaction is carried out in gas phase at high temperatures
and low pressures. Preferred catalyst systems for paraffin
dehydrogenation include alkali and alkaline earth metal promoters
as well. A preferred catalyst for the system is platinum/lithium on
alumina.
[0057] In an embodiment, the HDO paraffins are pressurized to about
10 bar and preheated to about 580.degree. C. before entering a
dehydrogenation reactor. It is important to note that the
conditions provided in this embodiment are applicable to the
dehydrogenation of the hydroisomerized product described earlier.
The reactor is packed with Pt/Li-on-alumina catalyst. The reactor
geometry is selected to provide low pressure drop while ensuring
sufficient contact time to achieve desired conversion, and
preferably approach the thermodynamic equilibrium conversion for
the endothermic reactions. Preferred contact times are expressed by
liquid hourly space velocities (LHSV) in the range of about 1
h.sup.-1 to about 10 h.sup.-1. The LHSV may be about 1.2 h.sup.-1,
about 1.4 h.sup.-1, about 1.6 h.sup.-1, about 1.8 h.sup.-1, about
2.0 h.sup.-1, about 2.2 h.sup.-1, about 2.4 h.sup.-1, about 2.6
h.sup.-1, about 2.8 h.sup.-1, about 3.0 h.sup.-1, about 3.0
h.sup.-1, about 3.2 h.sup.-1, about 3.4 h.sup.-1, about 3.6
h.sup.-1, about 3.8 h.sup.-1, about 4.0 h.sup.-1, about 4.2
h.sup.-1, about 4.4 h.sup.-1, about 4.6 h.sup.-1, about 4.8
h.sup.-1, about 5.0 h.sup.-1, about 5.2 h.sup.-1, about 5.4
h.sup.-1, about 5.6 h.sup.-1, about 5.8 h.sup.-1, about 6.0
h.sup.-1, about 6.2 h.sup.-1, about 6.4 h.sup.-1, about 6.6
h.sup.-1, about 6.8 h.sup.-1, about 7.0 h.sup.-1, about 7.2
h.sup.-1, about 7.4 h.sup.-1, about 7.6 h.sup.-1, about 7.8
h.sup.-1, about 8.0 h.sup.-1, about 8.2 h.sup.-1, about 8.4
h.sup.-1, about 8.6 h.sup.-1, about 8.8 h.sup.-1, about 9.0
h.sup.-1, about 9.2 h.sup.-1, about 9.4 h.sup.1, about 9.6 h.sup.1,
about 9.8 h.sup.-1, and ranges between any two of these values or
above any one of these values. It should be noted that although
space velocities are expressed in terms of liquid feed, in some
embodiments of the dehydrogenation conditions the reactor feed and
products are in the vapor phase. In some embodiments, a plurality
of reactors is configured in series, with provisions for heating
each reactor feed. In some embodiments, between about 5 wt % and
about 40 wt % of the HDO n-paraffins are converted to linear
olefins. The conversion of HDO n-paraffins to linear olefins may be
about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about
30 wt %, about 35 wt %, and ranges in between any two of these
values or above any one of these values. In some embodiments,
between about 10 wt % and about 30 wt % of the HDO n-paraffins are
converted to linear olefins. The reactor effluent is cooled to
condense a linear hydrocarbon product composition from hydrogen,
where the linear hydrocarbon product composition is primarily in
the C.sub.16-C.sub.18 range. The hydrogen may be partially recycled
to the reactor to mitigate coking in the reactor. A
hydrogen-to-hydrocarbon mole ratio of about 1:1 to about 20:1 is
utilized. The hydrogen-to-hydrocarbon mole ratio may be about 2:1,
about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1,
about 9:1, about 10:1, about 11:1, about 12:1, about 13:1, about
14:1, about 15:1, about 16:1, about 17:1, about 18:1, about 19:1,
and ranges between any two of these values or above any one of
these values. In some embodiments, the hydrogen-to-hydrocarbon mole
ratio is from about 8:1 to about 12:1.
[0058] The liquid product of this embodiment of the dehydrogenation
of the HDO product is a straight-chain hydrocarbon composition
comprising of n-paraffins and linear olefins. The composition
comprises 50-90 wt % n-paraffins in the C.sub.16-C.sub.18 range,
10-40 wt % C.sub.16-C.sub.18 linear internal olefins in the
C.sub.16-C.sub.18 range, and 0-10 wt % linear alpha olefins in the
C.sub.16-C.sub.18 range. The composition may have n-paraffins in
the C.sub.16-C.sub.18 range in the amount of about 55 wt %, about
60 wt %, about 65 wt %, about 70 wt %, about 75 wt %, about 80 wt
%, about 85 wt %, and ranges in between any two of these values or
below any one of these values. The composition may have linear
internal olefins in the C.sub.16-C.sub.18 range in the amount of
about 15 wt %, about 20 wt %, about 25 wt %, about 30 wt %, about
35 wt %, and ranges between any two of these values or above any
one of these values. The composition may have linear alpha olefins
in the C.sub.16-C.sub.18 range in the amount of about 0 wt % to
about 5 wt % or about 5 wt % to about 10 wt %.
[0059] Due the presence of linear internal olefins, the pour point
of the straight-chain hydrocarbon composition is lowered. Compared
to fully saturated hydrocarbons, this composition offers superior
biodegradability, making it attractive as a drilling base
fluid.
[0060] The olefinic fluid has a biodegradability of at least about
40% after about 23 days of exposure to microorganisms. The
biodegradability may be about 42%, about 44%, about 46%, about 48%,
about 50%, about 52%, about 54%, about 56%, about 58%, about 60%,
about 62%, about 64%, about 66%, about 68%, about 70%, about 72%,
about 74%, about 76%, about 78%, about 80%, and ranges between any
two of these values or greater than any one of these values. The
olefinic fluid has a kinematic viscosity of less than about 10 cSt
at 40.degree. C. The olefinic fluid may have a kinematic viscosity
at 40.degree. C. of about 9 cSt, about 8 cSt, about 7 cSt, about 6
cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2 cSt, about 1
cSt, and ranges in between any two of these values or below any one
of these values. The olefinic fluid of the present technology may
contain aromatics in the amount of about 0.9 wt %, about 0.8 wt %,
about 0.7 wt %, about 0.6 wt %, about 0.5 wt %, about 0.4 wt %,
about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, and ranges between
any two of these values or below any one of these values. In some
embodiments, the olefinic fluid contains less than 0.1 wt % total
aromatics. In some embodiments, the olefinic fluid is free of
benzene. In some embodiments, the olefinic fluid is used as a
hydraulic fracturing fluid, as a drilling fluid, or a combination
of the two.
Acid-Catalyzed Oligomerization:
[0061] It is to be understood that the term "oligomerization" as
used herein refers to the formation of a compound from 2, 3, 4, 5,
6, 7, 8, 9 or 10 monomers, where the compound formed by
oligomerization is an "oligomer" or an "oligomerized product." For
example, a dimer is a compound made from the oligomerization of 2
monomers, a trimer is a compound made from the oligomerization of 3
monomers, and a tetramer is a compound made from the
oligomerization of 4 monomers. The olefins produced by
dehydrogenation of the bio-derived paraffins or by
dehydrochlorination of the chlorinated product, described above,
can be oligomerized to produce fluids having a higher average
molecular weight, higher boiling range, and higher viscosity. Since
most of the carbon-carbon double bonds in the linear olefins are
mainly in the internal positions (as indicated in the
aforementioned section describing the internal olefins), the
branched dimers are characterized by mainly C.sub.2+ chain
branching. Such fluids, having a kinematic viscosity greater than
about 10 cSt at 40.degree. C. are excellently suited for various
mineral oil and lubricating oil applications. The oligomerized
product may have a kinematic viscosity at 40 .degree. C. of about
12 cSt, about 14 cSt, about 16 cSt, about 18 cSt, about 20 cSt,
about 22 cSt, about 24 cSt, about 26 cSt, about 28 cSt, about 30
cSt, and ranges in between any two of these values or greater than
any one of these values. In some embodiments, the oligomerized
product has a kinematic viscosity greater than about 20 cSt at
40.degree. C.
[0062] Acids for olefin oligomerization include, but are not
limited to, Lewis acids such as boron trifluoride and aluminum
trichloride. Heterogeneous catalysts such as zeolites are another
class of catalysts for olefin oligomerization. The reactions are
conducted in a continuous stirred tank reactor using between about
1 wt % and about 15 wt % of the Lewis acid catalyst based on a
oligomerization reactor hydrocarbon feed basis. The Lewis acid
catalyst may be at about 2 wt %, about 3 wt %, about 4 wt %, about
5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %,
about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt %, about
14 wt %, and ranges between any two of these values. In some
embodiments, the Lewis acid catalyst is from about 2 wt % to about
8 wt %. The reactor operates at a temperature in about the
0.degree. C. to 200.degree. C. range, under about 1 bar to about 10
bar pressure. The reactor may operate at a temperature of about
10.degree. C., about 20.degree. C., about 30.degree. C., about
40.degree. C., about 50.degree. C., about 60.degree. C., about
70.degree. C., about 80.degree. C., about 90.degree. C., about
100.degree. C., about 110.degree. C., about 120.degree. C., about
130.degree. C., about 140.degree. C., about 150.degree. C., about
160.degree. C., about 170.degree. C., about 180.degree. C., about
190.degree. C., and ranges in between any two of these values. In
some embodiments, the temperature is from about 20.degree. C. to
about 120.degree. C. The reactor may operate at a pressure of about
2 bar, about 3 bar, about 4 bar, about 5 bar, about 6 bar, about 7
bar, about 8 bar, about 9 bar, and ranges in between any two of
these values or above any one of these values. Reactor residence
times are in the range of about 20 minutes to about 120 minutes.
The reactor residence time may be about 30 minutes, about 40
minutes, about 50 minutes, about 60 minutes, about 70 minutes,
about 80 minutes, about 90 minutes, about 100 minutes, about 110
minutes, and ranges in between any two of these values. In some
embodiments, the reactor residence time is from about 30 minutes to
about 90 minutes. The reactor effluent includes products of the
oligomerization reaction. Unreacted hydrocarbons, if present, may
be separated from the oligomerized product. The oligomerization
product is predominately dimers and tetramers of the linear
internal olefins. In some embodiments, the dimers and tetramers are
greater than 60 wt % of the oligomerized product. The
oligomerization product of this embodiment includes long-chain
branched hydrocarbons. The unreacted linear hydrocarbons include
the paraffin feed to the dehydrogenation reactor and the olefinic
fluid not reacted under acid-catalyzed oligomerization
conditions.
[0063] The oligomerized product may include a dimer, trimer,
tetramer, or a mixture of any two or more thereof. The oligomerized
product of the present technology may contain aromatics in the
amount of about 0.9 wt %, about 0.8 wt %, about 0.7 wt %, about 0.6
wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt
%, about 0.1 wt %, and ranges between any two of these values or
below any one of these values. In some embodiments, the
oligomerized product contains less than 0.1 wt % total aromatics.
In some embodiments, the oligomerized product is free of benzene.
The oligomerized product has a biodegradability of at least about
40% after about 23 days of exposure to microorganisms. The
biodegradability may be about 42%, about 44%, about 46%, about 48%,
about 50%, about 52%, about 54%, about 56%, about 58%, about 60%,
about 62%, about 64%, about 66%, about 68%, about 70%, about 72%,
about 74%, about 76%, about 78%, about 80%, and ranges between any
two of these values or greater than any one of these values. In
some embodiments, the oligomerized product is used as a drilling
fluid, a hydraulic fracturing fluid, a metal working fluid, a
protecting agent, or a combination of any two or more thereof.
Peroxide-Initiated Oligomerization:
[0064] Organic peroxide treatment may be used to initiate
oligomerization of HDO and/or hydroisomerized HDO products. As
stated above, it is to be understood that the term
"oligomerization" as used herein refers to the formation of a
compound from 2, 3, 4, 5, 6, 7, 8, 9 or 10 monomers, where the
compound formed by oligomerization is an "oligomer." For example, a
dimer is a compound made from the oligomerization of 2 monomers, a
trimer is a compound made from the oligomerization of 3 monomers,
and a tetramer is a compound made from the oligomerization of 4
monomers. The product composition, comprising dimers and co-dimers
of the linear and/or branched paraffins, has a kinematic viscosity
greater than about 10 cSt at 40 C. The product is thus well suited
for use in various mineral oil and lubricating oil
applications.
[0065] Organic peroxides generate free radicals that extract
hydrogen atoms from secondary and tertiary carbons of the
paraffinic hydrocarbons, providing free radical sites therein for
subsequent coupling reactions. The organic peroxides for the
reaction are of the formula R-O-O-R' where R and R' are each
independently H, alkyl, or aryl. In some embodiments, organic
peroxides for the reaction include dialkyl peroxides including, but
not limited to, di-tert butyl peroxide (DTBP), 2,5-dimethyl
2,5-di(t-butylperoxy)hexane, dicumyl peroxide, dibenzoyl peroxide,
dipropyl peroxide, ethyl propyl peroxide, tert-butyl tert-amyl
peroxide, or combinations of any two or more thereof.
[0066] Peroxide-initiated oligomerization may be carried out in
batch or continuous reactors. Preferred batch reactor embodiments
are agitated tanks with provisions for heat transfer/temperature
control. These include jackets, internal coils, or pump-around heat
exchange. Continuous flow reactors include those approaching
plug-flow behavior such as tubular reactors (including, but not
limited to, static mixers) and fixed-bed vessels packed with inert
media like ceramic balls. As with the batch reactors, these plug
-flow reactors may include provisions for heat transfer/temperature
control. A low capital cost embodiment of the continuous reactor
for peroxide-initiated oligomerization is the jacketed pipe or the
pipe-in-pipe reactor.
[0067] The reactor feed comprising HDO and/or hydroisomerized HDO
paraffins includes between about 2 wt % and about 40 wt % organic
peroxide and the reactor is controlled at a temperature from about
50.degree. C. to about 250.degree. C. The organic peroxide may be
in the amount of about 3 wt %, about 4 wt %, about 5 wt %, about 6
wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %,
about 12 wt %, about 14 wt %, about 16 wt %, about 18 wt %, about
20 wt %, about 22 wt %, about 24 wt %, about 26 wt %, about 28 wt
%, about 30 wt %, about 32 wt %, about 34 wt %, about 36 wt %,
about 38 wt %, and ranges between any two of these values or above
any one of these values. In some embodiments, the organic peroxide
is in the amount of about 5 wt % to about 20 wt %. The reactor
temperature may be about 60.degree. C., about 70.degree. C., about
80.degree. C., about 90.degree. C., about 100.degree. C., about
110.degree. C., about 120.degree. C., about 130 .degree. C., about
140.degree. C., about 150.degree. C., about 160.degree. C., about
170.degree. C., about 180.degree. C., about 190.degree. C., about
200.degree. C., about 210.degree. C., about 220.degree. C., about
230.degree. C., about 240.degree. C., and ranges in between any two
of these values. In some embodiments, the temperature is between
about 70.degree. C. and about 200.degree. C. The reactor is
controlled at a suitable pressure, high enough to ensure reactor
contents are in liquid phase. This pressure is typically from about
1 bar to about 10 bar. The reactor may operate at a pressure of
about 2 bar, about 3 bar, about 4 bar, about 5 bar, about 6 bar,
about 7 bar, about 8 bar, about 9 bar, and ranges in between any
two of these values or above any one of these values. Batch cycle
times, or residence times of continuous flow reactors, are in the
range from about 10 minutes to about 120 minutes. The reactor
residence time may be about 10 minutes, about 20 minutes, about 30
minutes, about 40 minutes, about 50 minutes, about 60 minutes,
about 70 minutes, about 80 minutes, about 90 minutes, about 100
minutes, about 110 minutes, and ranges in between any two of these
values. In some embodiments, the reactor residence time is from
about 20 minutes to about 90 minutes.
[0068] In the batch mode, all the peroxide may be charged at once
following addition of the paraffinic feedstock. The peroxide may
also be introduced in increments over the batch cycle time. In
other embodiments of peroxide-initiated oligomerization, the
organic peroxide is fed to the batch reactor continuously during
all or a portion of the batch reaction cycle time, preferably using
a metering pump or control valve. This mode of operation is also
referred to as "semi-batch" in the art.
[0069] The reactor effluent comprises oligomerization products,
mainly dimers and trimers of the HDO and/or hydroisomerization
paraffins. The unreacted paraffins, making up between about 0 wt %
and about 60 wt % of the effluent composition, are optionally
stripped (preferably via atmospheric or vacuum distillation) to
yield a oligomerized fluid product having a kinematic viscosity
greater than about 10 cSt at 40.degree. C. The oligomerized product
may have a kinematic viscosity at 40.degree. C. of about 12 cSt,
about 14 cSt, about 16 cSt, about 18 cSt, about 20 cSt, about 22
cSt, about 24 cSt, about 26 cSt, about 28 cSt, about 30 cSt, and
ranges in between any two of these values or greater than any one
of these values. In some embodiments, the oligomerized product has
a kinematic viscosity greater than about 20 cSt at 40.degree. C.
This product is well-suited for use in various lubricating
applications where a combination of high thermal stability, low
ecotoxicity, and good low temperature properties is desired. The
unreacted paraffins in the effluent composition may be about 1 wt
%, about 2 wt %, 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %,
about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 12
wt %, about 14 wt %, about 16 wt %, about 18 wt %, about 20 wt %,
about 22 wt %, about 24 wt %, about 26 wt %, about 28 wt %, about
30 wt %, about 32 wt %, about 34 wt %, about 36 wt %, about 38 wt
%, about 40 wt %, about 50 wt % and ranges between any two of these
values or above any one of these values.
[0070] The oligomerized product may include a dimer, trimer,
tetramer, or a mixture of any two or more thereof. The oligomerized
product has a biodegradability of at least about 40% after about 23
days of exposure to microorganisms. The biodegradability may be
about 42%, about 44%, about 46%, about 48%, about 50%, about 52%,
about 54%, about 56%, about 58%, about 60%, about 62%, about 64%,
about 66%, about 68%, about 70%, about 72%, about 74%, about 76%,
about 78%, about 80%, and ranges between any two of these values or
greater than any one of these values. The oligomerized product of
the present technology may contain aromatics in the amount of about
0.9 wt %, about 0.8 wt %, about 0.7 wt %, about 0.6 wt %, about 0.5
wt %, about 0.4 wt %, about 0.3 wt %, about 0.2 wt %, about 0.1 wt
%, and ranges between any two of these values or below any one of
these values. In some embodiments, the oligomerized product
contains less than 0.1 wt % total aromatics. In some embodiments,
the oligomerized product is free of benzene. In some embodiments,
the oligomerized product is used as a drilling fluid, a hydraulic
fracturing fluid, a metal working fluid, a protecting agent, or a
combination of any two or more thereof.
[0071] In another aspect, a method is provided involving protecting
a substance by applying the above-described paraffinic fluids. In
the method, the paraffinic fluid includes a hydrodeoxygenated
product; where the hydrodeoxygenated product is produced by
hydrodeoxygenating a bio-derived feed; the bio-derived feed
comprises bio-derived fatty acids, fatty acid esters, or a
combination thereof; the hydrodeoxygenated product comprises
n-paraffins; the paraffinic fluid contains less than 1 wt %
aromatics; and the n-paraffins have a kinematic viscosity of less
than about 10 cSt at 40.degree. C. and have a biodegradability of
at least 40% after about 23 days of exposure to microorganisms. In
some embodiments, the hydrodeoxygenated product includes
n-paraffins in the range of about 80 wt % to about 100 wt %;
cycloparaffins in the range of about 0 wt % to about 10 wt %; less
than about 1 wt % total aromatics. In some embodiments, the
paraffinic fluid further includes a hydroisomerized product
produced by at least partially hydroisomerizing the
hydrodeoxygenated product; where the hydroisomerized product
comprises isoparaffins where at least about 80 wt % of the
isoparaffins are mono-methyl branched paraffins; the mono-methyl
branched paraffins comprise less than about 30 wt % terminal
branched isoparaffins; and the isoparaffins have a kinematic
viscosity of less than about 10 cSt at 40.degree. C. and have a
biodegradability of at least about 40% after about 23 days of
exposure to microorganisms.
[0072] Thus, in some embodiments of the method, the substance is a
food crop, a metal, or wood. In some embodiments, protecting
involves solvating the substance. In such embodiments, the
substance includes pesticides, herbicides, paints, inks, or
coatings. In some embodiments of the method, protecting involves
cleaning the substance with the paraffinic fluid In such
embodiments, the substance comprises fabric, metal, or plastic. In
some embodiments of the method, protecting involves lubricating the
substance where the substance is metal. Such a method is
exemplified by the protecting applications listed for dry cleaning
fluids, industrial solvents, crop protection solvents/coating oils,
grain de-dusting oils, metal working fluids, industrial cleaning
fluids, lubricating base oils, polymerization fluids, transformer
oils, cosmetic oils, food preparation oils, and drilling fluids and
hydraulic fracturing fluids of the present technology.
Dry Cleaning Fluids:
[0073] Bio-based synthetic fluids of this technology may be used as
a substitute for petroleum-based solvents and perchloroethylene for
dry cleaning of apparel. These fluids comprise hydrocarbons in the
C.sub.10-C.sub.15 range. The paraffinic nature of the fluid
(specifically its non-corrosive, non-polar properties) allows it to
be used with many sensitive fabrics. They remove oil and grease
effectively, aid in removing water-soluble dirt when combined with
effective detergents, and are virtually odorless. The kinematic
viscosities of these fluids are less than 10 cSt at 40.degree. C.
For reducing risk of fire, the flash point is generally above
38.degree. C. Dry cleaning fluids of this technology include
hydrocarbons in the C.sub.10-C.sub.15 range.
Industrial Solvents:
[0074] Bio-based synthetic fluids of this technology may be used as
solvents for paints, inks, adhesives, and coatings. These fluids
comprise paraffinic hydrocarbons in the C.sub.5-C.sub.20 range. Due
to virtual absence of aromatic hydrocarbons and odors, these fluids
meet increasingly stringent regulatory requirements. The bio-based
synthetic fluids are characterized by selective solvency as
characterized by an aniline number greater than about 80.degree.
C., and a Kauri-Butanol value greater than about 19. They are an
effective substitute for petroleum-based solvents, including
ISOPAR.RTM. and SOLTROL.RTM. products. (ISOPAR.RTM. and
SOLTROL.RTM. are trademarks of ExxonMobil Chemical and Chevron
Phillips Chemical respectively.) The viscosities of these fluids
are less than about 10 cSt at 40.degree. C., with volatility (flash
point and distillation/boiling range) adjusted according to the
specific application. As such, the lighter hydrocarbons, such as
those in the C.sub.5-C.sub.7 range, may be stripped/distilled in
order to provide industrial solvents having higher flash points and
thus with a reduced risk of fire.
Crop protection Solvents/Coating Oils:
[0075] Bio-based synthetic fluids of this technology may be used as
agricultural solvents and spray oils. These fluids include
paraffinic hydrocarbons in the C.sub.5-C.sub.20 range for solvent
applications (e.g. for dissolving pesticides and herbicides), and
in the C.sub.16-C.sub.36 range for coating oil applications.
Examples of crop protection solvent applications include dissolving
and spraying pesticides. These include applications where the
solvent is used to extract a natural herbicide for crop protection.
In these cases, selective solvency, as indicated by an aniline
number greater than about 80.degree. C., and a Kauri-Butanol value
greater than about 19, is a key attribute of the paraffinic
solvent.
[0076] When used as coating oil, the fluid is applied to the plant
leaves forming a film that protects the plant from fungi and pests.
Because the coating oil is a non-toxic chemical, as defined by an
eco-toxicity where LC.sub.50>3.5 mg/L (as described above), the
pests cannot become immune to the product. The spray oil naturally
bio-degrades and evaporates during the growth cycle of the plant.
And because the bio-based fluids are naturally free-of sulfur, they
do not leave a sulfonic residue. Typically, for coating oil
applications, the fluid viscosity is greater than about 10 cSt at
40.degree. C.
Grain De-Dusting Oil:
[0077] This application is similar to the crop protection coating
oil. Bio-based synthetic fluids of the present technology that
include hydrocarbons in the C.sub.16-C.sub.36 range provide the
required performance, mitigating dust accumulation when handling
grain. For this application, fluid viscosity is greater than about
10 cSt at 40.degree. C.
Metal Working Fluids:
[0078] Bio-based synthetic fluids of this technology may be used as
metal working fluids, including metal lubricating and metal rolling
fluids. For applications such as aluminum rolling (e.g. for
preparing rolls of aluminum foils) paraffinic hydrocarbons in the
C.sub.11-C.sub.20 range, having kinematic viscosities less than
about 10 cSt at 40.degree. C. and flash points above about
60.degree. C. are most suitable.
[0079] For applications involving more severe metal-metal contact
where lubricating properties are desired, chlorinated paraffins
from chlorination of the HDO product as described above, or
bio-derived synthetic fluids of the present technology having a
carbon number in the C.sub.16-C.sub.36 range and a kinematic
viscosity greater than about 10 cSt at 40.degree. C. are desired.
These fluids cool and lubricate metal surfaces, reducing friction
and tool wear while removing residual metallic pieces.
Industrial Cleaning Fluids:
[0080] Bio-based synthetic fluids of this technology are suitable
substitutes for petroleum kerosene for use as industrial cleaners.
Unlike the petroleum kerosene that can have up to 30% aromatic
hydrocarbons, the bio-based synthetic fluids contain virtually no
aromatics and are therefore low in toxicity and odor, and meet
stringent regulatory requirements for occupational exposure.
Lubricating Base Oils:
[0081] Bio-based synthetic fluids of this technology, comprising
oligomerized hydrocarbons, have kinematic viscosities greater than
about 10 cSt at 40.degree. C., preferably greater than about 20 cSt
at 40.degree. C., and viscosity index values (measure of viscosity
stability within operating temperature range) suitable for lube
base oil applications.
Polymerization Fluids:
[0082] Bio-based synthetic fluids of this technology may be used
for various solution and slurry polymerization processes such as
the linear low density polyethylene process. Additionally, these
fluids may be used for foam blowing processes, as an
environmentally friendly substitute for chlorinated hydrocarbons.
Examples of such foam blowing processes include production of
foamed polystyrene (e.g. STYROFOAM.RTM.) and foamed polyurethane.
Isoparaffinic hydrocarbons (e.g. HDO hydroisomerization products)
in the C.sub.5-C.sub.9 range are particularly well-suited for these
applications.
Transformer Oils:
[0083] Bio-based synthetic fluids of this technology are suitable
for use as transformer fluids due to their low dielectric constants
(from about 2 to about 3 at in the range from about 50.degree. C.
to about 200.degree. C.) and very low water solubility.
Oligomerized bio-based fluids having carbon numbers in the
C.sub.20-C.sub.36 range are preferred due to their very high flash
points.
Cosmetic Oils:
[0084] Bio-based synthetic fluids of this technology may be used as
ingredients in baby lotions, cold creams, ointments and cosmetics.
The odorless, tasteless, and inherently non-toxic attributes of
these fluids make them attractive for these applications. The
fluids of this technology in the C.sub.16-C.sub.36 range having a
kinematic viscosity greater than about 10 cSt at 40 C are
particularly well-suited for use in cosmetics.
Food Preparation Oils:
[0085] Bio-based synthetic fluids of this technology may be used
for food contact applications. Due to their properties in
preventing water absorption, and with their inherent non-toxicity
and low odor, these bio-based synthetic fluids may be used to
preserve wooden cutting boards, salad bowls and other wooden
kitchenware/utensils. Rubbing small amounts of the oils on the
wooden kitchenware fills cracks therein and prevents water/food
accumulation which can lead to formation of bacteria in addition to
degradation of the wooden article.
Drilling Fluids and Hydraulic Fracturing Fluids:
[0086] Bio-based synthetic fluids of this technology may be used as
base fluids for drilling mud applications, including for offshore
applications where a good balance of thermal stability,
eco-toxicity and bio-degradability is desired.
[0087] In an aspect, a method is provided which involves producing
an orifice in a substrate by at least injecting a paraffinic fluid
into the substrate, wherein the paraffinic fluid comprises a
hydrodeoxygenated product; the hydrodeoxygenated product is
produced by hydrodeoxygenating a bio-derived feed; the bio-derived
feed comprising bio-derived fatty acids, fatty acid esters, or a
combination thereof; the hydrodeoxygenated product comprises
n-paraffins; the paraffinic fluid contains less than about 1 wt %
aromatics; and the n-paraffins have a kinematic viscosity of less
than about 10 cSt at 40.degree. C. and have a biodegradability of
at least about 40% after about 23 days of exposure to
microorganisms. The paraffinic fluid may be any one of the
compositions provided by the present technology, including, but not
lmited to, the oligermized product, the chlorinated product, the
olefinic fluid, the HDO product, the hydroisomerized product, or
mixtures of any two or more thereof. As described above, the
paraffinic fluids of the present technology have flash points,
thermal stabilities, viscosities, eco-toxicities and
biodegradabilities excellently suited for such a method. In some
embodiments, the hydrodeoxygenated product includes n-paraffins in
the range of about 80 wt % to about 100 wt %; cycloparaffins in the
range of about 0 wt % to about 10 wt %; and less than about 1 wt %
total aromatics. In some embodiments, the paraffinic fluid further
includes a hydroisomerized product produced by at least partially
hydroisomerizing the hydrodeoxygenated product; wherein the
hydroisomerized product comprises isoparaffins where at least about
80 wt % of the isoparaffins are mono-methyl branched paraffins; the
mono-methyl branched paraffins comprise less than about 30 wt %
terminal branched isoparaffins; and the isoparaffins have a
kinematic viscosity of less than about 10 cSt at 40.degree. C. and
have a biodegradability of at least about 40% after about 23 days
of exposure to microorganisms.
[0088] In some embodiments, the paraffinic fluid has a kinematic
viscosity less than about 10 cSt at 40.degree. C. In such
embodiments, the paraffinic fluid may have a kinematic viscosity at
40.degree. C. of about 9 cSt, about 8 cSt, about 7 cSt, about 6
cSt, about 5 cSt, about 4 cSt, about 3 cSt, about 2 cSt, about 1
cSt, and ranges in between any two of these values or below any one
of these values. In some embodiments, the paraffinic fluid has a
kinematic viscosity greater than about 10 cSt at 40.degree. C. In
such embodiments, the paraffinic fluid may have a kinematic
viscosity at 40.degree. C. of about 12 cSt, about 14 cSt, about 16
cSt, about 18 cSt, about 20 cSt, about 22 cSt, about 24 cSt, about
26 cSt, about 28 cSt, about 30 cSt, and ranges in between any two
of these values or greater than any one of these values. In some
embodiments, the paraffinic fluid has a kinematic viscosity greater
than about 20 cSt at 40.degree. C.
[0089] In some embodiments, the substrate comprises a soil
substrate, a topsoil substrate, a subsoil substrate, a clay
substrate, a sand substrate, a rock substrate, or a stone
substrate. In some embodiments, the bio-derived fatty acids, fatty
acid esters, or a combination thereof comprises algae oils, beef
tallow, camelina oil, canola oil, rapeseed oil, castor oil, choice
white grease, coconut oil, coffee bean oil, corn oil, cottonseed
oil, fish oils, hemp oil, Jatropha oil, linseed oil, mustard oil,
palm oil, palm kernel oil, poultry fat, soybean oil, sunflower oil,
tall oil, tall oil fatty acid, Tung oil, used cooking oils, yellow
grease, products of the food industry, or combinations of any two
or more thereof. In some embodiments, the bio-derived fatty acids,
fatty acid esters, or a combination thereof comprise soybean oil,
corn oil, cottonseed oil, canola oil, coconut oil, sunflower oil,
palm oil, palm kernel oil, rapeseed oil, or a combination of any
two or more thereof. In some embodiments, the step of producing an
orifice comprises hydraulic fracturing of the substrate with the
paraffinic fluid.
Integrated Process for Production of Bio-Based Industrial
Fluids:
[0090] An embodiment of the inventive method for producing
bio-based industrial fluids is presented in FIG. 1. Referring to
FIG. 1, a bio-based feed 102 comprising fatty acids and/or fatty
acid esters is combined with a compressed treat gas 104 to form
reactor feed stream 106 and achieve hydrodeoxygenation (HDO) in HDO
unit 110. The bio-based feed 102 comprises any one or more of the
oils, fats, or greases recited earlier herein in this application.
The bio-based feed 102 and treat gas 104 are pumped and compressed
respectively to a pressure within the range described earlier
herein.
[0091] The treat gas 104 for the HDO reaction is a hydrogen-rich
gas, with a hydrogen concentration in the range of about 70 mol %
to about 100 mol %. In some embodiments, the hydrogen concentration
is between about 82 mol % and about 99 mol %. The main impurities
present in the treat gas 104 include methane, ethane, propane,
n-/iso-butane, hydrogen sulfide, carbon monoxide, carbon dioxide,
ammonia, and water.
[0092] The HDO unit 110 comprises a preheater to raise the
temperature of reactor feed 106 to achieve HDO reactor operation
within the temperature range described previously in the
application. In addition to the preheater, the HDO unit 110
includes an HDO reactor, separator drums/vessels, and a product
stripper. The drums/vessels separate a water byproduct 112 and an
HDO gas 114 from HDO product 116. The product stripper is employed
for removal of residual byproduct ammonia, hydrogen sulfide, and
carbon oxides, dissolved in the HDO product 116. The HDO product
116 is a paraffinic hydrocarbon composition comprising n-paraffins
in the C.sub.15-C.sub.18 range, with elemental sulfur and elemental
nitrogen less than about 5 wppm and elemental oxygen less than
about 0.1 wt %. In some embodiments, elemental sulfur and elemental
nitrogen are less than 1 wppm in the paraffinic hydrocarbon
composition. In some embodiments, the HDO product 116 is partially
recycled to the HDO reactor as a solvent/diluent for bio-based feed
102.
[0093] The HDO gas 114, containing same byproducts in addition to
light hydrocarbons such as methane and propane, is optionally
subjected to treatment (e.g. scrubbing with a solvent, water, or
caustic/amine solutions) to reduce the concentration of these
molecules in the gas 114. In some embodiments, the gas 114 is
partially recycled to the HDO reactor.
[0094] The HDO product 116 is combined with treat gas 118 to form a
hydroisomerization unit feed 119. The treat gas is a hydrogen-rich
gas stream having the specifications of treat gas 104, but
preferably containing less than about 10 ppm hydrogen sulfide,
ammonia, or carbon monoxide. If needed, the HDO product 116 and
treat gas 118 are pressurized/compressed to a value within the
hydroisomerization operating pressure range specified earlier in
this application.
[0095] The hydroisomerization unit 120 comprises a feed preheater,
a hydroisomerization reactor, and separation drums for separating
the hydroisomerization product 124 from the hydroisomerization gas
122. The hydroisomerization gas 122 may contain light hydrocarbons
formed in the hydroisomerization reactor via hydrocracking side
reactions therein.
[0096] The preheater in the hydroisomerization unit 120 raises the
temperature of the feed for operating the hydroisomerization
reactor within the temperature range indicated earlier in this
application.
[0097] The hydroisomerization gas 122 is combined with the treat
gas 104 and/or the treat gas 118, via a compression stage if
desired.
[0098] The hydroisomerization product 124, comprising paraffinic
hydrocarbons in the C.sub.5-C.sub.18 range, is directed to
oligomerization unit 130, where it is combined with an organic
peroxide initiator 126 according to conditions and limitations
provided previously. In embodiments where a batch oligomerization
reactor is employed, the oligomerization unit 130 is equipped with
a plurality of feed tanks. In these embodiments, one tank is used
to charge the oligomerization reactor while the other is being
filled with hydroisomerization product 124. The oligomerization
effluent 132 includes both oligomerized and unconverted components
of hydroisomerization product 124. As such, the oligomerization
effluent 132 is a paraffinic hydrocarbon composition in the
C.sub.5-C.sub.37+ range, characterized by a high degree of C.sub.2+
chain branching.
[0099] The oligomerization effluent is directed to a fractionation
unit 140. The fractionation unit may be one distillation column
with side draws, or a plurality of columns operating at different
pressures. Therein the oligomerization effluent is fractionated
into Fraction 142 comprising hydrocarbons in the C.sub.5-C.sub.15
range, Fraction 144 comprising hydrocarbons in the
C.sub.16-C.sub.18 range, and Fraction 146 comprising hydrocarbons
in the C.sub.19-C.sub.37+ range. Fraction 144 may be used for
solvents, drilling fluids, hydraulic fracturing fluids, and other
industrial fluid applications where kinematic viscosity values are
less than about 10 cSt at 40.degree. C. Fraction 146 may be used
for lubricating oils, dielectric fluids, grain de-dusting fluids,
mineral oil, and other applications where the kinematic viscosity
is greater than about 10 cSt at 40 C. In some embodiments, it is
necessary to further fractionate the fluid fraction comprising
C.sub.37+ fractions in order to meet the maximum boiling
temperature specified for the fluid.
[0100] Fraction 142 may be partially or completely recycled to
oligomerization unit 130. Alternatively, Fraction 142 may be
further fractionated into a C.sub.5-C.sub.9 ranged and
C.sub.10-C.sub.15 ranged fractions for use as other solvents or
fuels. The fluid fractions are preferably additized with an
anti-oxidant, and other additives specific to the application,
before drumming and shipping. The anti-oxidant is preferably a
hindered phenol introduced at a concentration between about 2 and
about 200 wppm. In some embodiments, the anti-oxidant is at a
concentration between about 10 wppm and about 100 wppm.
[0101] The present invention, thus generally described, will be
understood more readily by reference to the following examples,
which are provided by way of illustration and are not intended to
be limiting of the present invention.
EXAMPLES
Example 1
Demonstration of the Bio-Degradability of a Bio-Based Synthetic
Hydrocarbon Fluids
[0102] Canola oil was hydrodeoxygenated in a 100 cc tubular reactor
packed with 20 cc Mo catalyst (top layer) and 80 cc NiMo catalyst
(bottom layer) and then pressurized to 1600 psig with hydrogen. The
catalysts were commercially available products obtained in oxide
form. The catalysts were sulfided in the reactor using dimethyl
disulfide (DMDS), following a ramp-hold temperature profile. The
first hold was 12 hrs at 400.degree. F. (wherein H.sub.25
breakthrough was confirmed), and the second hold was about 10 hrs
at 700.degree. F. The temperatures were lowered to about
450.degree. F. before introduction of 100% canola oil (spiked with
100 ppm sulfur as DMDS). After a break-in period of partial
hydrodeoxygenation, the reactor temperature was raised to 640 F.
The liquid hourly space velocity of canola oil was maintained at 1
vol/vol/hr, along with a 10,000 SCF/Bbl gas-to-oil ratio.
[0103] The canola oil feed and HDO product were both analyzed for
elemental oxygen. The feed was 11.1 wt % oxygen whereas the HDO
product was below detection limit (<0.1 wt % oxygen). The HDO
product had a flash point of 138.degree. C., a viscosity of 3.68
cSt at 40.degree. C., and density of 0.800 kg/L.
[0104] The HDO product was subjected to biodegradability test
according to ASTM D5864-05. After 23 days of exposure to
microorganisms at the conditions specified in the test method, with
room temperature in the 20-25.degree. C. range, the paraffinic HDO
product degradation as measured by CO.sub.2 production was found to
be 44.2%. By comparison, the biodegradability of poly alpha olefins
is reported to be in the 0-25% range.
Example 2
Hydroisomerized HDO Product Fractions
[0105] HDO paraffins were hydroisomerized (HI) according to the
conditions described in this technology, using a Pt/Pd-on-amorphous
silica/alumina catalyst. The hydroisomerized products were
fractionated into different cuts using both laboratory as well as
commercial scale distillation columns. The fractionation cuts'
boiling ranges corresponded to commercial grades of petroleum-based
paraffinic fluids such as ISOPAR.RTM. L, ISOPAR.RTM. M, ISOPAR.RTM.
V, SOLTROL.RTM. 170, and SOLTROL.RTM. 220. The results are
summarized in Table 1.
TABLE-US-00001 TABLE 1 Comparison of Bio-Based Isoparaffin Fluid
Fractions (HI Cuts) to Commercial Petro-Solvents ISOPAR GRADE L M V
ISOPAR and Equivalent Products ISOPAR HI Cut 2 ISOPAR SOL-170 HI
Cut 3 ISOPAR SOL-220 HI Cut 4 HI BTMS Solvency Kauri-butanol value,
ASTM D1133 27 25 25 24.6 23 23 NA.sup.3 20.5 19 Aniline Point
(.degree. C.) 85 80 91 91 86 92 NA 94 98 Volatility Flash Point,
ASTM D56 (.degree. C.) 64 60 93 87 87 129 100 121 124 Distillation,
ASTM D86 IBP (.degree. C.) 189 165 223 .gtoreq.216 198 273
.gtoreq.218 228 273 Distillation, ASTM D86 EP (.degree. C.) 207 209
254 .ltoreq.246 243 312 .ltoreq.315 281 304 Specific Gravity @ 15.6
C., ASTM D1250 0.77 0.77 0.79 0.78 0.77 0.83 NA 0.78 0.784
Composition, wt % Saturates 99.9 >99 99.9 >99 99.8 NA >99
99.7 Aromatics <0.01 <1 <0.05 0.01 <1 <0.5 NA <1
0.3 Notes: 1. ISOPAR is a trademark of ExxonMobil Chemical 2.
SOLTROL ("SOL") is a trademark of Chevron Phillips Chemical
.sup.3NA = Data not available
[0106] As observed in Table 1, the bio-based fluids, HI Cuts 2-4
and HI Btms, have the desired selective solvency for use as
industrial solvents: Kauri-Butanol values greater than about 19,
and aniline points greater than about 80.degree. C.
[0107] The HI Btms fraction was further analyzed for comparison
with two commercial petroleum-based drilling fluids, recognized for
their relatively low ecotoxicity, high flash points, and low pour
points. These products are offered for offshore applications. Table
2 provides a summary of the results.
TABLE-US-00002 TABLE 2 Comparison of Bio-Based Isoparaffinic Fluid
(HI Btms) to Commercial Petro-Based Drilling Fluids Property
CLAIRSOL NS.sup.(a) ESCAID 120.sup.(b) HI Btms Specific Gravity
0.82 0.818 0.784 Flash Point, .degree. C. 122 101 124 Pour Point,
.degree. C. -18 -24 <-12 Aromatics, wt % <0.5 0.9 <0.5
Viscosity at 20.degree. C., cSt Viscosity at 40.degree. C., cSt 3.4
2.36 3.49 Aniline Pt., .degree. C. 84 98 Distillation, .degree. C.
IBP 261 235 273 FBP 293 270 304 Notes: .sup.(a)CLAIRSOL is
tradename of Petrochem Carless, a leading supplier of drilling base
fluids in Europe .sup.(b)ESCAID is tradename of ExxonMobil
Chemical, a leading supplier of drilling base fluids
[0108] The table shows that the bio-based drilling fluid (or
drilling mud base fluid) meets all the performance parameters
presently provided by the petroleum-based drilling fluids.
Example 3
Peroxide-Initiated Oligomerization of Paraffins
[0109] 100 parts by weight of a hydroisomerized HDO product is
introduced to a round-bottom flask reactor equipped with a
mechanical stirrer, a reflux condenser, a temperature indicator,
and a heating mantle. The hydroisomerized HDO product is analyzed
via gas chromatography (GC) and is found to consist mainly of
C.sub.9-C.sub.18 n-paraffins and iso-paraffins. Upon reaching about
200.degree. C., 20 parts by weight of LUPEROX 101 organic peroxide
[2,5-dimethyl 2,5-di(t-butylperoxy)hexane; purchasable from
Aldrich] is added in 10 equal parts over 5 hours. Upon reaching the
6.sup.th hour, the reactor is cooled and analyzed via GC where
increase in carbon number is confirmed. The product is distilled to
remove the lighter, un-reacted components and the byproducts of
peroxide decomposition. The higher carbon number product is then
tested for biodegradability according to D5864 guidelines and
expected to display at least 40+% biodegradation after 23 days of
exposure to micro-organisms.
[0110] While certain embodiments have been illustrated and
described, it should be understood that changes and modifications
can be made therein in accordance with ordinary skill in the art
without departing from the technology in its broader aspects as
defined in the following claims.
[0111] The embodiments, illustratively described herein may
suitably be practiced in the absence of any element or elements,
limitation or limitations, not specifically disclosed herein. Thus,
for example, the terms "comprising," "including," "containing,"
etc. shall be read expansively and without limitation.
Additionally, the terms and expressions employed herein have been
used as terms of description and not of limitation, and there is no
intention in the use of such terms and expressions of excluding any
equivalents of the features shown and described or portions
thereof, but it is recognized that various modifications are
possible within the scope of the claimed technology. Additionally,
the phrase "consisting essentially of" will be understood to
include those elements specifically recited and those additional
elements that do not materially affect the basic and novel
characteristics of the claimed technology. The phrase "consisting
of" excludes any element not specified.
[0112] The present disclosure is not to be limited in terms of the
particular embodiments described in this application. Many
modifications and variations can be made without departing from its
spirit and scope, as will be apparent to those skilled in the art.
Functionally equivalent methods and compositions within the scope
of the disclosure, in addition to those enumerated herein, will be
apparent to those skilled in the art from the foregoing
descriptions. Such modifications and variations are intended to
fall within the scope of the appended claims. The present
disclosure is to be limited only by the terms of the appended
claims, along with the full scope of equivalents to which such
claims are entitled. It is to be understood that this disclosure is
not limited to particular methods, reagents, compounds compositions
or biological systems, which can of course vary. It is also to be
understood that the terminology used herein is for the purpose of
describing particular embodiments only, and is not intended to be
limiting.
[0113] In addition, where features or aspects of the disclosure are
described in terms of Markush groups, those skilled in the art will
recognize that the disclosure is also thereby described in terms of
any individual member or subgroup of members of the Markush
group.
[0114] As will be understood by one skilled in the art, for any and
all purposes, particularly in terms of providing a written
description, all ranges disclosed herein also encompass any and all
possible subranges and combinations of subranges thereof. Any
listed range can be easily recognized as sufficiently describing
and enabling the same range being broken down into at least equal
halves, thirds, quarters, fifths, tenths, etc. As a non-limiting
example, each range discussed herein can be readily broken down
into a lower third, middle third and upper third, etc. As will also
be understood by one skilled in the art all language such as "up
to," "at least," "greater than," "less than," and the like, include
the number recited and refer to ranges which can be subsequently
broken down into subranges as discussed above. Finally, as will be
understood by one skilled in the art, a range includes each
individual member.
[0115] All publications, patent applications, issued patents, and
other documents referred to in this specification are herein
incorporated by reference as if each individual publication, patent
application, issued patent, or other document was specifically and
individually indicated to be incorporated by reference in its
entirety. Definitions that are contained in text incorporated by
reference are excluded to the extent that they contradict
definitions in this disclosure.
[0116] Other embodiments are set forth in the following claims.
* * * * *