U.S. patent application number 13/933033 was filed with the patent office on 2015-01-01 for method of processing adulterated biomass feedstocks.
This patent application is currently assigned to Syntroleum Corporation. The applicant listed for this patent is Syntroleum Corporation. Invention is credited to Ramin Abhari, Peter Z. Havlik, E. Gary Roth, H. Lynn Tomlinson.
Application Number | 20150005551 13/933033 |
Document ID | / |
Family ID | 52116234 |
Filed Date | 2015-01-01 |
United States Patent
Application |
20150005551 |
Kind Code |
A1 |
Havlik; Peter Z. ; et
al. |
January 1, 2015 |
METHOD OF PROCESSING ADULTERATED BIOMASS FEEDSTOCKS
Abstract
A method is provided that involves contacting a feed stream
including a biorenewable feedstock and adulterants with a catalyst
in a fixed bed hydroprocessing reactor to produce a hydroprocessed
product with less adulterants than the feed stream.
Inventors: |
Havlik; Peter Z.; (Tulsa,
OK) ; Abhari; Ramin; (Bixby, OK) ; Roth; E.
Gary; (Bristow, OK) ; Tomlinson; H. Lynn;
(Tulsa, OK) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Syntroleum Corporation |
Tulsa |
OK |
US |
|
|
Assignee: |
Syntroleum Corporation
Tulsa
OK
|
Family ID: |
52116234 |
Appl. No.: |
13/933033 |
Filed: |
July 1, 2013 |
Current U.S.
Class: |
585/240 |
Current CPC
Class: |
C10G 3/46 20130101; C10G
3/49 20130101; C10G 3/50 20130101; C10G 3/47 20130101; C10G
2300/1011 20130101; Y02P 30/20 20151101; Y02E 50/13 20130101; Y02E
50/10 20130101 |
Class at
Publication: |
585/240 |
International
Class: |
C10G 3/00 20060101
C10G003/00 |
Claims
1. A method comprising contacting a feed stream comprising a
biorenewable feedstock and one or more of polymers, drugs,
pesticides, or food preservatives with a hydrotreatment catalyst in
a fixed bed hydroprocessing reactor to produce a hydroprocessed
product with less polymers, drugs, pesticides, or food
preservatives than the feed stream; wherein the amount of the one
or more of polymers, drugs, pesticides, or food preservatives in
the feed stream is about 0.1 wppm to about 1000 wppm based on the
biorenewable feedstock; the fixed bed hydroprocessing reactor is at
a temperature less than about 680.degree. F.; and is at a pressure
from about 200 psig to about 4,000 psig.
2. The method of claim 1, wherein the hydroprocessed product
comprises at least 80 wt % paraffins falling within the range of
C.sub.ii to C.sub.24, where the paraffins comprise C.sub.16 and
C.sub.18 paraffins; from about 0.1 wt % to about 7.0 wt %
cycloparaffins; and from about 0.001 wt % to about 1.0 wt %
aromatics.
3. (canceled)
4. The method of claim 1, wherein the one or more of polymers,
drugs, pesticides, or food preservatives comprise acrylonitrile
butadiene styrene thermoplastic, polyacrylate rubber,
ethylene-acrylate rubber, polyester urethane, bromo isobutylene
isoprene rubber, polybutadiene rubber, chloro isobutylene isoprene
rubber, polychloroprene, chlorosulphonated polyethylene,
epichlorohydrin polymer, ethylene propylene rubber, ethylene
propylene diene monomer polymer, polyether urethane,
tetrafluoroethylene/propylene rubbers, perfluorocarbon elastomers,
fluoroelastomer, fluoro silicone, fluorocarbon rubber, high density
polyethylene, hydrogenated nitrile butadiene rubber, polyisoprene,
isobutylene isoprene rubber, low density polyethylene, polyethylene
terephthalate, acrylonitrile butadiene rubber, polyethylene,
polyisobutene, polypropylene, polystyrene, poly vinyl chloride,
polyvinylidene chloride, polyurethane, styrene butadiene, styrene
ethylene butylene styrene copolymer, polysiloxane, vinyl methyl
silicone, acrylonitrile butadiene carboxy monomer rubber, styrene
butadiene carboxy monomer rubber, thermoplastic polyether-ester,
styrene butadiene block copolymer, styrene butadiene carboxy block
copolymer, polyesters, polyamides, or polyacetals.
5. The method of claim 1, wherein the one or more of polymers,
drugs, pesticides, or food preservatives comprise polyvinylidene
chloride.
6. The method of claim 1, wherein the one or more of polymers,
drugs, pesticides, or food preservatives further comprise a polymer
additive.
7. (canceled)
8. The method of claim 1, wherein the one or more of polymers,
drugs, pesticides, or food preservatives comprise styrenated
phenol, 2-tert-butyl-4-methylphenol, 2- and
3-tert-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol,
2,6-distyrenated p-cresol, 2,6-di-tert-butyl-4-nonylphenol,
2,4-bis-(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-tria-
zine, 2,5-di-tert-amylhydroquinone, mono-tert-butylhydroquinone,
hydroquinone monomethyl ether, 2,5-di-t-butyl hydroquinone,
tris(p-nonylphenyl)phosphite,
tris(2,4-di-tert-butylphenyl)phosphite, distearyl pentaerythritol
diphosphite, dilauryl-3,3'-thio-dipropionate,
distearyl-3,3'-thio-diproprionate, ditridecyl-thio-dipropionate, or
thiodipropionic acid.
9. The method of claim 1, wherein the one or more of polymers,
drugs, pesticides, or food preservatives comprise acephate,
acetochlor, aldicarb, atrazine, bifenthrin, chloropicrin,
chlorothalonil, chlorphyrifos, 2,4-dichlorophenoxyacetic acid,
dichloropropene, dimethenamid, diuron, ethephon, fenoxycarb,
glyphosate, 2-methyl-4-chlorophenoxyacetic acid, metham sodium,
metham potassium, methyl bromide, metolachlor, paraquat,
pendimethalin, propanil, simazine, or trifluralin.
10. The method of claim 1, wherein the feed stream comprises a
biorenewable feedstock, a polymer, and a polymer additive.
11. The method of claim 1, wherein from about 100 to about 15,000
reactor volumes of biorenewable feedstock are processed prior to
shutdown of the fixed bed hydroprocessing reactor.
12. The method of claim 1, wherein the liquid hourly space velocity
of the biorenewable feedstock through the fixed bed hydroprocessing
reactor is from about 0.2 hr.sup.-1 to about 10.0 hr.sup.-1.
13. (canceled)
14. The method of claim 1, wherein the biorenewable feedstock
comprises animal fats, animal oils, plant fats, plant oils,
vegetable fats, vegetable oils, or greases.
15. The method of claim 1, wherein the biorenewable feedstock
comprises animal fats, poultry oil, soybean oil, canola oil,
rapeseed oils, palm oil, palm kernel oil, jatropha oil, castor oil,
camelina oil, algae oil, seaweed oil, halophile oils, rendered
fats, restaurant greases, brown grease, yellow grease, waste
industrial frying oils, fish oils, tall oil, or tall oil fatty
acids.
16. The method of claim 1, wherein the biorenewable feedstock
comprises animal fats, restaurant greases, brown grease, yellow
grease, or waste industrial frying oils.
17. The method of claim 1, wherein the hydroprocessed product is
fractionated to provide a middle distillate fraction.
18. The method of claim 1, wherein the feed stream further
comprises a diluent and the volume ratio of diluent to biorenewable
feedstock falls within the range from about 0.5:1 to about
20:1.
19. The method of claim 1, wherein the hydroprocessed product is
suitable as a diesel fuel, a diesel fuel additive, a diesel fuel
blendstock, a turbine fuel, a turbine fuel additive, a turbine fuel
blendstock, an aviation fuel, an aviation fuel additive, or an
aviation fuel blendstock.
20. The method of claim 2, wherein the hydroprocessed product is
suitable as a diesel fuel.
21. The method of claim 17, wherein the middle distillate fraction
is suitable as a diesel fuel.
22. The method of claim 1, wherein the feed stream comprises a
biorenewable feedstock and any two or more of polymers, drugs,
pesticides, or food preservatives.
23. The method of claim 1, wherein the amount of the one or more of
polymers, drugs, pesticides, or food preservatives in the feed
stream is about 1 wppm to about 1000 wppm based on the biorenewable
feedstock.
24. The method of claim 1, wherein the amount of the one or more of
polymers, drugs, pesticides, or food preservatives in the feed
stream is about 10 wppm to about 1000 wppm based on the
biorenewable feedstock.
25. The method of claim 1, wherein the amount of the one or more of
polymers, drugs, pesticides, or food preservatives is reduced by at
least about 30%.
26. The method of claim 1, wherein at least a portion of the one or
more of polymers, drugs, pesticides, or food preservatives are
converted into hydroprocessed product.
27. The method of claim 1, wherein the fixed bed hydroprocessing
reactor is at a temperature from about 480.degree. F. to about
645.degree. F.
28. A method comprising contacting a feed stream comprising a
biorenewable feedstock and any two or more of polymers, drugs,
pesticides, or food preservatives with a hydrotreatment catalyst in
a fixed bed hydroprocessing reactor to produce a hydroprocessed
product with less of the any two or more of polymers, drugs,
pesticides, or food preservatives than the feed stream; wherein the
amount of the any two or more of polymers, drugs, pesticides, or
food preservatives in the feed stream is about 0.1 wppm to about
1000 wppm based on the biorenewable feedstock; the fixed bed
hydroprocessing reactor is at a temperature from about 480.degree.
F. to about 680.degree. F.; is at a pressure from about 200 psig to
about 4,000 psig; and the any two or more of polymers, drugs,
pesticides, or food preservatives are reduced by at least about
30%.
29. (canceled)
30. The method of claim 28, wherein the hydroprocessed product is
suitable as a diesel fuel, a diesel fuel additive, a diesel fuel
blendstock, a turbine fuel, a turbine fuel additive, a turbine fuel
blendstock, an aviation fuel, an aviation fuel additive, or an
aviation fuel blendstock.
31. A method comprising contacting a feed stream comprising a
biorenewable feedstock and one or more of drugs, pesticides, or
food preservatives with a hydrotreatment catalyst in a fixed bed
hydroprocessing reactor to produce a hydroprocessed product with
less drugs, pesticides, or food preservatives adulterants than the
feed stream; wherein the amount of one or more of drugs,
pesticides, or food preservatives in the feed stream is about 0.1
wppm to about 1000 wppm based on the biorenewable feedstock; the
fixed bed hydroprocessing reactor is at a temperature from about
480.degree. F. to about 680.degree. F.; and is at a pressure from
about 200 psig to about 4,000 psig.
32. The method of claim 31, wherein the amount of one or more of
drugs, pesticides, or food preservatives in the feed stream is
about 10 wppm to about 1000 wppm based on the biorenewable
feedstock.
33. The method of claim 31, wherein the hydroprocessed product is
suitable as a diesel fuel, a diesel fuel additive, a diesel fuel
blendstock, a turbine fuel, a turbine fuel additive, a turbine fuel
blendstock, an aviation fuel, an aviation fuel additive, or an
aviation fuel blendstock.
34. The method of claim 1, wherein the feed stream comprises a
biorenewable feedstock and a polymer.
Description
FIELD
[0001] The present technology relates generally to the processing
of adulterated biorenewable feedstocks for manufacture of high
quality hydroprocessed products. More particularly, and not by way
of limitation, the present technology provides a method to produce
a high quality hydroprocessed product with less adulterants than
the feed stream.
BACKGROUND
[0002] Biomass is a renewable alternative to fossil raw materials
in the production of fuels and chemicals. The increase of renewable
products and biofuels production is part of the government's
strategy of sustainability, improving energy security and reducing
greenhouse gas emissions.
[0003] However, there is the potential for many sources of biomass
to become contaminated with manufactured adulterants due to
handling and processing. These adulterants can negatively impact
both the processibility of the biomass feedstock and the
performance of the finished products. Therefore, a great deal of
time and expense has been invested in pretreatment of biomass to
remove potential adulterants as well as native components that can
negatively impact production (e.g. phosphorus, metals).
SUMMARY
[0004] In one aspect, a method is provided involving contacting a
feed stream comprising a biorenewable feedstock and adulterants
with a catalyst in a fixed bed hydroprocessing reactor to produce a
hydroprocessed product with less adulterants than the feed stream;
wherein the fixed bed reactor is at a temperature less than about
750.degree. F. (400.degree. C.) and the fixed bed hydroprocessing
reactor is at a pressure from about 200 psig (13.8 barg) to about
4,000 psig (275 barg).
[0005] In some embodiments, the hydroprocessed product comprises at
least 80 wt % paraffins falling within the range of C.sub.11 to
C.sub.24, where the paraffins comprise C.sub.16 and C.sub.18
paraffins; from about 0.1 wt % to about 7.0 wt % cycloparaffins;
and from about 0.001 wt % to about 1.0 wt % aromatics. In some
embodiments of such a hydroprocessed product, the hydroprocessed
product is suitable for use as a diesel fuel.
[0006] In some embodiments, the adulterants include polymers,
monomers of polymers, drugs, pesticides, polymer additives, food
preservatives, or mixtures of any two or more thereof. In some
embodiments, the adulterants comprise acrylonitrile butadiene
styrene thermoplastic, polyacrylate rubber, ethylene-acrylate
rubber, polyester urethane, bromo isobutylene isoprene rubber,
polybutadiene rubber, chloro isobutylene isoprene rubber,
polychloroprene, chlorosulphonated polyethylene, epichlorohydrin,
ethylene propylene rubber, ethylene propylene diene monomer,
polyether urethane, tetrafluoroethylene/propylene rubbers,
perfluorocarbon elastomers, fluoroelastomer, fluoro silicone,
fluorocarbon rubber, high density polyethylene, hydrogenated
nitrile butadiene, polyisoprene, isobutylene isoprene rubber, low
density polyethylene, polyethylene terephthalate, ethylene vinyl
acetate, acrylonitrile butadiene, polyethylene, polyisobutene,
polypropylene, polystyrene, poly vinyl choloride, polyvinylidene
chloride, polyurethane, styrene butadiene, styrene ethylene
butylene styrene copolymer, polysiloxane, vinyl methyl silicone,
acrylonitrile butadiene carboxy monomer, styrene butadiene carboxy
monomer, thermoplastic polyether-ester, styrene butadiene block
copolymer, styrene butadiene carboxy block copolymer, polyesters,
polyamides, polyacetals, or mixtures of any two or more thereof. In
some embodiments, the adulterants include polyvinylidene
chloride.
[0007] In some embodiments, the adulterants comprise a polymer
additive. In some embodiments, the adulterants comprise acetamide,
benzyl benzoate, benzyl butyl phthalate, bis(2-ethylhexyl)adipate,
bis(2-ethylhexyl)phthalate, bisphenol A, bisphenol AF,
1,2-cyclohexane dicarboxylic acid diisononyl ester, dibutyl
phthalate, dibutyl sebacate, diethylene glycol dinitrate,
diisobutyl phthalate, diisodecyl phthalate, diisononyl phthalate,
dimethyl methylphosphonate, 2,4-dinitrotoluene, dioctyl adipate,
diisodecyl adipate, dioctyl terephthalate, dipropylene glycol,
epoxidized soybean oil, ethyl butyrate, ethylene carbonate, furoin,
neopentyl glycol, phthalate, polybutene, polycaprolactone,
propylene carbonate, triacetin, tributyl phosphate, tricresyl
phosphate, triethyl phosphate, triethylene glycol dinitrate,
trimethylolethane trinitrate, asbestine, barium borate, brominated
flame retardant, bromoform, calcium borate, chlorendic acid,
decabromodiphenyl ether, 1,2-dibromoethane, dimethyl chlorendate,
dimethyl methylphosphonate, heptazine, hexabromocyclododecane,
octabromodiphenyl ether, pentabromodiphenyl ether, polybrominated
biphenyl, polybrominated diphenyl ethers, polychlorinated biphenyl,
tetrabromobisphenol A, tris(2,3-dibromopropyl) phosphate,
tris(2-chloroethyl) phosphate, zinc borate, or mixtures of any two
or more thereof.
[0008] In some embodiments, the adulterants include pesticides. In
some embodiments, the adulterants include acephate, acetochlor,
aldicarb, atrazine, bifenthrin, chloropicrin, chlorothalonil,
chlorphyrifos, 2,4-dichlorophenoxyacetic acid, dichloropropene,
dimethenamid, diuron, ethephon, fenoxycarb, glyphosate,
2-methyl-4-chlorophenoxyacetic acid, metham sodium, metham
potassium, methyl bromide, metolachlor, paraquat, pendimethalin,
propanil, simazine, trifluralin, or mixtures of any two or more
thereof. In some embodiments, the adulterants include a polymer and
a polymer additive.
[0009] In some embodiments, from about 100 to about 15,000 reactor
volumes of biorenewable feedstock are processed prior to shutdown
of the fixed bed hydroprocessing reactor. In some embodiments, the
liquid hourly space velocity of the feed stream through the fixed
bed hydroprocessing reactor is from about 0.2 hr.sup.-1 to about
10.0 hr.sup.-1. In some embodiments, the reactor comprises a
hydrotreatment catalyst.
[0010] In some embodiments, the biorenewable feedstock comprises
animal fats, animal oils, plant fats, plant oils, vegetable fats,
vegetable oils, or greases. In some embodiments, the biorenewable
feedstock comprises animal fats, poultry oil, soybean oil, canola
oil, rapeseed oils, palm oil, palm kernel oil, jatropha oil, castor
oil, camelina oil, algae oil, seaweed oil, halophile oils, rendered
fats, restaurant greases, brown grease, yellow grease, waste
industrial frying oils, fish oils, tall oil, or tall oil fatty
acids. In some embodiments, the biorenewable feedstock comprises
animal fats, restaurant greases, brown grease, yellow grease, or
waste industrial frying oils. In some embodiments, the biorenewable
feedstock comprises the fatty acid distillate from vegetable oil
deodorization.
[0011] In some embodiments, the hydroprocessed product is suitable
as a diesel fuel, a diesel fuel additive, a diesel fuel blendstock,
a turbine fuel, a turbine fuel additive, a turbine fuel blendstock,
an aviation fuel, an aviation fuel additive, or an aviation fuel
blendstock. In some embodiments, the hydroprocessed product is
fractionated to provide a middle distillate fraction. In some
embodiments, the middle distillate fraction is suitable for use as
a diesel fuel.
[0012] In some embodiments, the feed stream further comprises a
diluent and the volume ratio of diluent to biorenewable feedstock
falls within the range from about 0.5:1 to about 20:1.
BRIEF DESCRIPTION OF THE FIGURES
[0013] FIGS. 1A and 1B illustrate solids contaminants which may
become associated with fats and oils and greases (FOG).
[0014] FIG. 2 illustrates the concentrations of dissolved
polyethylene from samples of animal fats, fish oils, yellow
greases, vegetable oils, and waste vegetable oils, according to the
Examples.
DETAILED DESCRIPTION
[0015] 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).
[0016] As used herein, "about" will mean up to plus or minus 10% of
the particular term.
[0017] 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.
[0018] As used herein, "alkyl" groups include straight chain and
branched alkyl groups having from 1 to about 22 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.
[0019] 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 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.
[0020] The term "aromatics" as used herein is synonymous with
"aromates" and means both cyclic aromatic hydrocarbons that do not
contain heteroatoms as well as heterocyclic aromatic compounds. The
term includes monocyclic, bicyclic and polycyclic ring systems. The
term also includes aromatic species with alkyl groups and
cycloalkyl groups. Thus, aromatics include, but are not limited to,
benzene, azulene, heptalene, phenylbenzene, indacene, fluorene,
phenanthrene, triphenylene, pyrene, naphthacene, chrysene,
anthracene, indene, indane, pentalene, and naphthalene, as well as
alkyl and cycloalkyl substituted variants of these compounds. In
some embodiments, aromatic species contains 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 includes groups containing fused rings,
such as fused aromatic-aliphatic ring systems (e.g., indane,
tetrahydronaphthene, and the like).
[0021] "Oxygenates" as used herein means carbon-containing
compounds containing at least one covalent bond to oxygen. Examples
of functional groups encompasses by the term include, but are not
limited to, carboxylic acids, carboxylates, acid anhydrides,
aldehydes, esters, ethers, ketones, and alcohols, as well as
heteroatom esters and anhydrides such as phosphate esters and
phosphate anhydrides. Oxygenates may also be oxygen containing
variants of aromatics, cycloparaffins, and paraffins as described
herein.
[0022] The term "paraffins" as used herein means non-cyclic,
branched or unbranched alkanes. An unbranched paraffin is an
n-paraffin; a branched paraffin is an iso-paraffin.
"Cycloparaffins" are cyclic, branched or unbranched alkanes.
[0023] 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.
The term also encompasses alkyl alcohols, alkyl carboxylic acids,
alkyl aldehydes, alkyl ketones, alkyl esters, and alkyl ethers.
[0024] Adulterants as used herein refer to human synthesized
compounds and substances that may become associated with a
biorenewable feedstock. Examples of adulterants include, but are
not limited to, polymers, oligomers, additives associated with
polymers and oligomers, (e.g. plasticizers; inorganic additives
incorporated into a polymer), residual monomers or plasticizers
incorporated into the polymers and oligomers, pesticides (also
known as biocides, and including but not limited to insecticides,
fumigants, fungicides, herbicides, and plant growth regulators),
preservatives, drugs, man-made halogenated organics, and man-made
organometallic complexes.
[0025] Hydroprocessing as used herein describes the various types
of catalytic reactions that occur in the presence of hydrogen
without limitation. Examples of the most common hydroprocessing
reactions include, but are not limited to, hydrogenation,
hydrodesulfurization (HDS), hydrodenitrogenation (HDN),
hydrotreating (HT), hydrocracking (HC), aromatic saturation or
hydrodearomatization (HDA), hydrodeoxygenation (HDO),
decarboxylation (DCO), hydroisomerization (HI), hydrodewaxing (HD),
hydrodemetallization (HDM), decarbonylation, methanation, and
reforming. Depending upon the type of catalyst, reactor
configuration, reactor conditions, and feedstock composition,
multiple reactions can take place that range from purely thermal
(i.e. do not require catalyst) to catalytic. In the case of
describing the main function of a particular hydroprocessing unit,
for example an HDO reaction system, it is understood that the HDO
reaction is merely one of the predominant reactions that are taking
place and that other reactions may also take place.
[0026] Decarboxylation (DCO) is understood to mean hydroprocessing
of an organic molecule such that a carboxyl group is removed from
the organic molecule to produce CO.sub.2, as well as
decarbonylation which results in the formation of CO.
[0027] Pyrolysis is understood to mean thermochemical decomposition
of carbonaceous material with little to no diatomic oxygen or
diatomic hydrogen present during the thermochemical reaction. The
optional use of a catalyst in pyrolysis is typically referred to as
catalytic cracking, which is encompassed by the term as pyrolysis,
and is not be confused with hydrocracking
[0028] Hydrotreating (HT) involves the removal of elements from
groups 3, 5, 6, and/or 7 of the Periodic Table from organic
compounds. Hydrotreating may also include hydrodemetallization
(HDM) reactions. Hydrotreating thus involves removal of heteroatoms
such as oxygen, nitrogen, sulfur, and combinations of any two more
thereof through hydroprocessing. For example, hydrodeoxygenation
(HDO) is understood to mean removal of oxygen by a catalytic
hydroprocessing reaction to produce water as a by-product;
similarly, hydrodesulfurization (HDS) and hydrodenitrogenation
(HDN) describe the respective removal of the indicated elements
through hydroprocessing.
[0029] Hydrogenation involves the addition of hydrogen to an
organic molecule without breaking the molecule into subunits.
Addition of hydrogen to a carbon-carbon or carbon-oxygen double
bond to produce single bonds are two nonlimiting examples of
hydrogenation. Partial hydrogenation and selective hydrogenation
are terms used to refer to hydrogenation reactions that result in
partial saturation of an unsaturated feedstock. For example,
vegetable oils with a high percentage of polyunsaturated fatty
acids (e.g. linoleic acid) may undergo partial hydrogenation to
provide a hydroprocessed product wherein the polyunsaturated fatty
acids are converted to mono-unsaturated fatty acids (e.g. oleic
acid) without increasing the percentage of undesired saturated
fatty acids (e.g. stearic acid). While hydrogenation is distinct
from hydrotreatment, hydroisomerization, and hydrocracking,
hydrogenation may occur amidst these other reactions.
[0030] Hydrocracking (HC) is understood to mean the breaking of a
molecule's carbon-carbon bond to form at least two molecules in the
presence of hydrogen. Such reactions typically undergo subsequent
hydrogenation of the resulting double bond.
[0031] Hydroisomerization (HI) is defined as the skeletal
rearrangement of carbon-carbon bonds in the presence of hydrogen to
form an isomer. Hydrocracking is a competing reaction for most HI
catalytic reactions and it is understood that the HC reaction
pathway, as a minor reaction, is included in the use of the term
HI. Hydrodewaxing (HDW) is a specific form of hydrocracking and
hydroisomerization designed to improve the low temperature
characteristics of a hydrocarbon fluid.
[0032] Hydrocarbonaceous is defined as being primarily composed of
organic molecules containing carbon and hydrogen (i.e.
hydrocarbon), but also include constituents of other organic
molecules such as those comprised of atoms selected from groups 3
through group 7 of the Periodic Table (e.g. boron, nitrogen,
oxygen, phosphorus, sulfur, and/or halogens).
[0033] "Aviation fuel" as used herein includes both jet fuel and
aviation gasoline. Jet fuel also goes by the term aviation turbine
fuel.
[0034] "Turbine fuel" as used herein includes, but is not limited
to, a fuel combusted with compressed air to drive an electric
generator, or to power ships and tanks. Turbine fuels are typically
diesel or kerosene boiling range fuels.
[0035] The present technology provides methods and systems for the
hydroprocessing of feed streams that include adulterants, such that
the hydroprocessed product produced has less adulterants.
Accordingly, the present technology also provides compositions with
a reduced level of adulterants. Contrary to the requirements for
purified biorenewable feedstocks, the present technology allows for
the processing of contaminated, and therefore cheaper, biorenewable
feedstocks.
[0036] Thus, in an aspect, a method is provided that involves
contacting a feed stream, where the feed stream includes a
biorenewable feedstock and adulterants, with a catalyst in a fixed
bed hydroprocessing reactor to produce a hydroprocessed product
with less adulterants than the feed stream. The fixed bed
hydroprocessing reactor is at a temperature less than about
750.degree. F. (400.degree. C.), and is at a pressure from about
200 psig (13.8 barg) to about 4,000 psig (275 barg). The
hydroprocessed product possesses less adulterants than the feed
stream in its undistilled form, although in some embodiments the
hydroprocessed product may be further distilled. In some
embodiments, the fixed bed hydroprocessing reactor is a continuous
fixed bed hydroprocessing reactor. In some embodiments, the
hydroprocessed product is suitable as a diesel fuel, a diesel fuel
additive, a diesel fuel blendstock, a turbine fuel, a turbine fuel
additive, a turbine fuel blendstock, an aviation fuel, an aviation
fuel additive, an aviation fuel blendstock, or a combination of any
two or more thereof.
[0037] In some embodiments, the process converts at least a portion
of the adulterants into hydroprocessed product. In some such
embodiments, the method converts at least about 0.01 wt % of the
adulterants into hydroprocessed product. The weight percent of the
adulterants converted into hydroprocessed product may be about 0.05
wt %, about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 5 wt %,
about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, about
30 wt %, about 35 wt %, about 40 wt %, about 45 wt %, about 50 wt
%, about 55 wt %, about 60 wt %, about 65 wt %, about 70 wt %,
about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %, about
95 wt %, about 98 wt %, about 99 wt %, or any ranges including and
in between any two of these values or above any one of these
values.
[0038] The amount of adulterants in the feed stream may be about
0.01 wppm based on the biorenewable feedstock. The amount of
adulterants as based on the biorenewable feedstock may be about
0.05 wppm, about 0.1 wppm, about 0.5 wppm, about 0.1 wppm, about 5
wppm, about 10 wppm, about 15 wppm, about 20 wppm, about 25 wppm,
about 30 wppm, about 35 wppm, about 40 wppm, about 45 wppm, about
50 wppm, about 55 wppm, about 60 wppm, about 65 wppm, about 70
wppm, about 75 wppm, about 80 wppm, about 85 wppm, about 90 wppm,
about 95 wppm, about 100 wppm, about 105 wppm, about 110 wppm,
about 115 wppm, about 120 wppm, about 125 wppm, about 130 wppm,
about 135 wppm, about 140 wppm, about 145 wppm, about 150 wppm,
about 155 wppm, about 160 wppm, about 165 wppm, about 170 wppm,
about 175 wppm, about 180 wppm, about 185 wppm, about 190 wppm,
about 195 wppm, about 200 wppm, about 225 wppm, about 250 wppm,
about 275 wppm, about 300 wppm, about 325 wppm, about 350 wppm,
about 375 wppm, about 400 wppm, about 425 wppm, about 450 wppm,
about 475 wppm, about 500 wppm, about 550 wppm, about 600 wppm,
about 650 wppm, about 700 wppm, about 750 wppm, about 800 wppm,
about 850 wppm, about 900 wppm, about 1000 wppm, and ranges
including and between any two of these values and above any one of
these values.
[0039] The amount of adulterants in the feed stream may be reduced
by about 0.01%. The amount of adulterants may be reduced by about
0.05%, about 0.1%, about 0.5%, about 1%, about 5%, about 10%, about
15%, about 20%, about 25%, about 30%, about 35%, about 40%, about
45%, about 50%, about 55%, about 60%, about 65%, about 70%, about
75%, about 80%, about 85%, about 90%, about 95%, about 98%, about
99%, about 100%, or ranges including and between any two of these
values and above any one of these values. The reduction in the
amount of adulterants may be measured by directly determining the
adulterants in the hydroprocessed product and comparing with the
amount of adulterants in the feed stream. Alternatively, the
reduction in the amount of adulterants may be measured by
concentrating the adulterant such as through distillation,
reaction, extraction, or combinations which are well known to those
skilled in analytical chemistry. Such techniques can improve the
resolution of the adulterant concentration in the respective
composition tested.
[0040] Adulterants of the present technology are typically
associated with the biorenewable feedstock employed. In some
embodiments, the adulterants include polymers, monomers of
polymers, pesticides, additives, halogenated organic compounds, or
mixtures of any two or more thereof. In some embodiments, the
adulterants include dissolved adulterants, solubilized adulterants,
particulate adulterants, or mixtures of any two or more thereof. In
some embodiments, the particulate adulterants are less than about 1
mm in diameter. In some embodiments, the particulate adulterants
are less than about 100 .mu.m in diameter. In some embodiments, the
particulate adulterants are less than about 80 .mu.m in diameter.
In some embodiments, the particulate adulterants are less than
about 50 .mu.m in diameter. In some embodiments, the particulate
adulterants are less than about 10 .mu.m in diameter. In some
embodiments, the particulate adulterants are less than about 1
.mu.m in diameter. In some embodiments, the particulate adulterants
are less than about 0.1 .mu.m in diameter.
[0041] Association of the adulterants may occur through a variety
of routes and sources. For example, in meat processing plants and
the rendering of tallow, animal carcasses and packaged goods may be
wrapped in plastic films, some of which may end up in the rendered
fats. Two common plastic films are polyethylene (PE) and
polyvinylidene chloride (PVDC). In facilities where packaged meats
are recycled (e.g. when product is past its shelf life, pieces of
packaging material, plastic liners, and even used latex gloves may
become mixed in with the rendered fat. Some of the polymeric
materials and the associated additives may be incorporated into the
fat as particulate material, solubilized material, or a mixture of
both. Similarly, in recovering waste vegetable oils and restaurant
greases, contamination by packages from the fried foods,
plasticware, transfer hoses, and a multitude of other sources of
contamination may occur. While various pretreatment steps may
reduce particulate matter and even solubilized material to some
degree, the solubilized polymeric adulterant may still persist in
the material. Some adulterants may be monomers incorporated within
the polymer or provided by decomposition of the polymer.
[0042] Pesticides, wood preservatives, and drugs are other
adulterants that may be associated with the biorenewable feedstock.
Many drugs and pesticides are fat soluble and may enter the food
chain through consumption of plants, grain, seeds, as well as
runoff into the water system in the case of fish (e.g. fish oil).
These adulterants may end up in animal fat as well as plant oils
and algal oils. Drugs are typically more common in animal fats than
in other sources of fatty acids, where the primary source may be in
the application of veterinary medicine. Wood preservatives are
expected to be less prevalent in fats and oils than pesticides, but
may enter the food supply in a similar fashion to pesticides.
[0043] Food preservatives, including anti-oxidants, are other type
of adulterant that may be present in oils and fats from packaged
food operations. Preservatives are added to packaged foods to
increase the shelf life of the food.
[0044] A partial list of polymers is provided in Table 1.
TABLE-US-00001 TABLE 1 Examples of Polymers Abbrev. Name ABS
Acrylonitrile butadiene styrene rubber ACM Polyacrylate Rubber AEM
Ethylene-acrylate Rubber AU Polyester Urethane BIIR Bromo
Isobutylene Isoprene BR Polybutadiene CIIR Chloro Isobutylene
Isoprene CR Polychloroprene CSM Chlorosulphonated Polyethylene ECO
Epichlorohydrin EP Ethylene Propylene EPDM Ethylene Propylene Diene
Monomer EU Polyether Urethane FEPM Tetrafluoroethylene/propylene
rubbers FFKM Perfluorocarbon elastomers FKM Fluoroelastomer FMQ
Fluoro Silicone FPM Fluorocarbon Rubber HDPE High density
Polyethylene HNBR Hydrogenated Nitrile Butadiene IR Polyisoprene
IIR Isobutylene Isoprene rubber LDPE Low density polyethylene NBR
Acrylonitrile Butadiene PE Polyethylene PIB Polyisobutene PP
Polypropylene PS Polystyrene PVC Poly vinyl choloride PVDC
Polyvinylidene chloride PU Polyurethane SBR Styrene Butadiene SEBS
Styrene Ethylene Butylene Styrene Copolymer SI Polysiloxane VMQ
Vinyl Methyl Silicone XNBR Acrylonitrile Butadiene Carboxy Monomer
XSBR Styrene Butadiene Carboxy Monomer YBPO Thermoplastic
Polyether-ester YSBR Styrene Butadiene Block Copolymer YXSBR
Styrene Butadiene Carboxy Block Copolymer -- Latex products --
Synthetic rubbers -- Natural rubbers -- Neoprene -- Chloroprene
derivatives -- Fluorinated Polymers -- Polyesters -- Polyamides --
Polyacetals
[0045] In some embodiments, the adulterants include acrylonitrile
butadiene styrene thermoplastic, polyacrylate rubber,
ethylene-acrylate rubber, polyester urethane, bromo isobutylene
isoprene rubber, polybutadiene rubber, chloro isobutylene isoprene
rubber, polychloroprene, chlorosulphonated polyethylene,
epichlorohydrin, ethylene propylene rubber, ethylene propylene
diene monomer, polyether urethane, tetrafluoroethylene/propylene
rubbers, perfluorocarbon elastomers, fluoroelastomer, fluoro
silicone, fluorocarbon rubber, high density polyethylene,
hydrogenated nitrile butadiene, polyisoprene, isobutylene isoprene
rubber, low density polyethylene, polyethylene terephthalate,
ethylene vinyl acetate, acrylonitrile butadiene, polyethylene,
polyisobutene, polypropylene, polystyrene, poly vinyl choloride,
polyvinylidene chloride, polyurethane, styrene butadiene, styrene
ethylene butylene styrene copolymer, polysiloxane, vinyl methyl
silicone, acrylonitrile butadiene carboxy monomer, styrene
butadiene carboxy monomer, thermoplastic polyether-ester, styrene
butadiene block copolymer, styrene butadiene carboxy block
copolymer, polyesters, polyamides, polyacetals, or mixtures of any
two or more thereof.
[0046] In some embodiments, the adulterants include a polymer
additive. A partial list of polymer additives is provided in Table
2.
TABLE-US-00002 TABLE 2 Examples of Associated Polymer Additives 1
Plastic stabilizers 2 UV Stabilizers 3 Plasticizers 4 Acetamide 5
Benzyl benzoate 6 Benzyl butyl phthalate 7 Bis (2-ethylhexyl)
adipate 8 Bis (2-ethylhexyl) phthalate 9 Bisphenol A 10 Bisphenol
AF 11 Centralite 12 1,2-Cyclohexane dicarboxylic acid diisononyl
ester 13 Dibutyl phthalate 14 Dibutyl sebacate 15 D cont. 16
Diethylene glycol dinitrate 17 Diisobutyl phthalate 18 Diisodecyl
phthalate 19 Diisononyl phthalate 20 Dimethyl methylphosphonate 21
2,4-Dinitrotoluene 22 Dioctyl adipate 23 Dioctyl terephthalate 24
Dipropylene glycol 25 Epoxidized soybean oil 26 Ethyl butyrate 27
Ethylene carbonate 28 Furoin 29 Neopentyl glycol 30 Phthalate 31
Polybutene 32 Polycaprolactone 33 Propylene carbonate 34 Triacetin
35 Tributyl phosphate 36 Tricresyl phosphate 37 Triethyl phosphate
38 Triethylene glycol dinitrate 39 Trimethylolethane trinitrate 40
Flame retardants 41 Asbestine 42 Barium borate 43 Brominated flame
retardant 44 Bromoform 45 Calcium borate 46 Chlorendic acid 47
Chlorinated paraffins 48 Cubicle curtain 49 Decabromodiphenyl ether
50 Defender M 51 1,2-Dibromoethane 52 Dimethyl chlorendate 53
Dimethyl methylphosphonate 54 Fire-safe polymers 55 Heptazine 56
Hexabromocyclododecane 57 Metepa 58 Noflan 59 Octabromodiphenyl
ether 60 Pentabromodiphenyl ether 61 Phos-Chek 62 Polybrominated
biphenyl 63 Polybrominated diphenyl ethers 64 Polychlorinated
biphenyl 65 Tetrabromobisphenol A 66 Tris (2,3-dibromopropyl)
phosphate 67 Tris (2-chloroethyl) phosphate 68 Zinc borate 69
Halogenated Organics
[0047] In some embodiments, the adulterants include acetamide,
benzyl benzoate, benzyl butyl phthalate, bis(2-ethylhexyl) adipate,
bis(2-ethylhexyl) phthalate, bisphenol A, bisphenol AF,
1,2-cyclohexane dicarboxylic acid diisononyl ester, dibutyl
phthalate, dibutyl sebacate, diethylene glycol dinitrate,
diisobutyl phthalate, diisodecyl phthalate, diisononyl phthalate,
dimethyl methylphosphonate, 2,4-dinitrotoluene, dioctyl adipate,
diisodecyl adipate, dipropylene glycol, epoxidized soybean oil,
ethyl butyrate, ethylene carbonate, furoin, neopentyl glycol,
phthalate, polybutene, polycaprolactone, propylene carbonate,
triacetin, tributyl phosphate, tricresyl phosphate, triethyl
phosphate, triethylene glycol dinitrate, trimethylolethane
trinitrate, asbestine, barium borate, brominated flame retardant,
bromoform, calcium borate, chlorendic acid, decabromodiphenyl
ether, 1,2-dibromoethane, dimethyl chlorendate, dimethyl
methylphosphonate, heptazine, hexabromocyclododecane,
octabromodiphenyl ether, pentabromodiphenyl ether, polybrominated
biphenyl, polybrominated diphenyl ethers, polychlorinated biphenyl,
tetrabromobisphenol A, tris(2,3-dibromopropyl)phosphate,
tris(2-chloroethyl)phosphate, zinc borate, or mixtures of any two
or more thereof. In some embodiments, the adulterants include both
a polymer and a polymer additive.
[0048] In some embodiments, the adulterants comprise hindered
phenol, hydroquinone, phosphite, or thioester anti-oxidants. In
some embodiments, the adulterants include styrenated phenol,
alkylated hindered phenols, 2-tert-butyl-4-methylphenol, 2- and
3-tert-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol,
2,6-distyrenated p-cresol, 2,6-di-tert-butyl-4-nonylphenol,
2,4-bis-(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-tria-
zine, 2,5-di-tert-amylhydroquinone, mono-tert-butylhydroquinone,
hydroquinone monomethyl ether, 2,5-di-t-butyl hydroquinone,
tris(p-nonylphenyl)phosphite,
tris(2,4-di-tert-butylphenyl)phosphite, distearyl pentaerythritol
diphosphite, dilauryl-3,3'-thio-dipropionate,
distearyl-3,3'-thio-diproprionate, ditridecyl-thio-dipropionate,
thiodipropionic acid, or mixtures of any two or more thereof.
[0049] In some embodiments, the adulterants include pesticides,
such as insecticides, fumigants, fungicides, herbicides, and plant
growth regulators. In some embodiments, the adulterants include
1-bromo-3-chloro-5,5-dimethylhydantoin, ethyl
(R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionate,
2-methyl-4-chlorophenoxyacetic acid, methyl
2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)methylamino]carbonyl]amino]s-
ulfonyl]benzoate, abamectin, acephate, acetamiprid, acetochlor
(2-Chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide),
aldicarb (2-methyl-2-(methylthio)propanal
O--(N-methylcarbamoyl)oxime), amitraz, 3-amino-1,2,4-triazole,
ancymidol, anilazine, atrazine, azinphos-methyl, azinphos-ethyl,
azoxystrobin, bentazon, bifenthrin, bendiocarb, bensulide,
boscalid, brodifacoum, bromadiolone, bromethalin, bromoxynil,
(3aR,7aS)-2-[(trichloromethyl)sulfanyl]-3a,4,7,7a-tetrahydro-1H-isoindole-
-1,3(2H)-dione, carbaryl, carbathiin, carbofuran, chloroneb,
chlorophacinone, chloropicrin, chlorothalonil, chlorphropham,
chlorphyrifos, chlormequat chloride, clethodim,
clodinafop-propargyl, clofentezine, clopyralid, clothianidin,
cyfluthrin ([(R)-cyano-[4-fluoro-3-(phenoxy)phenyl]methyl]
(1R,3R)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate),
cyhalothrin, cymoxanil, cypermethrin, cyprodinil, cyromazine,
daminozide, dazomet, (Z,E)-tetradeca-9,12-dienyl acetate,
deltamethrin, desmedipham, diazinon (O,O-diethyl
O-[4-methyl-6-(propan-2-yl)pyrimidin-2-yl]phosphorothioate),
dicamba, dichlobenil, diclofop-methyl, dicloran,
2,4-dichlorophenoxyacetic acid ("2,4-D"), dichloropropene,
dichlorvos, dicofol, didecyl dimethyl ammonium chloride,
difenoconazole, difenzoquat, dimethenamid, dimethoate,
dimethomorph, dinocap, diphacinone, diquat, diuron
(3-(3,4-dichlorophenyl)-1,1-dimethylurea), dodemorph acetate,
dodine, endosulfan, S-ethyl N,N-dipropylcarbamothioate,
ethalfluralin, ethametsulfuron-methyl, ethephon, etridiazole,
fenbuconazole, fenbutatin-oxide, fenhexamid, fenoxaprop-p-ethyl,
fenoxycarb, ferbam, florasulam, fluazifop-p-butyl, fludioxonil,
fluoroxypyr, flusilazole, folpet, glufosinate, glyphosate,
hexazinone, imazamethabenz, imazamox, imazethapyr, imidacloprid,
iprodione, isoxaben, kinoprene, kresoxim-methyl, linuron,
malathion, mancozeb, maneb (manganese
ethylene-1,2-bisdithiocarbamate, polymer),
2-methyl-4-chlorophenoxyacetic acid (MCPA),
4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB), mecoprop,
mefenoxam, metalaxyl, metham sodium, metham potassium,
methamidophos, methomyl, methoxyfenozide, methoprene, methyl
bromide, metiram, metolachlor
((S)-2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(1-methoxypropan-2-yl)acetami-
de), metribuzin, metsulfuron methyl, myclobutanil, naled
(1,2-dibromo-2,2-dichloroethyl dimethyl phosphate), napropamide,
naptalam, nicosulfuron, nonanoic acid, oxadiazon, oxamyl,
oxycarboxin, oxyfluorfen, paclobutrazol, paraquat
(1,1'-dimethyl-4,4'-bipyridinium dichloride), pendimethalin,
permethrin, phenmediphan, phosalone, phosmet, pirimicarb,
prohexadione calcium, prometryne, propanil, propiconazole,
propyzamide, pyraclostrobin, pyrethrin I, pyrethrin II, pyridaben,
quinclorac, quintozene, rimsulfuron, sethoxydim, simazine
(6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine), spinosyn A,
spinosyn D, tebuconazole, tebufenozide, tefluthrin, terbacil,
terbufos, tetrachlorvinphos, thiabendazole, thiamethoxam,
thifensulfuron methyl, thiophanate methyl, thiram
(dimethylcarbamothioylsulfanyl N,N-dimethylcarbamodithioate),
tralkoxydim, triadimenol, triallate, tribenuron methyl,
trichlorfon, trifluralin, triforine, trinexapac, trinexapac-ethyl,
triticonazole, uniconazole, vinclozolin, warfarin, or mixtures of
any two or more thereof. In some embodiments, the adulterants
include carbamates, organophospates, and phenoxy components. In
some embodiments, the adulterants include acephate, acetochlor
(2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide),
aldicarb (2-methyl-2-(methylthio)propanal
O--(N-methylcarbamoyl)oxime), atrazine, bifenthrin, chloropicrin,
chlorothalonil, chlorphyrifos, 2,4-dichlorophenoxyacetic acid
("2,4-D"), dichloropropene, dimethenamid, diuron
(3-(3,4-dichlorophenyl)-1,1-dimethylurea), ethephon, fenoxycarb,
glyphosate, 2-methyl-4-chlorophenoxyacetic acid (MCPA), metham
sodium, metham potassium, methyl bromide, metolachlor
((S)-2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(1-methoxypropan-2-yl)acetami-
de), paraquat (1,1'-dimethyl-4,4'-bipyridinium dichloride),
pendimethalin, propanil, simazine, trifluralin, or mixtures of any
two or more thereof.
[0050] Any of the previously described adulterants may also be
included in the feed stream as mixtures of any two or more thereof
of the adulterants. Combinations of any two or more members of the
above recited groupings of adulterants as well as combinations of
any two or more of the above recited adulterants are within the
scope of the present technology and presently described method. In
some embodiments, the adulterants include polyvinylidene chloride
and a polymer additive. In some embodiments, the adulterants
include polyvinylidene chloride and a pesticide.
[0051] The fixed bed reactor is at a temperature less than about
750.degree. F. (400.degree. C.). In some embodiments, the
temperature is from about 70.degree. F. (20.degree. C.) to about
750.degree. F. (400.degree. C.). In some embodiments, the
temperature is from about 140.degree. F. (60.degree. C.) to about
750.degree. F. (400.degree. C.). In some embodiments, the fixed bed
reactor is at a temperature falling in the range from about
480.degree. F. (250.degree. C.) to about 750.degree. F.
(400.degree. C.). The fixed bed reactor may operate at a
temperature of about 80.degree. F. (25.degree. C.), about
100.degree. F. (38.degree. C.), about 150.degree. F. (65.degree.
C.), about 200.degree. F. (95.degree. C.), about 250.degree. F.
(120.degree. C.), about 300.degree. F. (150.degree. C.), about
350.degree. F. (175.degree. C.), about 400.degree. F. (205.degree.
C.), about 450.degree. F. (230.degree. C.), about 500.degree. F.
(260.degree. C.), about 540.degree. F. (280.degree. C.), about
570.degree. F. (300.degree. C.), about 610.degree. F. (320.degree.
C.), about 645.degree. F. (340.degree. C.), about 680.degree. F.
(360.degree. C.), about 720.degree. F. (380.degree. C.), and ranges
including and in between any two of these values. The weighted
average bed temperature (WABT) is commonly used in fixed bed,
adiabatic hydroprocessing reactors to express the "average"
temperature of the reactor which accounts for the nonlinear
temperature profile between the inlet and outlet of the
reactor.
WABT = i = 1 N ( WABT i ) ( Wc i ) ##EQU00001## WABT i = T i in + 2
T i out 3 ##EQU00001.2##
[0052] In the equation above, T.sub.i.sup.in and T.sub.i.sup.out
refer to the temperature at the inlet and outlet, respectively, of
catalyst bed i. As shown, the WABT of a reactor system with N
different catalyst beds may be calculated using the WABT of each
bed (WABT.sub.i) and the weight of catalyst in each bed
(Wc.sub.i).
[0053] The feed stream is combined with a hydrogen-rich treat gas.
The ratio of hydrogen-rich treat gas to biorenewable feedstock is
in the range of about 2,000 to about 10,000 SCF/bbl (in units of
normal liter of gas per liter of liquid (Nl/l), about 355 Nl/l to
about 1780 Nl/l). The ratio of hydrogen-rich treat gas to
biorenewable feedstock may be about 2,500 SCF/bbl (about 445 Nl/l),
about 3,000 SCF/bbl (about 535 Nl/l), about 3,500 SCF/bbl (about
625 Nl/l), about 4,000 SCF/bbl (about 710 Nl/l), about 4,500
SCF/bbl (about 800 Nl/l), about 5,000 SCF/bbl (about 890 Nl/l),
about 5,500 SCF/bbl (about 980 Nl/l), about 6,000 SCF/bbl (about
1070 Nl/l), about 6,500 SCF/bbl (about 1160 Nl/l), about 7,000
SCF/bbl (about 1250 Nl/l), about 7,500 SCF/bbl (about 1335 Nl/l),
about 8,000 SCF/bbl (about 1425 Nl/l), about 8,500 SCF/bbl (about
1515 Nl/l), about 9,000 SCF/bbl (about 1600 Nl/l), about 9,500
SCF/bbl (about 1690 Nl/l), and ranges including and in between any
two of these values. The hydrogen-rich treat gas contains contain
from about 70 mol % to about 100 mol % hydrogen. In terms of mass
ratio, the ratio of the feed stream to hydrogen-rich treat gas is
from about 5:1 to 25:1. The ratio of the feed stream to
hydrogen-rich treat gas may be 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 22:1, about 23:1, about 24:1, and ranges
including and in between any two of these values or greater than
any one of these values.
[0054] In some embodiments, the fixed bed reactor includes a
hydrogenation catalyst. The hydrogenation catalyst may include Co,
Mo, Ni, Pt, Pd, Ru, W, NiMo, NiW, CoMo, or combinations of any two
or more thereof. In some embodiments, the hydrogenation catalyst
includes NiMo, NiW, CoMo, and combinations of any two or more
thereof. Supports for the hydrogenation catalyst include alumina
and alumina with silicon oxides and/or phosphorus oxides. It should
be noted that one of ordinary skill in the art can select an
appropriate hydrogenation catalyst to provide a particular result
and still be in accordance with the present technology.
[0055] In some embodiments, the fixed bed reactor includes a
hydrotreatment catalyst. The hydrotreatment catalyst may include
Co, Mo, Ni, Pt, Pd, Ru, W, NiMo, NiW, CoMo, or combinations of any
two or more thereof. In some embodiments, the hydrotreatment
catalyst includes NiMo, NiW, CoMo, and combinations of any two or
more thereof. Supports for the hydrotreatment catalyst include
alumina and alumina with silicon oxides and/or phosphorus oxides.
It should be noted that one of ordinary skill in the art can select
an appropriate hydrotreatment catalyst to provide a particular
result and still be in accordance with the present technology.
[0056] In some embodiments, the fixed bed reactor includes a
hydroisomerization catalyst. The hydroisomerization catalyst may be
a bifunctional catalyst. 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, mesoporous
material (MCM), zirconia and/or anion-modified zirconia, or
aluminum silicate zeolite (ZSM). In some embodiments the metal
includes platinum, palladium, or tungsten. In some embodiments, the
support includes HF-treated alumina, silica alumina, zirconia,
zirconium sulfate, SAPO-11, SAPO-31, SAPO-41, MCM-41, Zeolite Y,
mordenite, ZSM-22, and ZSM-48. In some embodiments, the
hydroisomerization catalyst includes Pt/Pd-on-ASA or Pt-on-SAPO-11.
However, it should be noted that one of ordinary skill in the art
can select an appropriate hydroisomerization catalyst to provide a
particular result and still be in accordance with the present
technology.
[0057] To maintain the active metal sulfide functionality of the
hydrotreatment and/or hydroisomerization catalyst despite the
negligible presence of organic sulfur in most biorenewable
feedstocks, the feed stream may be supplemented with a sulfur
compound that decomposes to hydrogen sulfide when heated and/or
contacted with a catalyst. In some embodiments, the sulfur compound
includes methyl mercaptan, ethyl mercaptan, n-butyl mercaptan,
dimethyl sulfide (DMS), dimethyl disulfide (DMDS),
dimethylsulfoxide (DMSO), diethyl sulfide, di-tert-butyl
polysulfide (TBPS), di-octyl polysulfide, di-tert-nonyl polysulfude
(TNPS), carbon disulfide, thiophene, or mixtures of any two or more
thereof. The concentration of the sulfur compound in the feed
stream may be from about 50 ppm to about 2,000 ppm by weight
sulfur. The feed stream may include a fossil-fuel fraction wherein
the fossil-fuel fraction provides the sulfur, either in combination
with or in the absence of the above mentioned sulfur compounds.
[0058] The fixed bed reactor is at a pressure falling in the range
from about 200 psig (about 13.8 barg) to about 4,000 psig (about
275 barg). The pressure may be about 300 psig (21 barg), about 400
psig (28 barg), about 500 psig (34 barg), about 600 psig (41 barg),
about 700 psig (48 barg), about 800 psig (55 barg), about 900 psig
(62 barg), about 1,000 psig (69 barg), about 1,100 psig (76 barg),
about 1,200 psig (83 barg), about 1,300 psig (90 barg), about 1,400
psig (97 barg), about 1,500 psig (103 barg), about 1,600 psig (110
barg), about 1,700 psig (117 barg), about 1,800 psig (124 barg),
about 1,900 psig (131 barg), about 2,000 psig (138 barg), about
2,200 psig (152 barg), about 2,400 psig (165 barg), about 2,600
psig (179 barg), about 2,800 psig (193 barg), about 3,000 psig (207
barg), about 3,200 psig (221 barg), about 3,400 psig (234 barg),
about 3,600 psig (248 barg), about 3,800 psig (262 barg), about
3,900 psig (269 barg), and any ranges including and in between any
two of these values. In some embodiments, the pressure is from
about 1,000 psig (69 barg) to about 2,000 psig (138 barg).
[0059] In some embodiments, the feed stream further comprises a
diluent. The diluent may include a recycled hydroprocessed product,
a distilled fraction of the hydroprocessed product, a petroleum
hydrocarbon fluid, a synthetic hydrocarbon product stream from a
Fischer-Tropsch process, a hydrocarbon product stream produced by
fermentation of sugars (e.g. farnesene), natural hydrocarbons such
as limonene and terpene, natural gas liquids, or mixtures of any
two or more thereof. In some embodiments, the hydrocarbonaceous
diluent includes a recycled hydroprocessed product, a distilled
fraction of the hydroprocessed product, a petroleum hydrocarbon
fluid, or mixtures of two or more thereof. The ratio of
hydrocarbonaceous diluent to biorenewable feedstock falls within
the range from about 0.5:1 to about 20:1. The ratio of
hydrocarbonaceous diluent to biorenewable feedstock may be about
1:1, 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 including and between any two of these
values.
[0060] In some embodiments, the hydroprocessed product includes a
hydrogenated product. In some embodiments, the hydrogenated product
includes a hydrogenated free fatty acid, a hydrogenated fatty acid
ester, or mixtures thereof. In some embodiments, the hydrogenated
fatty acid ester includes a hydrogenated triglyceride. In some
embodiments, the hydrogenated product includes a partially
hydrogenated product. In some embodiments, the hydrogenated product
includes a fully hydrogenated product. For example, in some
embodiments, the hydrogenated product includes a partially
hydrogenated free fatty acid, a partially hydrogenated fatty acid
ester, or mixtures thereof. In some embodiments, the hydrogenated
product includes a partially hydrogenated triglyceride. In some
embodiments, the hydrogenated product includes a fully hydrogenated
free fatty acid, a fully hydrogenated fatty acid ester, or mixtures
thereof. In some embodiments, the hydrogenated product includes a
fully hydrogenated triglyceride.
[0061] In some embodiments, the hydroprocessed product includes at
least 80 wt % paraffins falling within the range of C.sub.11 to
C.sub.24, where the paraffins include C.sub.16 and C.sub.18
paraffins; from about 0.1 wt % to about 7.0 wt % cylcoparaffins;
and from about 0.001 wt % to about 1.0 wt % aromatics. In some
embodiments of such a hydroprocessed product, the hydroprocessed
product is suitable as a diesel fuel, a diesel fuel additive, a
diesel fuel blendstock, a turbine fuel, a turbine fuel additive, a
turbine fuel blendstock, an aviation fuel, an aviation fuel
additive, or an aviation fuel blendstock. In some embodiments of
such a hydroprocessed product, the hydroprocessed product is
suitable as a diesel fuel.
[0062] In some embodiments, the hydroprocessed product may contain
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 %, about 99 wt %, and any range in
between any two of these values or above any one of these values.
In some embodiments, the paraffins include at least about 50% wt %
C.sub.16 and C.sub.18 paraffins. In some embodiments, the paraffins
include at least about 55% wt % C.sub.16 and C.sub.18 paraffins. In
some embodiments, the paraffins include at least about 60 wt %
C.sub.16 and C.sub.18 paraffins. In some embodiments, the paraffins
include C.sub.12, C.sub.16, and C.sub.18 paraffins. In some
embodiments, the paraffins include C.sub.14, C.sub.16, and C.sub.18
paraffins. In some embodiments, the paraffins include C.sub.12,
C.sub.14, C.sub.16, and C.sub.18 paraffins. In some embodiments,
the paraffins include iso-paraffins and n-paraffins. In some
embodiments where the paraffins include iso-paraffins and
n-paraffins, the ratio of iso-paraffins to n-paraffins is at least
about 4:1. The ratio of iso-paraffins to n-paraffins may be about
4.5:1, about 5:1, about 5.5:1, about 6:1, about 6.5:1, 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,
about 30:1, and ranges including and between any two of these
values or above any one of these values. In some embodiments, the
ratio of iso-paraffins to n-paraffins is greater than about 5:1. In
some embodiments, the ratio of iso-paraffins to n-paraffins is
between about 5:1 and about 10:1.
[0063] In some embodiments, at least 70 wt % of the iso-paraffins
are mono-methyl branched paraffins. The mono-methyl branched
paraffins may be about 72 wt %, about 74 wt %, about 76 wt %, about
78 wt %, about 80 wt %, 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 %, about 99 wt %, and ranges including
and between any two of these values or above any one of these
values. Examples of the mono-methyl branched paraffins include, but
are not limited to, 4-methyl heptadecane, 3-methyl hexadecane, and
2-methyl pentadecane. The conversion of the n-paraffins to
iso-paraffins may produce different amounts of mono-methyl terminal
branched products (i.e. 2-methyl branched). Thus, in some
embodiments of the mono-methyl branched iso-paraffins, less than
about 30 wt % are terminal branched. In some embodiments, less than
about 20 wt % of the mono-methyl branched iso-paraffins are
terminal branched. In some embodiments, less than about 15 wt % of
the mono-methyl branched iso-paraffins are terminal branched. In
some embodiments, less than about 10 wt % of the mono-methyl
branched iso-paraffins are terminal branched. In some embodiments,
less than about 5 wt % of the mono-methyl branched iso-paraffins
are terminal branched. However, in some embodiments, greater than
about 30 wt % of the mono-methyl branched paraffins are terminal
branched.
[0064] In some embodiments, the hydroprocessed product contains
about 0.1 wt % to about 7.0 wt % cycloparaffins. The hydroprocessed
product may have cycloparaffins in the amount of about 6 wt %,
about 5 wt %, about 4 wt %, about 3 wt %, about 2 wt %, about 1 wt
%, 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 any range including and in between any two of
these values or below any one of these values.
[0065] In some embodiments, the hydroprocessed product contains
from about 1.0 wt % to about 0.001 wt % aromatics. The
hydroprocessed 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
%, about 0.09 wt %, about 0.08 wt %, about 0.07 wt %, about 0.06 wt
%, about 0.05 wt %, about 0.04 wt %, about 0.03 wt %, about 0.02 wt
%, about 0.01 wt %, about 0.009 wt %, about 0.008 wt %, about 0.007
wt %, about 0.006 wt %, about 0.005 wt %, about 0.004 wt %, about
0.003 wt %, about 0.002 wt %, about 0.001 wt %, and ranges
including and between any two of these values or below any one of
these values. In some embodiments, the hydroprocessed product
contains less than about 0.5 wt % total aromatics. In some
embodiments, the hydroprocessed product has less than about 0.01 wt
% benzene. The hydroprocessed product may contain benzene in the
amount of about 0.008 wt %, about 0.006 wt %, about 0.004 wt %,
about 0.002 wt %, about 0.001 wt %, about 0.0008 wt %, about 0.0006
wt %, about 0.0004 wt %, about 0.0002 wt %, about 0.0001 wt %,
about 0.00008 wt %, about 0.00006 wt %, about 0.00004 wt %, about
0.00002 wt %, about 0.00001 wt % and ranges including and between
any two of these values or less than any one of these values. Such
low values of benzene may be determined through appropriate
analytical techniques, including but not limited to two dimensional
gas chromatography of the composition. In some embodiments, the
hydroprocessed product has less than about 0.00001 wt % of
benzene.
[0066] In some embodiments, the hydroprocessed product has a sulfur
content less than about 5 wppm. The hydroprocessed product may have
a sulfur content of about 4 wppm, about 3 wppm, about 2 wppm, about
1 wppm, about 0.9 wppm, about 0.8 wppm, about 0.7 wppm, about 0.6
wppm, about 0.5 wppm, about 0.4 wppm, about 0.3 wppm, about 0.2
wppm, about 0.1 wppm, and ranges including and between any two of
these values or less than any one of these values. In some
embodiments, the hydroprocessed product has a sulfur content less
than about 2 wppm.
[0067] In some embodiments, the hydroprocessed product has less
than about 0.1 wt % oxygenates. The hydroprocessed product may have
oxygenates in the amount of about 0.09 wt %, about 0.08 wt %, about
0.07 wt %, about 0.05 wt %, about 0.04 wt %, about 0.03 wt %, about
0.02 wt %, about 0.01 wt %, and ranges including and between any
two of these values or below any one of these values. Such low
values of oxygenates can be detected through appropriate analytical
techniques, including but not limited to Instrumental Neutron
Activation Analysis.
[0068] In some embodiments, the biorenewable feedstock may be
pretreated. Such pretreatments include, but are not limited to,
degumming, neutralization, bleaching, deodorizing, or a combination
of any two or more thereof. One type of degumming is acid
degumming, which 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/or neutralization may include high
shear mixers and disk stack centrifuges. 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.
[0069] Bleaching as used herein is a filtration process common to
the processing of glyceride oils. Many types of processing
configurations and filtration media such as diatomaceous earth,
perlite, silica hydrogels, cellulosic media, clays, bleaching
earths, carbons, bauxite, silica aluminates, natural fibers and
flakes, synthetic fibers and mixtures thereof are known to those
skilled in the art. Bleaching can also be referred to by other
names such as clay treating which is a common industrial process
for petroleum, synthetic and biological feeds and products.
[0070] Additional types of filtration may be performed to remove
suspended solids from the biorenewable feedstock before and/or
after and/or in lieu of degumming and/or bleaching. In some
embodiments, rotoscreen filtration is used to remove solids larger
than about 1 mm from the biorenewable feedstock. Rotoscreen
filtration is a mechanically vibrating wire mesh screen with
openings of about 1 mm or larger that continuously removes bulk
solids. Other wire mesh filters of about 1 mm or larger housed in
different types of filter may be also be employed, including
self-cleaning and backwash filters, so long as they provide for
bulk separation of solids larger than 1 mm, such as from about 1 mm
to about 20 mm. In embodiments where bleaching through clay-coated
pressure leaf filter is not used, cartridge or bag filters with
micron ratings from about 0.1 to about 100 may be employed to
ensure that only the solubilized and or finely suspended (e.g.
colloidal phase) adulterants are present in the feed stream.
Filtration is typically performed at temperatures high enough to
ensure the feed stream is a liquid of about 0.1 to 100 cP
viscosity. This generally translates into a temperature range of
20.degree. C. to 90.degree. C. (about 70.degree. F. to about
195.degree. F. For example, FIGS. 1A and 1B illustrate the removal
of suspended solid adulterants by wire mesh screen and bag
filters.
[0071] In some embodiments, from about 100 to about 15,000 reactor
volumes of biorenewable feedstock are processed prior to shutdown
of the fixed bed hydroprocessing reactor. The reactor volumes of
biorenewable feedstock processed may be about 200, about 300, about
400, about 500, about 600, about 700, about 800, about 900, about
1,000, about 1,100, about 1,500, about 2,000, about 2,500, about
3,000, about 3,500, about 4,000, about 4,500, about 5,000, about
5,500, about 6,000, about 6,500, about 7,000, about 7,500, about
8,000, about 8,500, about 9,000, about 9,500, about 10,000, about
10,500, about 11,000, about 11,500, about 12,000, about 12,500,
about 13,000, about 13,500, about 14,000, about 14,500, or any
range including and between any two of these values or greater than
any one of these values.
[0072] In some embodiments, the liquid hourly space velocity (LHSV)
of the biorenewable feedstock through the fixed bed hydroprocessing
reactor is from about 0.2 h.sup.-1 to about 10.0 h.sup.-1. 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 3.2
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 including and between any two of these values
or above any one of these values.
[0073] In some embodiments, the biorenewable feedstock includes
free fatty acids, fatty acid esters (including mono-, di-, and
trigylcerides), or combinations thereof. In some embodiments, the
biorenewable feedstock includes animal fats, animal oils, plant
fats, plant oils, vegetable fats, vegetable oils, greases, or
mixtures of any two or more thereof. In some embodiments, the fatty
acid esters include fatty acid methyl ester, a fatty acid ethyl
ester, a fatty acid propyl ester, a fatty acid butyl ester, or
mixtures of any two or more thereof. In some embodiments, the
biorenewable feedstock comprises the fatty acid distillate from
vegetable oil deodorization. Depending on level of pretreatment,
fats, oils, and greases, may contain between about 1 wppm and about
1,000 wppm phosphorus, and between about 1 wppm and about 500 wppm
total metals (mainly sodium, potassium, magnesium, calcium, iron,
and copper). Plant and/or vegetable oils include, but are not
limited to, soybean oil, canola oil, rapeseed oil, tall oil, tall
oil fatty acid, palm oil, palm oil fatty acid distillate, palm
kernel oil, jatropha oil, sunflower oil, castor oil, camelina oil,
algae oil, seaweed oil, oils from halophiles, and mixtures of any
two or more thereof. These may be classified as crude, degummed,
and RBD (refined, bleached, and deodorized) grade, depending on
level of pretreatment and residual phosphorus and metals content.
However, any of these grades may be used in the present technology.
Animal fats and/or oils as used above includes, but is not limited
to, inedible tallow, edible tallow, technical tallow, floatation
tallow, lard, poultry fat, poultry oils, fish fat, fish oils, and
mixtures of any two or more thereof. Greases may include, but are
not limited to, yellow grease, brown grease, waste vegetable oils,
restaurant greases, trap grease from municipalities such as water
treatment facilities, and spent oils from industrial packaged food
operations, and mixtures of any two or more thereof.
[0074] In some embodiments, the biorenewable feedstock comprises
animal fats, poultry oil, soybean oil, canola oil, rapeseed oils,
palm oil, palm kernel oil, jatropha oil, castor oil, camelina oil,
algae oil, seaweed oil, halophile oils, rendered fats, restaurant
greases, brown grease, yellow grease, waste industrial frying oils,
fish oils, tall oil, tall oil fatty acids, or mixtures of any two
or more thereof. In some embodiments, the biorenewable feedstock
includes animal fats, restaurant greases, brown grease, yellow
grease, waste industrial frying oils, or mixtures of any two or
more thereof.
[0075] In some embodiments, the hydroprocessed product is
fractionated to provide a middle distillate fraction. In some
embodiments, the middle distillate fraction is suitable as a diesel
fuel. In some embodiments, the fractionation is conducted in a
distillation column equipped with a reboiler or stripping steam in
the bottom of the column, and a condenser at the top. The reboiler
or stripping steam provide the thermal energy to vaporize the
heavier fraction of the hydrocarbons while the condenser cools the
lighter hydrocarbon vapors to return hydrocarbon liquid back into
the top of the column. The distillation column is equipped with a
plurality of plates or beds of packing material wherein the rising
vapor and falling liquid come into counter-current contact. The
column's temperature profile from bottom to top is dictated by the
composition of the hydrocarbon feed and the column pressure. In
some embodiments, column pressures range from about 200 psig (about
13.8 barg) to about -14.5 psig (about -1 barg). The column is
equipped with one or a plurality of feed nozzles. A portion of the
condenser liquid (typically 10 to 90 vol %) is drawn off as
overhead distillate product while the rest is allowed to refluxed
back to the column. In some embodiments, the column separates the
product into a light and a heavy hydrocarbon fraction. In some
embodiments, a broad boiling hydrocarbon feed may be separated into
three or more fractions (e.g. a C.sub.5-C.sub.8 naphtha overhead
fraction, a C.sub.9-C.sub.14 jet fuel side draw, and a
C.sub.15-C.sub.18+ diesel bottoms fraction). While some embodiments
employ a plurality of draw-off nozzles to fractionate the feed into
multiple cuts in the same column, other embodiments achieve the
same separation using a plurality of columns in series, each
separating the feed into an overhead fraction and a bottom
fraction.
[0076] In some embodiments and in lieu of hydroisomerizing, the
paraffinic product from the HDO reaction, or a portion thereof, can
be hydrocracked, dehydrogenated, oligomerized, and/or reformed to
produce other products or chemical feedstocks.
[0077] The present technology, 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 technology.
EXAMPLES
Example 1
[0078] A fixed-bed hydroprocessing reactor containing two catalyst
beds was loaded with two types of hydrotreating catalyst. The
bottom bed was filled with a high activity NiMo catalyst and the
top bed with a lower activity Mo catalyst. Both catalysts were in
the oxide form when loaded and were sulfided during reactor
startup.
[0079] The feedstock processed was a mixture of commercially traded
animal fats, vegetable oils (including used cooking oil), and
greases (a "FOG" feed). The FOG feeds contained between 52% and 88%
unsaturated fatty acids, indicating that they would undergo
exothermic hydrodeoxygenation, as well as adulterants. PE is used
herein as an illustrative example of an adulterant associated with
the feedstock. FIG. 2 shows a histogram of over 125 samples of
adulterated feedstocks over the course of two years that were
analyzed for PE. The measured values of PE in the feedstocks ranged
from zero to 360 ppm, but individual shipments were known to
greatly exceed these values.
[0080] The reactor was pressurized with hydrogen and controlled at
about 1,800 psig pressure (124 barg). The feedstock was pumped to
the reactor at a rate equivalent to 0.72 to 1.1 LHSV (vol/h FOG
feed per vol NiMo catalyst). The feedstock was combined with heated
hydrocarbon diluent to achieve a reactor inlet temperature within
the 510.degree. F. (266.degree. C.) to 540.degree. F. (282.degree.
C.) range. The hydrocarbon diluent was the product of the reaction
and which was combined with feed at a 2:1 ratio (vol diluent:vol
feed). Hydrogen was introduced to the reactor at a rate of 5,000
SCF/bbl (890 Nl/l) along with the feed and diluent. Additional
hydrogen was introduced to the reactor as quench gas between the
top and bottom beds to control the outlet temperature to a value
between 680.degree. F. (360 C) to 710.degree. F. (377.degree. C.).
The WABT of the reactor was thus between about 620.degree. F.
(327.degree. C.) and 653.degree. F. (345.degree. C.). The
hydrodeoxygenated (HDO) product was further processed via
hydroisomerization and distillation to provide a hydrocarbon
product meeting diesel fuel specifications ("FOG diesel"). A
portion of the HDO product was recycled and used as diluent for the
feed as described herein.
[0081] Notably, as shown in Table 3, the hydroprocessing of
feedstocks consistently yielded high quality FOG diesel despite the
variable adulterant concentration of the feed.
TABLE-US-00003 TABLE 3 Comparison of PE Content of the FOG Feed and
Finished FOG Diesel Carbon Residue Description Year 1 Year 2
Average feedstock PE (ppm) over year 54 20 Average diesel 10%
carbon residue (wt %) 0.036 0.036 Average carbon residue, whole
diesel 36 36 (ppm)
Based upon the feedstocks processed during Year 1 and Year 2, the
estimated annual average PE in the feedstock was 54 ppm and 20 ppm,
respectively. During the same period of time (e.g. over 100 samples
tested), the annual averages of finished diesel carbon residue (per
ASTM D524) were 0.036 wt %. Converting to a whole diesel basis,
this is equivalent to 36 ppm for both Year 1 and Year 2 and
indicates the robustness of the present technology in successful
long-term processing of adulterated feedstocks into a finished
fuel. In addition, there were no engine performance related
problems associated with the renewable fuel, both in blended and
neat forms, ranging from the use of the fuel in conventional on and
off-road diesel applications to high performance race engines and
large locomotive engines.
Example 2
[0082] A portion of the renewable diesel product of Example 1 was
distilled to produce a biorenewable jet fuel fraction ("FOG
kerosene"). The distillation was performed to achieve a 270.degree.
C. cut-point (target final boiling point) for the jet fuel,
consistent with final boiling point specification of 300.degree. C.
max.
[0083] Table 4 provides a summary of the specification test results
for the biorenewable jet fuel according to the present technology
in comparison to the industry minimum standard for synthetic jet
fuel (D7566), a synthetic jet fuel produce by the Fischer-Tropsch
Gas-to-Liquid (GTL) process, and a petroleum jet fuel (JP-8). The
GTL jet fuel fraction ("GTL synthetic kerosene" in Table 4) was
produced from conversion of natural gas to syngas, followed by
Fischer-Tropsch synthesis. The GTL synthetic kerosene provides a
baseline for an "adulterant free" fuel. As observed in Table 4, the
thermal stability and existent gum values (indicators of residual
adulterants) for the biorenewable jet fuel produced by the present
method was the same as the "adulterant free" GTL synthetic
kerosene. Specifically, the thermal stability test at 325.degree.
C. produced no tube pressure drop (0 mm Hg) or discoloration
(rating 1). This is in contrast to a 2 mm Hg observed pressure drop
for the JP-8 fuel at the less severe test condition of 260.degree.
C.
TABLE-US-00004 TABLE 4 Jet Fuel Test Results for GTL Kerosene, FOG
Kerosene, and Petroleum Jet Fuel D7566 Specification for Synthetic
FOG Hydrocarbons GTL kerosene JP-8 in Aviation synthetic (renewable
Petroleum Turbine Fuel kerosene jet fuel) Jet Fuel Acidity, mg
KOH/g 0.015 max 0.003 0.001 0.003 Flash point, .degree. C. 38.0 min
38.5 45.5 51 Density @ 15 C, kg/L 0.730-0.770 0.734 0.761 0.804
Freezing point, .degree. C. -40.0 max -50.5 -48.7 -51 Net heat of
combustion, MJ/kg 42.8 min 43.8 44.2 43.2 Thermal stability Control
temperature, .degree. C. 325 min 360 360 260 Filter pressured drop,
mmHg 25 max 0 0 2 Tube rating 3 max 1 1 1 Existent gum, mg/100 mL 7
max 0.3 0.3 0.4
[0084] 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.
[0085] 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.
[0086] 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.
[0087] 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.
[0088] 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.
[0089] 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.
[0090] Other embodiments are set forth in the following claims.
* * * * *