NZ615840B2 - Low pour point renewable fuel blend - Google Patents
Low pour point renewable fuel blend Download PDFInfo
- Publication number
- NZ615840B2 NZ615840B2 NZ615840A NZ61584012A NZ615840B2 NZ 615840 B2 NZ615840 B2 NZ 615840B2 NZ 615840 A NZ615840 A NZ 615840A NZ 61584012 A NZ61584012 A NZ 61584012A NZ 615840 B2 NZ615840 B2 NZ 615840B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- fuel blend
- vol
- renewable fuel
- biologically derived
- normal paraffins
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 186
- 239000000446 fuel Substances 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 claims abstract description 58
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 239000003208 petroleum Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001603 reducing Effects 0.000 abstract description 22
- 229910052799 carbon Inorganic materials 0.000 description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 41
- 239000003921 oil Substances 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 150000004665 fatty acids Chemical class 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000012188 paraffin wax Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000002283 diesel fuel Substances 0.000 description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 239000008158 vegetable oil Substances 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 235000019482 Palm oil Nutrition 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 125000005456 glyceride group Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002540 palm oil Substances 0.000 description 5
- -1 platinum group metals Chemical class 0.000 description 5
- 238000004642 transportation engineering Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- 230000002378 acidificating Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 230000003197 catalytic Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000007655 standard test method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006606 decarbonylation reaction Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002194 fatty esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000000640 hydroxylating Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 238000009884 interesterification Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000813 microbial Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BVDRUCCQKHGCRX-UHFFFAOYSA-N 2,3-dihydroxypropyl formate Chemical compound OCC(O)COC=O BVDRUCCQKHGCRX-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 240000007842 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005466 alkylenyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001588 bifunctional Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000000828 canola oil Substances 0.000 description 1
- 235000019519 canola oil Nutrition 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000005824 corn Nutrition 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 230000001627 detrimental Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatoms Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
renewable fuel blend and a process for producing a renewable fuel blend are described. The blend includes biologically derived C13 to C18 normal paraffins, which are provided to the blend in quantities such that blend does not require a pour point reducing treatment to achieve a low pour point. In embodiments, the normal paraffins are produced in an upgrading process, such as a hydrotreating process. embodiments, the normal paraffins are produced in an upgrading process, such as a hydrotreating process.
Description
LOW POUR POINT RENEWABLE FUEL BLEND
FIELD OF THE INVENTION
This ion relates generally to fuels derived from biomass, and specifically to
methods and systems for efficiently making a renewable transportation fuel.
OUND OF THE INVENTION
Biofuels are of increasing interest for a number of reasons including: (1) they are a
renewable ce, (2) their production is less dependent on geopolitical considerations, (3)
they provide the possibility of a direct replacement of petroleum-based fuels in existing
es, and (4) the net greenhouse gas emissions can be substantially reduced by virtue of
C02 uptake by biofuel sors—particularly in the case of cellulosic feedstocks.
An easily—obtainable biofuel is vegetable oil, which largely comprises ides
and some free fatty acids. The properties of vegetable oil, however, make it generally
inappropriate for use as a direct replacement for petroleum diesel in vehicle engines. The
vegetable oils' viscosities are generally too high and they do not burn cleanly enough, thereby
leaving damaging carbon deposits on the engine. Additionally, vegetable oils tend to gel,
especially at low temperatures, y hindering their use in colder climates. These problems
are mitigated when the vegetable oils are d with petroleum fuels, but still remain an
impediment for long—tenn use in diesel engines.
somerization is often used to improve the low temperature properties of
vegetable oils blended with petroleum fuels. But requiring a hydroisomerization process step
for making blends that meet specifications adds significant cost. It is desirable to develop a
process for making renewable transportation fuels that contain vegetable oils without the
need for a hydroisomerization process step.
The foregoing has outlined rather broadly es of the present invention in
order that the detailed description of the invention that follows may be better understood.
Additional es and advantages of the invention will be described hereinafter which form
the subject of the claims of the invention.
SUMNLARY OF THE INVENTION
Accordingly, the present invention provides a renewable fuel composition having
a low pour point, such as a pour point of less than 0°C, and a method for preparing the
renewable fuel composition.
In embodiments, the process for producing a renewable fuel blend comprises
providing in a range of from 1 vol. % to 20 vol. % of biologically derived C13 to C18 normal
paraffins to a renewable fuel blend, such that a ratio AClg / (AC14 + AC16) is less than 0.5,
wherein:
AClg represents a quantity of biologically derived C18 normal paraffins, as a vol. % of
the renewable fuel blend;
AC16 represents a quantity of biologically derived C16 normal paraffins, as a vol. % of
the renewable fuel blend; and
AC14 represents a quantity of biologically derived C14 normal paraffins, as a vol. % of
the renewable fuel blend.
In embodiments, A C14 is in the range of from 0 to 10 vol. %, A C16 is in the range
of from 0 to 10 vol. %, and A C18 is in the range of from 0 to 5 vol. %.
In embodiments, biologically derived normal paraffins are blending with middle
distillate to produce the renewable fuel blend. In embodiments, a biologically d
feedstock is hydrotreated to form the biologically derived normal paraffins. In embodiments,
a biologically derived feedstock is pretreated, and at least a n of the pretreated products
are hydrotreated to form the normal paraffins.
In ments, the renewable fuel blend is ed by hydrotreating a middle
distillate and blending at least a portion of the hydrotreated product with ically derived
normal paraffins. In embodiments, the renewable fuel blend is ed by hydrotreating a
blend of biologically derived normal ns and middle distillate. In embodiments, the
biologically derived feedstock is pretreated, and at least a portion of the pretreated ts
are d with middle late and the blend hydrotreated to produce the renewable fuel
blend.
The present invention further provides a process for producing a renewable fuel
blend comprising pretreating at least one biologically derived oil to produce a biologically
derived feedstock; hydrotreating a blend of the biologically derived feedstock and a middle
distillate to produce at least one hydrotreated liquid t; and ring a renewable fuel
blend comprising in the range of from 1 vol. % to 20 vol. % of biologically derived C13 to
C18 normal paraffins, such that the ratio A C18 / (A C14 + A C16 ) is less than 0.5, wherein:
AClg represents a quantity of biologically derived C18 normal paraffins provided by
the biologically derived feedstock, as a vol. % of the renewable fuel blend;
AC16 ents a quantity of biologically derived C16 normal paraffins provided by
the biologically derived feedstock, as a vol. % of the renewable fuel blend; and
AC14 represents a quantity of biologically derived C14 normal paraffins provided by
the biologically derived feedstock, as a vol. % of the renewable fuel blend.
The present invention further provides a renewable fuel blend comprising in the
range of from 1 vol. % to 20 vol. % of biologically derived C13 to C18 normal ins, such
that the ratio A C18 / (A C14 + A C16) is less than 0.5, wherein:
AClg represents a quantity of biologically derived C18 normal paraffins, as a vol. % of
the renewable fuel blend;
AC16 represents a ty of biologically derived C16 normal paraffins, as a vol. % of
the renewable fuel blend; and
AC14 represents a ty of biologically derived C14 normal paraffins, as a vol. % of
the renewable fuel blend.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 illustrates an embodiment of the invention.
Fig. 2 and Fig. 3 are graphical representations of the changes in the pour points of
renewable fuel blends containing g quantities of normal paraffins.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a renewable fuel composition comprising
ically d normal paraffins, and to a s for making the renewable fuel
ition. As used herein, “renewable fuel” is produced, at least in part, from biologically
d feedstocks, i.e. feedstocks that are derived from a renewable biological resource,
organism, or . A biologically derived feedstock is intended to include feedstocks other
than those derived from petroleum crude oil, and may originate from a single biological
source or from multiple biological sources.
Introducing biologically derived materials into a ry stream for producing
transportation fuel is useful for reducing the carbon footprint of a eum refining
operation. The biologically d materials are converted along with petroleum fractions
into fuel blends that have the desired properties for fuels. For example, fats and free fatty
acids may be converted during a refinery process into normal paraffins, having a carbon
number in the C8 to C24 range, with a high proportion of the normal paraffins being in the C16
and C18 carbon number range. These paraffins have good fuel properties, but they tend to
produce fuel blends with high pour points. Typically, fuels made with biologically derived
als undergo a pour point reducing treatment, by, e.g. hydroisomerization or addition of
a pour point reducing additive to reduce the pour point to acceptable levels. In embodiments,
the present invention provides a renewable fuel blend and a process for preparing a renewable
fuel blend that does not require a pour point reducing treatment to achieve acceptably low
pour points.
Reference is made throughout this specification to hydrocarbons characterized by
a ular carbon number or carbon number range. As used herein, “carbon number” or
“Cn,” where “n” is an r, describes a hydrocarbon or hydrocarbon-containing molecule
or nt (e.g., an alkyl or alkenyl group) wherein “n” denotes the number of carbon atoms
in the fragment or molecule—irrespective of linearity or branching. Carbon number ranges
as disclosed herein (e. g., Cg to C12) refer to molecules having carbon s within the
indicated range (e. g., between 8 carbon and 12 carbon , including the end members of
the range. However, it is not required that every carbon number within a range be
represented within the molecules being described. Likewise, an open ended carbon number
range (e. g., C 35+) refers to molecules having a carbon number within the indicated range
(e. g., 35 or more carbon atoms), including the end member of the range. As described
herein, carbon number distributions are determined by true boiling point distribution and gas
liquid chromatography. As need Within this: cation the total quantity of paraffins and
iso-paraffins at a carbon number are determined by the ASTM D6442 is ofPetrc-lenm
Waxes by Gas {inrmnatograpl’xy g CC”) or an equivalent gas chrmnatography method./w v-
In embodiments, the present invention provides a method for selecting
biologically derived feedstocks to produce a low pour point ble fuel composition from
a fuel manufacturing process.
Biologically derived feedstock
In embodiments, the process ses supplying normal paraffins to a renewable
fuel blend, the normal paraffins being derived from a biologically d feedstock.
Biologically derived oils and fats are included in this class of feedstock. Any feedstocks
comprising glycerides and free fatty acids may be included in the biologically derived
feedstock. Most of the glycerides will be triglycerides, but monoglycerides and diglycerides
may also be present. In embodiments,“biologically—derived oil,” as defined herein, refers to
any glyceride—containing oil that is at least partially derived from a ical source such as,
but not limited to, crops, vegetables, microalgae, and the like. Such oils may further comprise
free fatty acids.
In embodiments, the biologically—derived feedstock is obtained from biological
hydrocarbonaceous ated oils (i.e. “biologically—derived oil,” as defined above) such as
animal, vegetable and seed fats and oils, glycerides, , fatty acids, and esters of fatty
acids. Some non-limiting examples of vegetable and seed oils e canola oil, castor oil,
corn oil, cottonseed oil, linseed oil, olive oil, palm oil, peanut oil, rapeseed oil, safflower oil,
sesame oil, soybean oil, sunflower oil, tung oil, and combinations thereof. Other sources of
glycerides include, but are not limited to, algae, animal tallow, and zooplankton.
The biologically derived normal paraffins may also be derived from a
arbon synthesis process, using, for e, a Fischer Tropsch type of reaction. In
this embodiment, a biologically sourced raw material is lly oxidized to syngas
(comprising H2 and CO), which is converted in a catalytic process to a mixture of oxygenated
and inic ts. Typically, any oxidizable source of organic carbon can potentially
be converted into useful products by this method. In the present process, a biologically
derived feedstock is a suitable feedstock for the hydrocarbon synthesis process. ularly
useful as a feedstock is osic biomass, i.e. vegetation which contains cellulose, and
which is convertible to normal paraffins or other components of transportation fuels.
Hydrocarbon synthesis via syngas conversion, microbial digestion, microbial fermentation
and chemical decomposition are examples of processes for converting cellulose in the
cellulosic biomass.
The glycerides and free fatty acids of typical vegetable and animal fat contain
aliphatic hydrocarbon chains in their structure which have about 8 to about 24 carbon atoms,
with a majority of the fats and oils containing high concentrations of fatty acids in the C14 to
C18 range.
The biologically—derived feedstock provides at least one or more of C14, C16, and
C18 normal paraffins, which are included in the renewable fuel blend. In ments, the
biologically—derived ock provides C14, C16, and C18 normal paraff1ns such that the pour
point of the ble fuel blend is not increased as the result of the normal paraff1n addition.
In embodiments, the biologically d feedstock provides one or more of C14, C16, and C18
normal paraff1ns to produce a low pour point ble fuel blend without the need of a pour
point reducing treatment. Important sources of biologically-derived oil, ing many of
the vegetable and seed oils, contain a significant quantity of C18 normal paraff1ns, which tend
to contribute to an increase in pour point. In the invention, use of one or more of these
materials as the biologically—derived feedstock is balanced by the addition of sources of C13
to C17 normal paraff1ns, including C14 and/or C16 normal paraff1ns, which contribute to a
decrease in pour point. While it is apparent that at least a portion of the C14 and/or C16
normal paraffins may be obtained from non—biological sources, the process provides for
supplying at least a portion of the C13 to C18 normal paraff1ns from ical sources. In
embodiments, at least a portion of the C14 and/or C16 normal paraff1ns are provided from algal
sources, including from algae that have been tailored to produce significant quantities of C14
and/or C16 fatty acids that can be converted to normal paraff1ns. In ments, at least a
portion of the C14 and/or C16 normal paraffins are produced in a syngas conversion process,
such as a Fischer Tropsch process, for converting syngas that is ed, at least in part
from partial oxidation of a renewable biological resource, including vegetation and other
cellulosic material.
Examples of the biologically—derived feedstock e one or more biologically
derived oils or cellulosic biomass, and the products from a preliminary conversion of
biologically derived oils or cellulosic s, such as fatty acids, esters, alcohols and
aldehydes, olef1ns. During preparation of normal paraff1ns, the biologically-derived
ock may be treated in one or more conversion processes, including, for example,
sis, deoxygenation, decarboxylation, decarbonylation, hydroxylation, saponification,
hydrolysis, fication, transesterification, interesterification, hydrogenation, hydrotreating
or hydrocracking. In embodiments, normal paraff1ns produced by the conversion process are
blended with middle distillate to produce the renewable fuel blend. In other embodiments, a
blend of biologically derived feedstock with middle distillate is hydrotreated to produce the
normal paraffins. Specific reaction products depend, at least in part, on at least one of the
ically derived feedstock, the conversion process, the catalyst used and the process
conditions under which the conversion is conducted.
Renewable fuel blend
The renewable fuel blend that is the subject of the present invention comprises
biologically derived hydrocarbons (i.e. organic molecules comprising carbon and hydrogen
and ally oxygen), at least some of which are normal paraffins. In embodiments, the
renewable fuel blend comprises biologically derived hydrocarbons and petroleum derived
hydrocarbons. In some such embodiments, the renewable fuel blend comprises up to 25 vol.
% biologically derived hydrocarbons. In some such embodiments, the renewable fuel blend
comprises from 80 to 99 vol. % petroleum derived hydrocarbons and from 1 to 20 vol. %
biologically derived hydrocarbons.
The renewable fuel blend is characterized by a low pour point and/or a low cloud
point t a pour point ng treatment. In embodiments, the renewable fuel blend has
a pour point of less than 0°C, and usually in the range of from 0°C to —65°C. Likewise, the
renewable fuel blend has a cloud point of less than 0°C, and usually in the range of from 0°C
to —65°C. In ments, a renewable fuel blend meets the pour point specifications of
ASTM D975 without the need for a pour point reducing treatment following the
hydrotreating treatment.
The renewable fuel blend comprises in the range of from 1 vol. % to 20 vol. %
ically derived C13 to C18 normal paraffins, such that the ratio AClg / (AC14 + AC16) is
less than 0.5,
AClg represents a quantity of biologically derived C18 normal paraffins, as a vol. % of
the renewable fuel blend;
AC16 represents a quantity of biologically derived C16 normal paraffins, as a vol. % of
the renewable fuel blend; and
AC14 represents a quantity of ically derived C14 normal paraffins, as a vol. % of
the renewable fuel blend.
In embodiments, A C14 is in the range of from 0 to 10 vol. %, A C16 is in the range
of from 0 to 10 vol. %, and A C18 is in the range of from 0 to 5 vol. %. In embodiments, the
ratio AC18/ (AC14 + AC16) is in the range of between 0.01 and 0.4. In embodiments, the
renewable fuel blend comprises in the range of from 3 vol. % to 15 vol. %, or in the range of
from 4 vol. % to 11 vol. % biologically derived normal paraffins. In embodiments, the
renewable fuel blend comprises at least 5 vol. % C13 to C17 ically derived normal
paraffins. In some such embodiments, the renewable fuel blend comprises at least 5 vol. %
C13 to C15 biologically derived normal paraffins. In embodiments, the renewable fuel blend
comprises less than 3 vol. %, or less than 2 vol. % biologically derived C18 normal paraffins.
In embodiments, the ble fuel blend comprises less than 3 vol. %, or less than 2 vol. %
C12 biologically d normal paraffins.
In embodiments, the following relationship provides the expected effect on the
pour point of the renewable fuel blend by addition of the biologically derived normal
paraffins:
A Pour Point = 47.41*A C18 — 20.04 * A C16 — 18.91 * A C14 (Eq. 1)
where:
A Pour Point represents the change in pour point with the addition of the biologically
derived C13 to (:18 normal paraffins to the renewable fuel blend, and
AC18, AC16, and AClg are as defined above.
Eq. 1 relates to a tion of the pour point of a ble fuel blend. Negative
values of Eq. 1 indicate the ties of C14 and/or C16 and/or C18 normal paraffins which,
when added to a fuel blend, cause a decrease in the pour point of the blend. A quantity of the
normal paraffins that results in Eq. 1 being equal to zero has no effect on pour point. The
quantity of the normal paraffins that gives a positive value for Eq. 1 has the effect of
sing the pour point of the blend.
In embodiments, the presence of the biologically derived normal paraffins in the
renewable fuel blend provides a pour point that is higher, such as in the region of 1°-5°C
2012/031531
higher, than the pour point of the fuel blend in the absence of the biologically derived normal
paraff1ns. In embodiments, the presence of the biologically derived normal paraffins in the
renewable fuel blend provides a pour point that is less than or equal to the pour point of the
fuel blend in the absence of the biologically derived normal paraff1ns. In this case, the
relationship of Eq. 2 holds:
47.41 * A018 — 20.04 * 4016 — 18.91 * AC14 : 0 (Eq. 2)
A renewable fuel blend ed according to Eq. 2 meets the pour point
specifications of ASTM D975 without the need for a pour point reducing treatment ing
the hydrotreating treatment. In an embodiment of the process, a middle distillate is blended
with C14, C16 and/or biologically derived C18 normal paraffins according to Eq. 2 to e a
renewable fuel blend having a pour point that is less than or equal to that of the middle
late without the need for a pour point reducing treatment. In embodiments, the
renewable fuel blend, prepared in the absence of a pour point reducing ent, has a pour
point of no more than 0°C, or has a pour point in the range of from 0° to -65°C. In
embodiments, the renewable fuel blend has a cloud point in the range of from 0°C to -65°C
The renewable fuel blend is a transportation fuel, which refers to hydrocarbonbased
fuels suitable for consumption by vehicles. Such fuels include, but are not limited to,
diesel, gasoline, jet fuel and the like. In embodiments, the renewable fuel blend is a diesel
fuel, which lly includes any fuel that can be used in a compression ignition engine or
the like, and which typically has a boiling point range of between 200° C. (about 392° F.) and
350° C. (about 662° F.). In some such embodiments, the renewable fuel blend meets the
ASTM International Standard Specification for Diesel Fuel Oils D975 (Rev. December
2008), which sets forth specifications for seven diesel fuel oil grades, including Grades 1—D
(referred to herein interchangeably as Grade 1 diesel fuel oil or No. 1 diesel fuel), 2—D (e. g.,
Grade 2 or No. 2 diesel fuel oil), and 4—D (e. g., Grade 4 or No. 4 diesel fuel oil). Each ASTM
specification or other reference on described herein is expressly orated by
reference in its entirety.
[003 5] Pour point is one useful measure of the quality of a renewable fuel blend. “Pour
point,” as defined herein, represents the lowest ature at which a fluid will pour or flow.
See, e. g., ASTM International Standard Test Methods D 5950—02(2007).
Cloud point is a useful measure of the quality of a renewable fuel blend. “Cloud
Point” as described , is the temperature of a liquid specimen when the smallest
observable cluster of hydrocarbon crystals first occurs upon cooling under prescribed
conditions. See, e. g.,. ASTM International Standard Test Methods D 2500—09.
[003 7] In general, the middle distillate that is a component of the renewable fuel blend is
either petroleum based, derived from biological sources (e.g. a biologically derived
feedstock), or a combination of the two. In ments, the middle distillate is petroleum
based. In embodiments, the middle distillate is recovered as a distillate fraction from a
vacuum distillation in refinery operations. In some such embodiments, the middle distillate
has the chemical and physical properties consistent with at least one diesel fuel specification.
Middle late fractions as described herein boil in the range of about 250°-700°F (121°-
37 1°C) as ine by ASTM D86—10a, “Standard Test Method for Distillation of
Petroleum Products at Atmospheric re”. In embodiments, during the preparation of the
renewable fuel blend, the middle distillate meets the flash point specification, the g
range specification, the sulfur ication, and the cloud point specification of a diesel fuel
meeting the specification requirements ofASTM D975 — 10c. In other embodiments, the
middle distillate is reated, with at least a portion of the liquid product red from
hydrotreating process being used to prepare the renewable fuel blend. In embodiments, the
biologically derived normal paraffins are blended with the middle distillate prior to
hydrotreating. In embodiments, the biologically d normal paraff1ns are blended with
the liquid product recovered from the hydrotreating process. In embodiments, the
biologically derived feedstock is blended with the middle distillate prior to hydrotreating.
Producing a renewable fuel blend
The process for producing the renewable fuel blend comprises ing in the
range of from 1 vol. % to 20 vol., % biologically derived C13 to C18 normal paraffins to the
ble fuel blend, such that the ratio AClg / (AC14 + AC16) is less than 0.5,
wherein:
AC18, AC16, and AClg are as defined above.
[003 9] In embodiments, AC14 is in the range of from 0 to 10 vol. %, AC16 is in the range
of from 0 to 10 vol. %, and AClg is in the range of from 0 to 5 vol. %. In embodiments, the
ratio AC18/ (AC14 + AC16) is in the range of between 0.01 and 0.4. In embodiments, the
WO 51016
process comprises providing in the range of from 3 vol. % to 15 vol. %, or from 4 vol. % to
11 vol. % biologically derived normal paraffins to the renewable fuel blend. In
embodiments, the process comprises providing at least 5 vol. % C13 to C17 biologically
d normal paraffins to the renewable fuel blend. In embodiments, the process comprises
providing at least 5 vol. % C13 to C15 ically derived normal ns to the renewable
fuel blend. In embodiments, the process comprises providing no more than 3 vol. %, or no
more than 2 vol. %, biologically derived C18 normal paraffins to the ble fuel blend. In
embodiments, the process comprises providing no more than 3 vol. %, or no more than 2 vol.
%, ically derived C12 normal paraffins to the renewable fuel blend.
In embodiments, the process ses providing C14 and/or C16 and biologically
derived C18 normal paraffins to the renewable fuel blend such that the relationship of Eq. 2
holds:
47.41*AC18 — 20.04*AC16 —18.91*AC14 S 0 (Eq. 1)
The renewable fuel blend prepared by the process has a pour point of no more
than 0°C, in the absence of a pour point reducing treatment. In embodiments, the renewable
fuel blend prepared in the process has a pour point in the range of from 0° to -65°C. In
embodiments, the renewable fuel blend prepared in the process has a cloud point in the range
of from 0°C to —65°C.
In embodiments, the process comprises blending the biologically derived normal
paraffins with middle distillate to produce the renewable fuel blend, wherein the normal
paraffins are produced by converting biologically derived oils or cellulosic biomass to the
normal paraffins in one or more conversion processes, such as, for example, by hydrotreating.
In embodiments, the normal paraffins are recovered from a process for hydroprocessing a
biologically derived feedstock comprising fatty acids. In ments, liquid products
recovered from the t from the hydrotreating process includes the C13 to C18 normal
ns, which may be separated from the remaining liquid products and blended with
middle distillate, to produce a renewable fuel blend having a pour point that is equal to or less
than the pour point of the middle distillate, without being subjected to a pour point ng
treatment. In embodiments, the pour point of the fuel blend comprising the biologically
derived normal paraffins and the middle distillate is at least 1°C, or at least 2°C, or at least
3°C lower than the pour point of the middle distillate. As before, the renewable fuel blend
prepared in this way, and containing the biologically d normal paraffins, has a resulting
pour point such that the relationship of Eq. 2 holds.
In embodiments, a biologically derived feedstock is blended with middle distillate,
and the blend is hydrotreated to form a renewable fuel blend comprising C13 to C18 normal
paraffins from the ically derived feedstock. In embodiments, the ble fuel blend
so prepared has a pour point that is equal to or less than the pour point of the middle distillate,
without being subjected to a pour point reducing treating. In embodiments, the renewable
fuel blend has a pour point that is equal to or less than the pour point of a similarly prepared
fuel blend, but in the absence of an added biologically derived feedstock in the feed to the
hydrotreating process. As before, the renewable fuel blend prepared in this way, and
containing the biologically derived normal paraffins, has a ing pour point such that the
relationship of Eq. 2 holds.
In embodiments, the biologically d ock is prepared an a preliminary
conversion process. In some such embodiments, the feed to the inary conversion
process comprises one or more of at least one biologically derived oil or cellulosic biomass.
The preliminary conversion process may involve one or more of pyrolysis, deoxygenation,
decarboxylation, decarbonylation, hydroxylation, saponification, hydrolysis, esterif1cation,
transesterification, interesterification, syngas conversion and arbon synthesis,
enation, hydrotreating or hydrocracking, prior to hydrotreating to convert the
intermediate products to liquid products comprising biologically derived C13 to C18 normal
paraffins.
A pour point reducing treatment process can be one or more processes useful for
reducing the pour point of middle late, diesel fuel, renewable fuel blend, biologically
derived hydrocarbon, and the like. Isomerization or hydroisomerization, including catalytic
isomerization or hydroisomerization, catalytic or solvent ng, filtering, clay treating
and adsorption and addition of pour point reducing additives are non-limiting examples of a
pour point reducing process. Thus, the process for preparing the renewable fuel blend
produces a low pour point t, including a pour point of no more than 0°C, t the
use of a pour point reducing process. Additional pour point reducing treatments, e. g. on
of pour point reducing additives, may be applied to the low pour point blend, if desired, to
further reduce the pour point.
Typical hydroisomerization conditions include a temperature between 200°F and
700°F, with a LHSV between 0.1 and 10. Hydrogen is employed such that the mole ratio of
hydrogen to hydrocarbon is between 1:1 and 15:1. Catalysts useful for isomerization
processes are lly bifunctional catalysts that include a dehydrogenation/ hydrogenation
component and an acidic component. The acidic component may e one or more of
amorphous mixed oxides such as silica-alumina; a ic material such as zeolite Y,
ultrastable Y, SSZ-32, Beta zeolite, mordenite, ZSM-5 and the like, or a non-zeolitic
molecular sieve such as SAPO—l 1, SAPO-31 and SAPO-41. The acidic component may
further include a halogen component, such as fluorine. The hydrogenation component may
be ed from the Group VIII noble metals such as platinum and/or palladium, from the
Group VIII non-noble metals such as nickel and tungsten, and from the Group VI metals such
as cobalt and molybdenum. If present, the platinum group metals will generally make up
from about 0.1% to about 2% by weight of the catalyst. If present in the catalyst, the non-
noble metal hydrogenation components generally make up from about 5% to about 40% by
weight of the catalyst. As used herein, the terms “isomerization” and “hydroisomerization”
are used interchangeably.
During solvent dewaxing, waxy molecules present in a petroleum or biologically
derived fluid are removed by chilling the fluid to permit the waxy molecules to agglomerate
into a suspended solid with solid particles large enough to be removed by filtering. The fluid
is generally mixed with a solvent, such as a 1:1 e of toluene and methylethylketone
prior to chilling to facilitate the process of separating the wax from the liquid portion of the
fluid.
The hydrotreating process refers to processes or ents that react a
hydrocarbon-based al with hydrogen, typically under pressure and with a catalyst.
Hydrotreating conditions include a reaction temperature between 400°F—900°F (204°C—
482°C); a pressure between 500 to 5000 psig (pounds per square inch gauge) (3.5—34.6 MPa);
a feed rate (LHSV) of 0.5 hr—1 to 20 hr—1 (v/v); and overall hydrogen consumption 300 to
2000 scf per barrel of liquid arbon feed (53.4—356 m3 H2 /m3 feed). The hydrotreating
catalyst will typically be a ite of a Group VI metal or compound f, and a Group
VIII metal or compound thereof supported on a porous refractory base such as alumina.
Examples of hydrotreating catalysts are alumina supported cobalt-molybdenum, nickel,
nickel-tungsten, cobalt-tungsten and nickel-molybdenum. Typically such hydrotreating
catalysts are presulflded.
The hydrotreating is conducted at on conditions and in the presence of a
catalyst to remove heteroatoms (including one or more of sulfur, en and oxygen) from
the feed to the hydrotreating. Hydrotreating is lly conducted at conditions to ensure
that no more than 15 wt. % of the feed to the reater is converted to lower molecular
weight products via carbon-carbon bond breaking, and to ensure that no more than 15 wt. %
of the normal paraff1ns in the feed to the hydrotreater, or generated during hydrotreating, are
converted to branched paraff1nic products via isomerization reactions.
In embodiments, the hydrotreating process for preparing the renewable fuel blend
from the blend of the biologically d feedstock with middle distillate further includes
reaction conditions such that at least 90 wt. % of the oxygen contained in the blend is
converted to H20, CO or C02. In embodiments, the hydrotreating step is conducted at
reaction ions such that less than 10 wt. % of the biologically derived normal paraff1ns
that are produced during hydrotreating are decarboxylated during hydrotreating. In
embodiments, the pour point of the ble fuel blend is lower than the pour point of the
middle distillate. In some such embodiments, the pour point of the renewable fuel blend is at
least 1°C, or 2°C, or 3°C lower than the pour point of the middle distillate from which it is
prepared.
Determination of biologically sources paraffins
The carbon content of biologically—derived resources and biologically—derived
products from a “new carbon” source may be determined by ASTM D6866—10. This test
method measures the 14C/lZC e ratio in a sample and es it to the 14C/lZC isotope
ratio in a standard 100% biobased material to give percent biobased content of the sample.
“Biobased materials” are organic materials in which the carbon comes from recently (on a
human time scale) fixated C02 present in the here using sunlight energy
(photosynthesis). On land, this C02 is captured or d by plant life (e. g., agricultural crops
or forestry materials). In the oceans, the C02 is captured or fixated by photosynthesizing
bacteria or phytoplankton. For example, a ed material has a 14C/12C isotope ratio
r than 0. In contrast, a fossil-based material has a 14C/12C isotope ratio of about 0.
WO 51016
The application of ASTM—D6866 to derive “biobased content” is built on the same
concepts as radiocarbon dating, but without use of the age equations. The analysis is
performed by deriving a ratio of the ty of radiocarbon (14C) in an unknown sample to
that of a modern reference rd. The ratio is reported as a percentage (percent modern
carbon). If the material being analyzed is a mixture of present day radiocarbon and fossil
carbon ining no radiocarbon), then the percent modern carbon value obtained correlates
ly to the quantity of biologically-derived material present in the sample.
The modern reference standard used in radiocarbon dating is a National Institute
of Standards and Technology standard with a known radiocarbon content equivalent
approximately to the year AD 1950. AD 1950 was chosen since it represented a time prior to
thermonuclear weapons testing which introduced large quantities of excess radiocarbon into
the atmosphere with each explosion (termed “bomb carbon”). The AD 1950 reference
represents 100 percent modern carbon. Bomb carbon in the atmosphere reached almost twice
normal levels in 1963 at the peak of testing and prior to the treaty halting the g. Its
distribution within the atmosphere has been approximated since its appearance, showing
values that are greater than 100 percent modern carbon for plants and s living since
AD 1950. It has gradually decreased over time with today's value being near 105.3 t
modern carbon (as of the year 2010). This means that a fresh biomass material such as corn
could give a arbon signature near 105.3 percent modern carbon.
ing fossil carbon with present day carbon into a material will result in a
dilution of the present day percent modern carbon content. By presuming 105.3 percent
modern carbon represents present day biologically—derived materials and 0 percent modern
carbon represents petroleum—derived materials, the measured percent modern carbon value
for that material will reflect the proportions of the two component types. A material derived
100% from present day soybeans would give a radiocarbon signature near 105.3 percent
modern carbon. If that material was d with 50% petroleum derivatives, it would give a
radiocarbon signature near 53 percent modern carbon.
A biomass content result is derived by assigning 100% equal to 105.3 percent
modern carbon and 0% equal to 0 percent modern carbon. In this regard, a sample measuring
99 percent modern carbon will give an equivalent ed content result of 94%.
2012/031531
In the example illustrated in Fig l, renewable fuel blend 10 is prepared as s:
mass units of palm oil 15 are blended with 90 mass units of middle distillate 20. The
middle distillate has a pour point of -7°C. During hydrotreating, the palm oil supplies to the
renewable fuel blend 2.8 mass units of C18 normal paraffins and 2.1 mass units of C16 normal
paraffins. To e a renewable fuel blend with a pour point equal to or less than —7°C, 5
mass units of C14 normal paraffin equivalent are added to the palm oil/middle distillate blend
prior to hydrotreating. This quantity of C14 normal paraffins is determined from the
relationship of Eq. 2, in order to produce a renewable fuel blend without requiring a pour
point reducing treatment to achieve a -7°C pour point. In the embodiment illustrated in Fig.
l, a biologically derived oil, such as algal oil 25 which has been ically tailored to
produce a significant quantity of C14 fatty acids, and little or no C18 fatty acids, is treated in a
inary conversion step 30 to produce a biologically derived feedstock 35 comprising
free fatty acids for supplying the 5 mass units of C14 normal paraffin equivalent (i.e. the
quantity of algae is added to provide 5 mass units of C14 normal paraffins in the renewable
fuel blend). The biologically derived feedstock 35 is ed with the palm oil 15 and the
middle distillate 20, and the blend 40 is hydrotreated in hydrotreating step 45. The renewable
fuel blend 10 recovered from the hydrotreated liquid effluent 50 is found to have a pour point
of —7°C or lower.
Example 1
A middle distillate having the properties shown in Table l was prepared.
Cloud point —6°C
Pour point —8°C
D86 distillation
Initial boiling point 375°F
50% by , 53 9°F
boiling point
Final boiling point 670°F
Flash point l76°F
0.8451 g/cm3
2012/031531
Example 2
The middle distillate of Example 1 was blended with various mixtures of normal
1ns to form fuel blends containing from 90 to 100 vol. % middle distillate, with varying
quantities of normal paraff1ns. The measured pour point of each blend is listed in in Table 2,
and ed with that of an estimated pour point, based on the equation:
Estimated pour point = 47.41 *AClg — 20.04*AC16 —18.91*AC14 — 8
(Eq- 3)
where:
AClg represents a quantity of C18 normal paraffins provided by the biologically
derived feedstock, as a vol. % of the renewable fuel blend;
AC16 represents a quantity of C16 normal paraffins provided by the biologically
derived feedstock, as a vol. % of the renewable fuel blend; and
AC14 represents a quantity of C14 normal paraffins provided by the biologically
derived feedstock, as a vol. % of the renewable fuel blend.
In this equation, the ept value, —8, represents the base case pour point in °C.
Figure 2 rates a set of blending relationships from the results in Table 2.
Each set of data points is a graphical representation of the change in pour point when a
normal paraffin is blended in varying quantities into middle distillate. One curve illustrates
the blend of C14 normal paraffin, one curve the blend of C16 normal in, and one curve
the blend of C18 with middle distillate. Also ed in Fig. 2 are lines which represent the
estimated pour point based on the relationship of Eq. 3. It will be noted that the estimated
pour points in each case closely match experimental . It will also be noted that C14 and
C16 normal paraffins have almost equal pour point reducing properties when blended with
this particular middle distillate, while C18 normal paraffins have a detrimental effect on pour
point at all concentrations.
Figure 3 illustrates another set of blending relationships from the results in Table
2. In each case, 10 vol. % normal paraffins were blended with the middle distillate of
Example 1. In one case, a blend of C14 and C18 normal paraff1ns with the middle distillate of
e 1 was ed, for a range of ratios between 10% C14 normal paraffin with no C18
normal paraffin, to 10% C18 normal paraffin with no C14 normal paraffin. A similar series of
test samples containing varying quantities of C16 and C18 normal ns was also screened
for changes in pour point.
The data illustrated in Fig. 3 is for a blend of 10 vol. % normal paraffins in the
middle distillate of Example 1. In one case, the renewable fuel blend included C14 and C18
normal paraffins, in varying quantities from 10% C14 to 10% C13 In the other case, the
renewable fuel blend included C16 and C18 normal paraffins, in varying quantities from 10%
C16 to 10% C18 normal paraffins. The lines connecting the experimental data represent the
ted pour point based on the predictive formula in Eq. 3.
Fig 3 again illustrates the close relationship between predicted and measured pour
points in the blends. Fig. 3 also shows that the ratio C14 (or C16):C18 of greater than 7:3 (i.e.
less than 30% C18) results in a renewable fuel blend with reduced pour point, with no pour
point reducing treatment.
Table 2
Change Of Pour Point For Blends Of Middle Distillate With ffins
C14 normal C16 normal C18 normal Pour Point, OC
Middle Cloud
paraffins, vol paraffin, vol paraffins, vol Pomt, OC
Distillate
% % %
Measured Estimate
from Eq. 3
Base case
100.0% 0.0% 0.0% 0.0% —8 —8 —6
Blends
92.5% 2.5% 2.5% 2.5% —8 —8 —6
93.4% 3.3% 3.3% 0.0% —9 —9 —6
93.4% 3.3% 0.0% 3.3% —7 —7 —6
95.0% 0.0% 5.0% 0.0% —9 —9 —7
90.0% 0.0% 10.0% 0.0% —10 —10 —8
95.0% 0.0% 0.0% 5.0% m —4
90.0% 5.0% 5.0% 0.0% —10 —10 —8
90.0% 0.0% 5.0% 5.0% —6 —7 —5
95.0% 5.0% 0.0% 0.0% —9 —9 —5
90.0% 0.0% 0.0% 10.0% —4 —3 —2
93.4% 0.0% 3.3% 3.3% —7 —7 —4
90.0% 10.0% 0.0% 0.0% —10 —10 —6
90.1% 3.3% 3.3% 3.3% —7 —8 —6
90.0% 5.0% 0.0% 5.0% —6 —7 —4
100.0% 0.0% 0.0% 0.0% —8 —8 —6
90.0% 0.0% 0.0% 10.0% —3 —3 —2
90.0% 5.0% 5.0% 0.0% —11 —10 —7
93.4% 3.3% 3.3% 0.0% —9 —9 —6
90.0% 5.0% 0.0% 5.0% —7 —7 —5
Example 4
A normal paraffin blend having the composition shown in Table 3 was prepared.
Table 3
Vol. % of normal
n blend
0.16
18.26
3.70
55.83
0.52
21.53
The normal paraffin blend was blended with a middle distillate, having physical
properties tabulated in Table 4.
50% by volume, 527°F
boiling point
Final boiling point 653°F
Flash point l40°F
Density 0.8301 g/cm3
Four blend products were prepared, ranging from 5 vol. % to 20 vol. % of the
normal paraffin blend. The pour points and cloud points of the blend products are tabulated
in Table 5.
Table 5
Quantity of normal ns in
blend product, vol. %
Cloud Point, °C
Pour Point, OC —l6 —17 —15
These data show that C13 to C17 normal paraffins, when blended at concentrations
up to 15 vol. % in middle distillate, improves both pour and cloud points of the blended
product ve to the middle distillate from which the blend product is made.
Claims (1)
- What is claimed l. A renewable fuel blend comprising in the range of from 1 vol. % to 20 vol. % of biologically derived C13 to C18 normal paraffins, such that the ratio AClg / (AC14 + AC16) is less than 05, wherein: AClg represents a quantity of biologically derived C18 normal paraffins, as a vol. % of the ble fuel blend; AC16 represents a quantity of biologically derived C16 normal paraffins, as a vol. % of the renewable fuel blend; and AC14 represents a quantity of biologically derived C14 normal ins, as a vol. % of the renewable fuel blend. The renewable fuel blend ing to Claim 1, wherein the ble fuel blend comprises from 3 vol. % to 15 vol. % biologically derived C13 to C18 normal paraffins. The renewable fuel blend according to Claim 1, n the renewable fuel blend comprises at least 5 vol. % C13 to C17 biologically derived normal paraffins. The renewable fuel blend according to Claim 1, wherein the ble fuel blend comprises no more than 3 vol. % biologically derived C18 normal paraffins. The renewable fuel blend according to Claim 1, wherein the ble fuel blend comprises no more than 3 vol. % biologically derived C12 normal ins. The renewable fuel blend according to Claim 1, wherein the ratio AClg / (AC14 + AC16) is in the range of between 0.01 and 0.4. The renewable fuel blend according to Claim 1, wherein the renewable fuel blend has a pour point in the range of from 0°C to —65°C. The renewable fuel blend according to Claim 1, wherein the ble fuel blend has a cloud point in the range of from 0°C to —65°C. The renewable fuel blend according to Claim 1 comprising from 80 to 99 vol. % petroleum derived hydrocarbons and from 1 to 20 vol. % biologically derived hydrocarbons, and having a boiling point range of between 200°C and 350°C. 10. The renewable fuel blend according to Claim 1, comprising biologically derived C13 to C18 normal paraffins such that the following relationship holds: 47.41*AC18 — 20.04*AC16 —18.91*AC14 S 0 wherein: AClg represents a quantity of ically derived C18 normal paraffins, as a vol. % of the renewable fuel blend; AC16 represents a quantity of biologically derived C16 normal paraffins, as a vol. % of the renewable fuel blend; and AC14 represents a quantity of biologically derived C14 normal paraffins, as a vol. % of the renewable fuel blend. 11. A process for producing a renewable fuel blend sing: a. pretreating at least one biologically d oil to produce a biologically derived ock; b. hydrotreating a blend of the biologically derived feedstock and a middle distillate to produce at least one hydrotreated liquid t; and c. recovering a renewable fuel blend comprising in the range of from 1 vol. % to 20 vol. % of biologically d C13 to C18 normal paraffins, such that the ratio AClg / (AC14 + AC16) is less than 0.5, wherein: AClg represents a quantity of biologically derived C18 normal paraffins provided by the biologically derived ock, as a vol. % of the renewable fuel blend; AC16 represents a quantity of biologically derived C16 normal ins provided by the biologically derived feedstock, as a vol. % of the renewable fuel blend; and AC14 represents a quantity of biologically derived C14 normal paraffins provided by the biologically derived feedstock, as a vol. % of the renewable fuel blend. 12. The process according to Claim 11, further comprising recovering a renewable fuel blend that comprises from 3 vol. % to 15 vol. % biologically derived C13 to C18 normal paraffins. 13. The process according to Claim 11, further comprising recovering a renewable fuel blend that comprises at least 5 vol. % biologically derived C13 to C17 normal paraffins. 14. The process according to Claim 11, further comprising recovering a ble fuel blend that comprises biologically derived C13 to C18 normal paraffins, such that the ratio AClg / (AC14 + AC16) is in the range ofbetween 0.01 and 0.4. 15. The process according to Claim 11, further comprising ring a renewable fuel blend that comprises ically derived C13 to C18 normal paraffins, such that the following relationship holds: 47.41*AC18 — 20.04*AC16 —18.91*AC14 S 0 wherein: AC18 represents a quantity of biologically derived C18 normal paraffins, as a vol. % of the renewable fuel blend; AC16 represents a quantity of biologically d C16 normal paraffins, as a vol. % of the renewable fuel blend; and AC14 represents a quantity of biologically derived C14 normal paraffins, as a vol. % of the renewable fuel blend. WO 51016 50—» 1
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/100,832 US9006501B2 (en) | 2011-05-04 | 2011-05-04 | Low pour point renewable fuel blend |
US13/100,832 | 2011-05-04 | ||
PCT/US2012/031531 WO2012151016A2 (en) | 2011-05-04 | 2012-03-30 | Low pour point renewable fuel blend |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ615840A NZ615840A (en) | 2015-06-26 |
NZ615840B2 true NZ615840B2 (en) | 2015-09-29 |
Family
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