U.S. patent application number 16/470316 was filed with the patent office on 2020-01-09 for hydrocarbon composition and method for producing a hydrocarbon composition.
This patent application is currently assigned to Neste Oyj. The applicant listed for this patent is Neste Oyj. Invention is credited to Anna Karvo, Tomi NYMAN, Virpi Ramo, Maija Rouhiainen.
Application Number | 20200010768 16/470316 |
Document ID | / |
Family ID | 60813868 |
Filed Date | 2020-01-09 |
United States Patent
Application |
20200010768 |
Kind Code |
A1 |
Rouhiainen; Maija ; et
al. |
January 9, 2020 |
HYDROCARBON COMPOSITION AND METHOD FOR PRODUCING A HYDROCARBON
COMPOSITION
Abstract
A method comprises conducting hydrodeoxygenation and optionally
isomerization of raw material, wherein the method further comprises
one or more solvent extraction steps and optionally hydrogenation
to remove aromatic and/or naphthenic hydrocarbons from the
material. The original aromatic and/or naphthenic content of the
raw material is less than 21 vol-%. In the method, the aromatic
and/or naphthenic content is reduced by more than 45%, preferably
by more than 60%. A composition contains hydrocarbons produced by
said method, wherein the total aromatic and/or naphthenic
hydrocarbon content of the composition is less than a predefined
low value, and C15-C20 i-paraffins are the main fraction of the
hydrocarbon content of the composition, weight basis.
Inventors: |
Rouhiainen; Maija; (Oulu,
FI) ; NYMAN; Tomi; (Vantaa, FI) ; Ramo;
Virpi; (Porvoo, FI) ; Karvo; Anna; (Porvoo,
FI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Neste Oyj |
Espoo |
|
FI |
|
|
Assignee: |
Neste Oyj
Espoo
FI
|
Family ID: |
60813868 |
Appl. No.: |
16/470316 |
Filed: |
December 14, 2017 |
PCT Filed: |
December 14, 2017 |
PCT NO: |
PCT/FI2017/050895 |
371 Date: |
June 17, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 2300/1014 20130101;
C10G 2300/1025 20130101; Y02P 30/20 20151101; C10G 67/14 20130101;
C10G 21/20 20130101; C10G 2300/1011 20130101; C10G 2300/1018
20130101; C10G 3/50 20130101; C10G 67/06 20130101; C10G 21/27
20130101; C10G 69/02 20130101; C10G 67/04 20130101; C10G 2300/1081
20130101 |
International
Class: |
C10G 67/04 20060101
C10G067/04; C10G 3/00 20060101 C10G003/00; C10G 67/14 20060101
C10G067/14; C10G 69/02 20060101 C10G069/02 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 16, 2016 |
FI |
20165977 |
Claims
1-18. (canceled)
19. A method for producing hydrocarbons with a very low aromatics
and/or naphthenics content, the method comprising: conducting
hydrodeoxygenation of raw material; and one or more solvent
extraction steps to remove aromatic and/or naphthenic hydrocarbons
from the raw material, wherein aromatics and/or naphthenics content
in the raw material is less than 2 vol-%; wherein the aromatics
and/or naphthenics content of the raw material is reduced by more
than 45%.
20. A method according to claim 19, wherein the method comprises:
conducting separation of a resulting material, wherein the
separation includes fractionation.
21. A method according to claim 19, wherein the method is carried
out in one or multiple reactors.
22. A method according to claim 19, wherein a solvent used in the
solvent extraction includes at least one of: N-methyl-2-pyrrolidone
(NMP), furfural, dimethyl formamide (DMF), dimethylsulphoxide
(DMSO), dimethyl isosorbide (DMI), polar solvent, aromatic solvent,
dipolar aprotic solvent, ionic liquid, deep eutectic solvent,
sulpholane, glycol, and phenol.
23. A method according to claim 19, wherein the raw material
comprises at least one of: paraffinic hydrocarbon, isoparaffinic
hydrocarbon, diesel, naphtha, natural gas, biogas, coal,
hydrotreated vegetable oil, vegetable oil, animal fat, fish fat,
microbial oil, algae oil, natural waste oil, and natural residue
oil.
24. A hydrocarbon composition produced by the method according to
claim 19.
25. The hydrocarbon composition according to claim 24, wherein a
total aromatic and/or naphthenic hydrocarbon content of the
hydrocarbon composition is less than a predefined low value, and
C.sub.15-C.sub.20 i-paraffins are a main fraction of the
hydrocarbon content of the hydrocarbon composition, on a weight
basis.
26. The hydrocarbon composition according to claim 24, wherein a
total aromatic and/or naphthenic hydrocarbon content of the
hydrocarbon composition is selected to be less than 10 000 ppm, or
4000 ppm or less, or 2000 ppm or less, or 1600 ppm or less, or 1200
ppm or less, or 1000 ppm or less, or 500 ppm or less, or 100 ppm or
less, or 50 ppm or less, or 30 ppm or less, or about 20 ppm, volume
basis.
27. The hydrocarbon composition according to claim 24, comprising:
80 wt-% C.sub.10-C.sub.20 i-paraffins or more, or about 93 wt-%,
based on a total weight of the hydrocarbon composition; and 20 wt-%
C.sub.10-C.sub.20 n-paraffins or less, based on the total weight of
the hydrocarbon composition.
28. The hydrocarbon composition according to claim 24, wherein
C.sub.14-C.sub.20 paraffins, C.sub.10-C.sub.15 paraffins,
C.sub.14-C.sub.16 paraffins, C.sub.15-C.sub.18 paraffins or
C.sub.17-C.sub.18 paraffins are the main fraction of the
hydrocarbon content of the hydrocarbon composition.
29. The composition according to claim 24, wherein the total
i-paraffinic content of the hydrocarbon composition is more than 80
wt-%, based on the total weight of the hydrocarbon composition.
30. The composition according to claim 24, wherein the total
n-paraffinic content of the hydrocarbon composition is less than 20
wt-%, based on the total weight of the hydrocarbon composition.
31. The composition according to claim 24, wherein the hydrocarbon
composition comprises C.sub.5-C.sub.10 i- and/or n-paraffins.
32. The hydrocarbon composition according to claim 24, wherein the
hydrocarbon composition is suitable for use as a solvent or a
solvent component.
33. The hydrocarbon composition according to claim 24, wherein the
hydrocarbon composition is in liquid form.
34. The hydrocarbon composition according to claim 24, wherein the
hydrocarbon composition is an emulsion.
35. The hydrocarbon composition according claim 24, wherein the
hydrocarbon composition is configured for a coating, paint,
lacquer, varnish, polish, ink, adhesive, sealant, resin, plastic,
catalyst, cleaning composition, peroxide desensitizer, pigment
dispersion, carrier fluid for an active ingredient, antioxidant,
biocide, insecticide, air freshener, crop protection composition,
detergent, grease removal composition, dry cleaning composition,
cosmetic, personal care composition, pharmaceutical, extender in a
dental impression material, vaccine, food ingredient, flavour
composition, fragrance, natural oil extraction, oil field chemical,
drilling mud composition, extraction process composition,
plasticizer for elastomer, paper processing chemical, lubricant,
functional fluid, transformer oil, metal working composition,
rolling or cutting fluid, water treatment composition, wood
treatment composition, construction chemical, mould release
material, explosive, mining chemical, solvent extraction
hydrocarbon composition, fuel component, heating oil, lamp oil, or
a combination thereof.
36. A method for applying a hydrocarbon composition according to
claim 19, in a coating, paint, lacquer, varnish, polish, ink,
adhesive, sealant, resin, plastic, catalyst, cleaning composition,
peroxide desensitizer, pigment dispersion, carrier fluid for an
active ingredient, antioxidant, biocide, insecticide, air
freshener, crop protection composition, detergent, grease removal
composition, dry cleaning composition, cosmetic, personal care
composition, pharmaceutical, extender in a dental impression
material, vaccine, food ingredient, flavour composition, fragrance,
natural oil extraction, oil field chemical, drilling mud
composition, extraction process composition, plasticizer for
elastomer, paper processing chemical, lubricant, functional fluid,
transformer oil, metal working composition, rolling or cutting
fluid, water treatment composition, wood treatment composition,
construction chemical, mould release material, explosive, mining
chemical, solvent extraction composition, fuel component, heating
oil, lamp oil, or a combination thereof.
37. A method according to claim 19, comprising: conducting
isomerization of the raw material and an hydrogenation step to
remove aromatic and/or naphthenic hydrocarbons from the raw
material; and reducing the aromatics and/or naphthenics content of
the raw material by more than 60%.
38. A method according to claim 20, wherein the method is carried
out in one or multiple reactors.
Description
FIELD OF THE INVENTION
[0001] The present disclosure relates to a hydrocarbon composition
and to a method for producing a hydrocarbon composition.
BACKGROUND
[0002] Isomerization refers to a chemical process by which a
compound is transformed into one or more of its isomeric forms,
i.e. forms having the same chemical composition but a different
structure or configuration and possibly different physical and
chemical properties. For example, branched-chain hydrocarbons are
better motor fuels than their straight-chain isomers. The
isomerization of straight-chain hydrocarbons to their corresponding
branched-chain isomers represents an example of isomerization
reactions of great industrial importance.
[0003] Isomerized hydrocarbon compositions with a lowered aromatic
content are commercially available in a chain length of C7-C14. The
dearomatization method used for obtaining these highly isomerized
hydrocarbon compositions is hydrogenation. In these compositions
the aromatic content is 1 ppm.
[0004] A method for obtaining isomerized hydrocarbon fractions is
disclosed in a patent application WO2015/101837, including a chain
length of C14-C15.
SUMMARY
[0005] An object is to provide a hydrocarbon composition with
extremely low aromatics content. The objects are achieved by a
method, composition, and use thereof, which are characterized by
what is stated in the independent claims. Preferred embodiments of
the invention are disclosed in the dependent claims.
[0006] An exemplary method is based on conducting
hydrodeoxygenation and optionally isomerization of raw material,
wherein the method further comprises one or more solvent extraction
steps and optionally hydrogenation to remove aromatic and/or
naphthenic hydrocarbons from the material. The original aromatic
and/or naphthenic content of the raw material is less than 2 vol-%.
In the method, the aromatic and/or naphthenic content is reduced by
more than 45%, preferably by more than 60%. An exemplary
composition contains hydrocarbons produced by said method, wherein
the total aromatic and/or naphthenic hydrocarbon content of the
composition is less than a predefined low value, and C15-C20
i-paraffins are the main fraction of the hydrocarbon content of the
composition, weight basis.
DETAILED DESCRIPTION OF EMBODIMENTS
[0007] The following embodiments are exemplary. Although the
specification may refer to "an", "one", or "some" embodiment(s) in
several locations, this does not necessarily mean that each such
reference is to the same embodiment(s), or that the feature only
applies to a single embodiment. Single features of different
embodiments may also be combined to provide other embodiments.
Furthermore, words "comprising", "containing" and "including"
should be understood as not limiting the described embodiments to
consist of only those features that have been mentioned and such
embodiments may contain also features/structures that have not been
specifically mentioned.
[0008] An embodiment discloses a method for dearomatization and/or
denaphthenization of raw material to produce a hydrocarbon product.
The method is based on the use of hydrodeoxygenation and solvent
extraction, and optionally isomerization and hydrogenation, in
combination. This means that the method comprises the consecutive
method steps of hydrodeoxygenation and solvent extraction, and
possibly isomerization and hydrogenation. The method may further
comprise a step of separating different hydrocarbon fractions by
fractionation. The method steps may be carried out in one or
multiple reactors.
[0009] The order of said method steps may differ from the one given
above. For example, 1.sup.st step may be solvent extraction,
2.sup.nd step may be hydrogenation, and 3.sup.rd step may be
solvent extraction, or 1.sup.st step may be hydrogenation, and
2.sup.nd step may be solvent extraction.
[0010] In an embodiment, one or more of said method steps may be
performed simultaneously.
[0011] A highly isomerized hydrocarbon product with very low
aromatic (or naphthenic) content may be produced with a process
combining hydrodeoxygenation, isomerization and solvent extraction
(and optionally hydrogenation and/or fractionation).
[0012] The method may be carried out in one or multiple
reactors.
[0013] The feedstock/raw material for the process may be paraffinic
hydrocarbon, isoparaffinic hydrocarbon, natural gas, biogas, coal,
diesel and/or naphtha or it may be of renewable and/or biological
origin, such as vegetable oil, hydrotreated vegetable oil, animal
fat, fish fat, microbial oil, algae oil and/or any other suitable
natural or biological oil, such as natural waste oil or natural
residue oil.
[0014] Solvent extraction provides an effective and inexpensive
method for aromatics and/or naphthenics removal. The method enables
further removal of aromatics and/or naphthenics from a raw material
having a low aromatics and/or naphthenics content.
[0015] Paraffins arranged in straight chains may be referred to as
normal paraffins i.e. n-paraffins, and paraffins arranged in
branched chains may be referred to as isoparaffins i.e i-paraffins.
A composition produced by the method may contain n- and i-paraffins
in different ratios depending on the processing parameters.
[0016] An embodiment discloses a hydrocarbon composition A and a
method for producing the hydrocarbon composition A. The hydrocarbon
composition A contains mainly C5-C10 i- and/or n-paraffins. In the
method for producing the hydrocarbon composition A, the steps of
hydrodeoxygenation, isomerization and solvent extraction are
combined with a fractionation step where i- and n-paraffins are
separated. The end product obtained contains over 90 wt-% C5-C10 i-
and/or n-paraffins.
[0017] Another embodiment discloses a hydrocarbon composition B and
a method for producing the hydrocarbon composition B. The
hydrocarbon composition B contains over 80 wt-% C10-C20 i-paraffins
and less than 20 wt-% n-paraffins. In the method for producing the
hydrocarbon composition B, the steps of hydrodeoxygenation,
isomerization and solvent extraction may be combined with a
fractionation step. End products with a variable content of C14-C20
paraffins (over 80 wt-% of i-paraffins) are obtained. The
fractionated end products may be, for example, mainly C10-C15
paraffins, mainly C14-C16 paraffins, mainly C15-C18 paraffins
and/or mainly C17-C18 paraffins.
[0018] In an embodiment, a composition is disclosed containing
highly isomerized hydrocarbons, wherein the total aromatic and/or
naphthenic hydrocarbon content of the composition is less than a
predefined low value, and i-paraffins are the main fraction of the
hydrocarbon content of the composition.
[0019] In an embodiment, the total aromatic and/or naphthenic
hydrocarbon content of the composition is less than 10 000 ppm,
preferably 4000 ppm or less, more preferably 2000 ppm or less, yet
more preferably 1600 ppm or less, yet more preferably 1200 ppm or
less, yet more preferably 1000 ppm or less, yet more preferably 500
ppm or less, yet more preferably 100 ppm or less, yet more
preferably 50 ppm or less, yet more preferably 30 ppm or less, most
preferably about 20 ppm, volume basis.
[0020] In an embodiment, the hydrocarbon composition is produced
from renewable and/or biological raw material. The renewable and/or
biological raw material comprises at least one of vegetable oil,
animal fat, fish fat, microbial oil, algae oil, natural waste oil,
and or natural residue oil.
[0021] The hydrocarbons may be C15-C20 hydrocarbons or C5-C10
hydrocarbons.
[0022] In an embodiment, the composition comprises 80 wt-% C10-C20
i-paraffins or more, preferably about 93 wt-%, based on the total
weight of the composition, and 20 wt-% C10-C20 n-paraffins or less,
based on the total weight of the composition. C14-C20 paraffins,
C10-C15 paraffins, C14-C16 paraffins, C15-C18 paraffins or C17-C18
paraffins are the main fraction of the hydrocarbon content of the
composition. The total i-paraffinic content of the composition is
more than 80 wt-%, based on the total weight of the composition.
The total n-paraffinic content of the composition is less than 20
wt-%, based on the total weight of the composition.
[0023] In an embodiment, the composition comprises about 90 wt-%
C5-C10 i- and/or n-paraffins, based on the total weight of the
composition.
[0024] In an embodiment, the hydrocarbon composition is produced by
a process comprising hydrodeoxygenation and optionally
isomerization of raw material, comprising at least one step of
solvent extraction, and optional steps of hydrogenation and/or
fractionation. The original aromatic/naphthenic content of the raw
material/feedstock is less than 2 vol-%. In the method, the
original aromatic/naphthenic content is reduced by more than 45%,
preferably by more than 60%.
[0025] In an embodiment, the composition is suitable for use as a
solvent or a solvent component.
[0026] In an embodiment, the composition is in liquid form.
[0027] In an embodiment, the composition is an emulsion.
[0028] In an embodiment, the composition may be used in a coating,
paint, lacquer, varnish, polish, ink, adhesive, sealant, resin,
plastic, catalyst, cleaning composition, peroxide desensitizer,
pigment dispersion, carrier fluid for an active ingredient,
antioxidant, biocide, insecticide, air freshener, crop protection
composition, detergent, grease removal composition, dry cleaning
composition, cosmetic, personal care composition, pharmaceutical,
extender in a dental impression material, vaccine, food ingredient,
flavour composition, fragrance, natural oil extraction, oil field
chemical, drilling mud composition, extraction process composition,
plasticizer for elastomer, paper processing chemical, lubricant,
functional fluid, transformer oil, metal working composition,
rolling or cutting fluid, water treatment composition, wood
treatment composition, construction chemical, mould release
material, explosive, mining chemical, solvent extraction
composition, fuel component, heating oil, lamp oil, or a
combination thereof.
[0029] In an embodiment, the method for producing the hydrocarbon
composition comprises conducting hydrodeoxygenation and optionally
isomerization of raw material, wherein the method further comprises
a step of solvent extraction and optionally hydrogenation. The
method may further comprise conducting separation of the resulting
material, wherein the separation may include fractionation or any
other suitable separation method. The method may be carried out in
one or multiple reactors.
[0030] In an embodiment, the solvent used in the solvent extraction
includes at least one of N-methyl-2-pyrrolidone (NMP), furfural,
dimethyl formamide (DMF), DMSO (dimethylsulphoxide), DMI (dimethyl
isosorbide), polar solvent, aromatic solvent, dipolar aprotic
solvent, ionic liquid, deep eutectic solvent, sulpholane, glycol,
and phenol.
[0031] A composition comprising highly isomerized hydrocarbons as
used herein refers to a composition where the degree of
isomerization is high. For example, the composition may comprise a
high weight percentage of i-paraffins compared to the weight
percentage of normal paraffins (n-paraffins), so that the main
fraction of the composition comprises i-paraffins. However, it is
also possible that the composition comprises an equal or higher
weight percentage of n-paraffins compared to the weight percentage
of i-paraffins. It is also possible that the composition comprises
a high weight percentage of i-paraffins but no n-paraffins, or vice
versa.
[0032] According to an exemplary aspect, provided is a method for
producing the composition comprising said paraffins. The method can
comprise hydrotreating a raw material of renewable/biological
origin to obtain a hydrotreated product comprising n-paraffins and
isomerizing the hydrotreated product to obtain an isomerized
product comprising i-paraffins and separation of said composition
by solvent extraction and possibly fractionation.
Example 1
[0033] A trace amount of aromatics from the composition B
containing approximately 90 wt-% i-paraffins and 0.31 vol-%
aromatic compounds were extracted with two different solvents,
according to a 4-step-working procedure. The chosen solvents were
N-methyl-2-pyrrolidone (NMP) and dimethylformamide (DMF). 10 vol-%
distilled water was added in both solvents to increase the
efficiency. 100 ml of the composition B was extracted three times
with the solvent in a 1:1 composition B to solvent ratio. A mixing
time of 2 min was used in each step. A 500 mL glass separation
funnel was used. After mixing, the extract was centrifuged to
separate the extract. Table 1 illustrates the aromatic contents (in
vol-%) of samples extracted in 3-step solvent extraction followed
by a washing step with water as analyzed by using a NM77 method (UV
spectrophotometric detection method). NMP=N-methyl-2-pyrrolidone,
DMF=dimethylformamide.
TABLE-US-00001 TABLE 1 NMP DMF Non-extracted composition B 0.31
0.31 Extract after step 1 0.2 0.16 Extract after step 3 0.12 0.16
Extract after step 3, washed with H.sub.2O 0.12 0.16
[0034] As can be seen from Table 1, both the tested solvents
clearly reduced the amount of aromatic residues in the composition
B. Already a single step solvent extraction procedure reduced the
amount of aromatics in the composition B by 35% in case of NMP, and
by 48% in case of DMF. After three solvent extraction steps, NMP
showed to be more effective leading to a 61% reduction in the
aromatic content of the composition B.
[0035] Thus, liquid-liquid extraction (solvent extraction) may be
applied for the separation of aromatics and/or naphthenics from the
compositions A and/or B. Solvents suitable for the extraction of
the aromatic/naphthenic compounds from the compositions A and/or B
may include, for example, N-methyl-2-pyrrolidone (NMP), furfural,
dimethyl formamide (DMF), DMSO (dimethylsulphoxide), DMI (dimethyl
isosorbide), and/or phenol. Water or some other cosolvent, such as
alcohol, may be used to enhance the separation process of the
aromatics from the composition. Also certain ionic liquids and/or
deep eutectic solvents, such as choline chloride, may be used to
remove aromatics from the composition.
[0036] In an embodiment, the method comprises performing the
consecutive (and/or simultaneous) steps of hydrodeoxygenation, and
optionally isomerization and hydrogenation, and one or more solvent
extraction steps until the aromatics and/or naphthenics content of
the material is reduced by more than 45%; for example, several
consecutive solvent extraction steps may be required until the
desired reduction of 45% in the aromatics and/or naphthenics
content of the material is achieved and hydrocarbons are produced
with an aromatics and/or naphthenics content of less than 10 000
ppm, preferably 4000 ppm or less, more preferably 2000 ppm or less,
yet more preferably 1600 ppm or less, yet more preferably 1200 ppm
or less, yet more preferably 1000 ppm or less, yet more preferably
500 ppm or less, yet more preferably 100 ppm or less, yet more
preferably 50 ppm or less, yet more preferably 30 ppm or less, most
preferably about 20 ppm, volume basis
[0037] It will be obvious to a person skilled in the art that, as
the technology advances, the inventive concept can be implemented
in various ways. The invention and its embodiments are not limited
to the examples described above but may vary within the scope of
the claims.
* * * * *