U.S. patent application number 15/589238 was filed with the patent office on 2017-08-24 for process and apparatus for producing hydrocarbons.
The applicant listed for this patent is UPM-KYMMENE CORPORATION. Invention is credited to Pekka Knuuttila, Jaakko Nousiainen.
Application Number | 20170240823 15/589238 |
Document ID | / |
Family ID | 40935848 |
Filed Date | 2017-08-24 |
United States Patent
Application |
20170240823 |
Kind Code |
A1 |
Knuuttila; Pekka ; et
al. |
August 24, 2017 |
PROCESS AND APPARATUS FOR PRODUCING HYDROCARBONS
Abstract
The invention relates to a process and an apparatus for
producing hydrocarbon components in the presence of a
hydrodesulphurization catalyst. The components obtained by the
process are suitable for use as fuel composition as such or as an
additive in fuel compositions, and in cosmetics or pharmaceutical
products.
Inventors: |
Knuuttila; Pekka; (Porvoo,
FI) ; Nousiainen; Jaakko; (Lappeenranta, FI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
UPM-KYMMENE CORPORATION |
Helsinki |
|
FI |
|
|
Family ID: |
40935848 |
Appl. No.: |
15/589238 |
Filed: |
May 8, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13382823 |
Jan 6, 2012 |
9677011 |
|
|
PCT/FI2010/050573 |
Jul 2, 2010 |
|
|
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15589238 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61K 8/31 20130101; C10G
3/46 20130101; C10G 3/50 20130101; Y02P 30/20 20151101; C10G
2400/02 20130101; C10G 45/58 20130101; C10G 2400/08 20130101; C10G
65/00 20130101; C10G 45/02 20130101; A61K 47/06 20130101; C10G
2300/1014 20130101; C10G 2400/04 20130101; C10G 2300/202 20130101;
C10G 2300/207 20130101; C10L 1/04 20130101 |
International
Class: |
C10G 65/00 20060101
C10G065/00; A61K 8/31 20060101 A61K008/31; A61K 47/06 20060101
A61K047/06; C10L 1/04 20060101 C10L001/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 7, 2009 |
FI |
20095767 |
Feb 2, 2010 |
FI |
20105092 |
Claims
1. A fuel composition, produced by the method comprising: providing
a terpene feed selected from a group consisting of crude sulphate
turpentine derived from kraft pulping process of wood (CST), crude
turpentine derived from mechanical pulping of wood, distillation
bottoms from turpentine distillation, turpentine evaporated from
crude tall oil, sulphur-containing C5 to C10 hydrocarbon streams
from wood processing, and mixtures thereof, at a WHSV of about 0.5
to about 10 measured in accordance with the following equation:
WHSV [ h - 1 ] = V feed [ g / h ] m catalyst [ g ] ##EQU00002##
wherein V.sub.feed[g/h] means a pumping velocity of the terpene
feed, and m.sub.catalyst[g] means an amount of the catalyst;
subjecting the terpene feed and a hydrogen gas, in a volumetric
ratio of hydrogen gas to the terpene feed of from about 100 to
about 1500 Nl/l, to a hydrogenation step at a temperature range of
from about 275.degree. C. to about 425.degree. C. and at a pressure
of 10 to 150 bar, in the presence of a hydrodesulphurization
catalyst selected from a group consisting of NiO/MoO.sub.3,
CoO/MoO.sub.3 and a mixture of NiO/MoO.sub.3 and CoO/MoO.sub.3 on a
support selected from Al.sub.2O.sub.3 and
Al.sub.2O.sub.3-SiO.sub.2, to produce hydrocarbon components
comprising C.sub.4-C.sub.28 hydrocarbons; and recycling at least a
portion of the hydrocarbon components back to the terpene feed
and/or to the hydrogenation step.
2. The fuel composition of claim 1, wherein the fuel composition is
selected from a group consisting of gasoline, diesel, naphtha and
jet fuel.
3. The fuel composition of claim 1, wherein the fuel composition
comprises a mixture of 1-isopropyl-4-methylbenzene,
1-isopropyl-4-methylcyclohexane and 2,6-dimethyloctane or isomers
thereof.
4. The fuel composition of claim 3, wherein the fuel composition
further comprises bicyclic C10 compounds.
5. The fuel composition of claim 1, wherein the fuel composition
comprises polycyclic hydrocarbons, monocyclic hydrocarbons, acyclic
hydrocarbons, and aromatic hydro-carbons.
6. The fuel composition of claim 1, for use in cosmetics or
pharmaceutical products.
7. The fuel composition of claim 1, for use as an additive in fuel
compositions.
8. A fuel composition comprising 10-15% polycyclic hydrocarbons,
20-50% monocyclic hydrocarbons, 7-15% acyclic hydrocarbons, and
15-50% aromatic hydrocarbons.
9. The fuel composition of claim 9, comprising a mixture of
1-isopropyl-4-methylbenzene, 1-isopropyl-4-methylcyclohexane and
2,6-dimethyloctane or isomers thereof.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional application of U.S. patent
application Ser. No. 13/382,823, filed Jan. 6, 2012, which is a 371
of International Application No. PCT/FI2010/050573, filed Jul. 2,
2010, which claims priority to Finland Application No. 20095767,
filed Jul. 7, 2009 and Finland Application No. 20105092, filed Feb.
2, 2010, the contents of which are incorporated hereby in their
entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to a process and an apparatus
for producing hydrocarbons. More particularly, the invention
relates a conversion of terpenes to hydrocarbon compounds which are
useful as various fuel grade compositions as such, or as fuel
blending components.
BACKGROUND OF THE INVENTION
[0003] There is an increasing interest on the use of hydrocarbon
components of biological origin from renewable sources in fuels to
replace the fossil starting materials. The use thereof is highly
desirable for environmental reasons. There is a lot of literature
relating to production of fuel composition from biological starting
materials like vegetable oils, such as tall oil.
[0004] US 2004/0230085 Al discloses a process for producing
hydrocarbon components from wood-based tall oil by a two-step
procedure in which a fatty acid fraction of tall oil (TOFA) is
subjected to a hydrodeoxygenation step to hydrogenate TOFA in the
presence of a desulphurization catalyst and then to an
isomerization step to branch the hydrocarbon chain. The products
obtained from the isomerization are predominantly i-paraffins which
are suitable for use as components in diesel fuels. The hydrocarbon
chain lengths suitable for diesel components are typically in the
range of C.sub.9-C.sub.20.
[0005] US 2009/0020089 Al discloses a fuel composition comprising
at least a tetra-methylcyclohexane and optionally an aromatic
isoprenoid compound, and a monocyclic and acyclic hydrocarbon
component. The fuel composition can be of petrol fuel grade, for
example. The tetramethylcyclohexane is produced by hydrogenation of
pinene in the presence of a hydrogenation catalyst. Pinene and the
starting materials for the optional components included in the fuel
composition are produced by microbiological methods using a host
cell.
[0006] Tall oil is retrieved from the kraft pulping process of
coniferous wood as a by-product. From the same process, also crude
turpentine is extracted as a by-product. Chemical compositions of
said substances differ from each other to a significant extent.
Tall oil is mainly composed of fatty acids and resin acids with a
chain length varying between C.sub.12 to C.sub.18, and fused ring
systems as abietic acids and sitosterols, while the crude
turpentine comprises an oil mixture of terpenes derived from pitch.
Terpenes are a wide range of volatile hydrocarbons having a
chemical formula of C.sub.10H.sub.16, including typically
unsaturated mono- and bicyclic hydrocarbons. Crude turpentine,
which contains terpenes, is formed in the kraft pulping process is
generally referred to as crude sulphate turpentine (CST). The main
terpene components included in the CST are .alpha.-pinene,
.beta.-pinene and and .DELTA.-3-carene. The major component is
typically .alpha.-pinene.
##STR00001##
[0007] The unsaturated bicyclic terpenes included in the
turpentine, having the formulas given above, are too reactive as
such for use as fuel components. Also, the high sulphur content of
the turpentine prevents using it for fuel application.
[0008] Processes for converting terpenes to cymenes are previously
known. In these processes, different types of catalysts are used
for the conversion. For example, alkali metal carbonate catalysts,
catalysts comprising noble metals or rare earth metals on a zeolite
support and a palladium catalyst supported on activated carbon or
alumina have been used.
[0009] CST comprising a large amount of terpene isomers also
contains a relatively high amount of sulphur, up to 6%, as a
contaminant. In order to be able to utilize the CST for further
applications sulphur has to be removed from it. In EP 0267833 A1
sulphur is removed from the terpenes included in the crude
turpentine through hydrogenation in the presence of a catalyst of
cobalt and molybdenum oxides on an inorganic support. It is desired
that any chemical transformation of the terpenes is avoided during
the hydrodesulphurization procedure.
[0010] At present, the crude sulphate turpentine is processed for
use as a solvent or odorants in pharmaceutical and cosmetic
industry. However, a wide range of utilization of the turpentine is
restricted because of the high level of sulphur, and no cost
efficient processes for desulphurization and refining the
turpentine are now present. Accordingly, a large amount of the
crude sulphate turpentine is now burned without further
processing.
BRIEF DESCRIPTION OF THE INVENTION
[0011] It has now been found that terpenes can be converted to
various fuel grade components by a one-step process by using a
conventional hydrodesulphurization (HDS) catalyst. The components
obtained in the process of the invention can be used as fuel
compositions as such or as fuel additives in the fuel compositions.
Examples of the fuel compositions are diesel, gasoline, naphta and
jet fuels.
[0012] For example, hydrocarbon components having a carbon number
typical for gasoline components, varying from C.sub.4 to C.sub.10,
are received from the process of the invention. Also, hydrocarbon
components having a carbon number typical for diesel components,
varying from C.sub.10 to C.sub.28, are received from the process of
the invention. A part of the produced components can also be
utilized in other products, such as in cosmetics or pharmaceutical
products.
[0013] It has been specifically found that an amount of aromatics,
especially paracymene obtained in the process, can be increased in
an appropriate manner by controlling the process parameters.
Paracymene has a particular value as a fuel component. Moreover, it
can be utilized for cosmetics and in pharmaceutical industry.
[0014] Drawback of the known processes for producing paracymene
from terpenes is that the catalytic activity of the catalysts used
is destroyed by the presence of sulphur even at low
concentrations.
[0015] In a specific embodiment of the invention, crude sulphate
turpentine is used as a starting material. The crude sulphate
turpentine may also comprise distillation bottoms products from
turpentine distillation. As stated above, the high sulphur content
of the turpentine prevents using it for fuel application. It was
surprisingly found that terpenes can be converted in one single
step to a form that contains only a small amount of sulphur, or to
a form where the sulphur can be easily removed by using a
conventional hydrodesulphurization catalyst while the crude
sulphate turpentine is converted to valuable products useful in a
fuel application. It is an advantage of the process that there is
no need of any pretreatment procedure in order to remove sulphur
from the CST prior to its further processing. In an embodiment, the
invention thus provides a simple, efficient and economical process
for the treatment of the crude sulphate turpentine to provide a
product that is usable for fuel applications.
[0016] It is thus an object of the present invention to provide a
process and an apparatus for producing hydrocarbon components which
may be utilized as fuel components. The object of the invention is
achieved by what is stated in the independent claims.
[0017] Another object of the invention is to provide a use of the
hydrocarbon components obtained by the process of the invention as
fuel composition or fuel additives in the fuel compositions. The
fuel composition can be gasoline, diesel, naphtha or jet fuel.
[0018] A further object of the invention is to provide a fuel
composition comprising hydrocarbon components produced by
subjecting a terpene feed and a hydrogen gas to a
hydrodesulphurization step in the presence of a
hydrodesulphurization catalyst.
[0019] A still further object of the invention is to provide an
additive to be used in a fuel composition comprising hydrocarbon
components produced by subjecting a terpene feed and a hydrogen gas
to a hydrodesulphurization step in the presence of a
hydrodesulphurization catalyst.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 shows an embodiment of an apparatus of the invention
comprising one hydrogenation reactor where a hydrodesulphurization
catalyst is packed in one layer in the reactor.
[0021] FIG. 2 shows another embodiment of an apparatus of the
invention comprising one hydrogenation reactor where a
hydrodesulphurization catalyst is packed in two separate layers in
the reactor.
[0022] FIG. 3 shows an embodiment of an apparatus of the invention
comprising two hydrogenation reactors where a hydrodesulphurization
catalyst is packed in one layer in each reactor.
[0023] FIG. 4 shows an embodiment of an apparatus of the invention
comprising a hydrogenation reactor and a hydrogen sulphide
separator.
DETAILED DESCRIPTION OF THE INVENTION
[0024] An object of the invention is to provide a process for
producing hydrocarbon components, comprising:
[0025] providing a terpene feed;
[0026] subjecting the terpene feed and a hydrogen gas feed to a
hydrogenation step in the presence of a hydrodesulphurization
catalyst to produce hydrocarbon components.
[0027] Terpenes constituting the starting material for the process
of the present invention can be obtained from any suitable source.
The hydrocarbons can contain heteroatoms and minor amounts of
heavier hydrocarbons as a contaminant. In an embodiment of the
invention, the terpene feed is composed of C.sub.10H.sub.16
terpenes. In another embodiment of the invention, the terpene feed
is substantially composed of crude turpentine. In the present
invention, the term `crude turpentine` is to be understood to
include crude turpentine of wood origin. Crude turpentine from any
source of this origin is suitable for the purpose of the invention.
In an embodiment of the invention, the crude turpentine is obtained
from kraft pulping process of coniferous wood as crude sulphate
turpentine which is predominantly composed of volatile unsaturated
C.sub.10H.sub.16terpene isomers derived from pitch. The crude
turpentine of this origin is also referred to as crude sulphate
turpentine (CST). Due to the process chemicals used in kraft
process, sulphur is included the crude turpentine as a contaminant,
amounting typically up to 6% by weight.
[0028] In another embodiment of the invention, the crude turpentine
is derived from mechanical pulping of wood, like from grinding and
pressure grinding, thermomechanical pulping, or chemimechanical
pulping. From these processes, turpentine can be retrieved in
gaseous form, provided that the process is equipped with gas
collecting means. Also from chipping of wood or saw mills
turpentine can be recovered in gaseous form.
[0029] In a further embodiment, crude turpentine is meant to
include distillation bottoms from turpentine distillation.
[0030] In a still further embodiment, crude turpentine is meant to
include turpentine separated from crude tall oil which is retrieved
from kraft pulping process of coniferous trees.
[0031] In a still further embodiment, crude turpentine is meant to
include one or more volatile unsaturated terpenes, especially
.alpha.-pinene, .beta.-pinene and .DELTA.-3-carene, which is/are
isolated from turpentine or any other source.
[0032] The crude turpentine can be used in purified or unpurified
form.
[0033] In a further embodiment of the invention, also a mixture of
various crude turpentines can be used as a terpene feed.
[0034] In another embodiment of the invention, sulphur-containing
C5 to C10 hydrocarbon streams from wood processing industry or side
streams from wood processing industry can be used as a terpene
feed.
[0035] The hydrogenation step in the process can be accomplished by
using a conventional hydrodesulphurization (HDS) catalyst known in
the art. It is to be noted that any catalysts conventionally used
for removal of heteroatoms from the organic compounds can be used
in the process of the invention. Heteroatoms are typically sulphur,
oxygen and nitrogen. Particularly, catalysts which are typically
referred to as (HDO) catalysts in the art can be used in the
process. HDO hydrodeoxygenation catalysts are especially intended
for oxygen removal but are usable for sulphur and nitrogen removal
as well. In the present invention, the HDS catalyst is selected
from a group consisting of NiO/MoO.sub.3, CoO/MoO.sub.3 and a
mixture of NiO/MoO.sub.3 and CoO/MoO.sub.3 on a support selected
from Al.sub.2O.sub.3 and Al.sub.2O.sub.3-SiO.sub.2. In a specific
embodiment of the invention, NiO/MoO.sub.3 on the Al.sub.2O.sub.3
support is used.
[0036] In the following, the invention will be further illustrated
in light of the crude sulphate turpentine (CST) as a starting
material, while it is to be understood that the invention is not
limited to this embodiment.
[0037] The HDS catalyst used in the present invention has a
capability of hydrogenating the olefinic bonds of the terpene
compounds included in CST. Moreover, compounds having bicyclic
terpene structure are decomposed and at least one of the bicyclic
rings is opened. In addition, the HDS catalyst is advantageously
capable of simultaneously removing undesirable sulphur compounds
present in the CST, like dimethyl sulphide, dimethyl disulphide and
methyl mercaptane, by converting the organic sulphur compounds to
gaseous hydrogen sulphide. Sulphur removal is generally called
hydrodesulphurization (HDS). Thus, in the present invention, CST
undergoes a HDS step in which the above chemical transformation
reactions are simultaneously taken place.
[0038] In the HDS step, light gaseous hydrocarbons, like methane,
are also formed. Generally, gaseous compounds including hydrogen
sulphide, methane and H.sub.2 formed in the HDS step can be easily
discarded from the process and separated from each other, if
desired.
[0039] It is characteristic of the HDS catalyst that sulphur has to
be present to maintain the catalytic activity of the catalyst.
Advantageously, when the hydrocarbon feed comprises CST, hydrogen
disulphide needed for catalytic activity of the catalyst is thus
simultaneously provided from the sulphur compounds inherently
present in CST. Gaseous hydrogen sulphide can be easily discarded
from the mixture of the gasoline components, if necessary.
[0040] It may be necessary to supply supplementary sulphur to the
process to maintain the catalytic activity of the catalyst.
Supplementary sulphur can be supplied in gaseous form like hydrogen
sulphide, or it can be any material that produces hydrogen sulphide
in the process, like organic sulphur compounds, such as dimethyl
disulphide. In an embodiment of the invention, supplementary
sulphur is provided by recirculating the H.sub.2S-containing gas
retrieved from the mixture of fuel components produced by the
process of the invention. The amount of supplementary sulphur
depends on the amount of sulphur in the CST. Generally, the H.sub.2
feed/H.sub.2S relation must be maintained over about 0.0001. This
means that an added amount of sulphur is in the range of about 100
to about 200 ppm. Sulphur can be fed to the initial crude
turpentine feed, for example, or to the hydrogenation step.
[0041] The amount of hydrogen gas needed to hydrogenate the
olefinic bonds of the terpene structure is determined by the amount
of the turpentine feed. A suitable amount of hydrogen can be
determined by a man having ordinary skills in the art. Typically,
the relation H.sub.2 feed/turpentine feed is in the range of about
100 to about 1500 Nl/l, preferably about 100 to about 350, more
preferably about 100 to about 300 (Nl=normal litre).
[0042] If desired, any hydrocarbon component can be isolated from
the mixture of the hydrocarbon components received in the process
of the invention.
[0043] In an embodiment of the invention, the mixture of
hydrodesulphurized hydrocarbon components is subjected to a
hydrogen sulphide removal step to remove any residual hydrogen
sulphide from the mixture.
[0044] Terpenic compounds present in the CST undergo a number of
chemical reactions including hydrogenation, isomerization,
dehydrogenation, hydrogenolysis and C-C bond cleavage. Favour of
the various reactions is influenced by the reactions conditions,
especially temperature and feeding speed (WHSV) of the CST to the
reaction. Various reactions of the initial components of the CST,
i.e. .alpha.-pinene and .DELTA.-3-carene, can be described, for
example, as follows:
##STR00002## ##STR00003##
[0045] Compounds obtained in the process of the invention can be
classified in unsaturated non-terpenic hydrocarbons, terpenes,
acyclic, polycyclic, monocyclic and aromatic hydrocarbons. The main
components obtained in the process of the invention are the
following compounds and their isomers:
##STR00004##
i.e. p-cymene
[0046] If no ring opening takes place completely in the HDS step,
bicyclic C10 compounds can also be formed, the structure of which
corresponds to that of the starting compounds except that the
olefinic bonds are reduced. It has been recognized that when
operating at lower temperatures, ring opening of the initial
compounds is reduced and the relative amount of the bicyclic
compounds is increased. The temperature in the HDS step can vary
from about 200 to about 450.degree. C., preferably from about
275.degree. C. to about 425.degree. C. The most preferable
operating temperature is about 400.degree. C. When operating at
temperatures over about 330.degree. C., there is a tendency that
the content of the aromatic hydrocarbons, especially
1-propyl-4-methylbenzene, also called cymene or p-cymene, is
increased. This effect has a benefit that the octane number of the
product is increased and the content of the bicyclic compounds are
reduced, respectively. The octane number of the product can thus be
controlled by means of process conditions. If desired, an octane
enhancer such as ethanol can be added to the product obtained by
the process of the invention.
[0047] The proportions of the various hydrocarbon components
produced in the process can be influenced by controlling the
temperature and/or WHSV through the catalyst layer. For example,
the HDS step can be carried out by using a gradient temperature
where the temperature of the catalyst layer in the inlet arranged
for terpene feed is higher than the temperature of the catalyst
layer in the outlet for product recovery. By controlling the
temperature and/or WHSV in the HDS step, the content of the
aromatics predominantly composed of cymenes, particularly p-cymene,
in the reaction mixture can be raised up to 50%. In this
embodiment, the temperature in the HDS step ranges from about
330.degree. C. to about 425.degree. C.
[0048] Recirculation of the product produced in the hydrogenation
step also provides means for affecting the proportions of the
hydrocarbon components in the mixture. Especially, recirculation
has an advantage that the content of aromatics, particularly
p-cymene, can be increased at lower temperatures.
[0049] Hydrodesulphurization of the CST is highly exothermic
reaction in which temperature can rise to a level which is
detrimental to the catalytic activity of the catalyst and/or
product quality. In some cases, it may be necessary to control the
temperature variations. Recirculation of the product, i.e. the
mixture of the hydrocarbon components, provides an efficient means
for constraining the exothermic reaction whereby the recycled
product stream acts as an inert media lowering the temperature of
the bed in a controlled manner. In an embodiment of the invention,
the hydrocarbon components obtained in the process are circulated
back to the initial turpentine feed and/or to the ongoing HDS
step.
[0050] The pressure in the HDS step can vary from about 10 to about
150 bar, preferably from about 20 to about 70 bar. More preferably,
the process of the invention is performed at a pressure of about 25
to about 50 bar.
[0051] The HDS step can be effected either in a single catalyst
layer or in two or more catalyst layers. The one or more catalyst
layers can be arranged in a single reactor or in several reactors
as described in more detail below.
[0052] After the HDS step, the sulphur is retrieved in the form of
gaseous hydrogen sulphide which easily evaporates from the product.
The sulphur content of the product mixture can be reduced to a
level of 10 ppm at most, the level being within the range
stipulated for gasoline fuels. However, in some cases it may be
necessary to remove the residual hydrogen sulphide from the product
received in the HDS step in order to achieve the above sulphur
level. This can be accomplished by various methods, like stripping,
flashing or bubbling with inert gas, for example nitrogen gas. If
desired, hydrogen sulphide retrieved can be led to the
hydrogenation step for maintaining the catalytic activity of the
catalyst.
[0053] Moreover, if appropriate, a pre-treatment step can be
accomplished prior to the HDS step. The pre-treatment step can
include one or several of the following procedures: distillation,
filtration and cleaning of the CST.
[0054] The process of the invention produces a mixture of
hydrocarbon components. In order to be able to utilize the obtained
hydrocarbon mixture in an optimum manner, the mixture is further
subjected to separation to separate the mixture into various fuel
grade hydrocarbon fractions. Separation can be realized
conveniently by distillation. Specifically, product streams having
distillation curves conforming to those of standardized diesel,
gasoline, naphtha and jet fuels are achieved. As a general,
hydrocarbons distilling at a temperate range from 180 to
370.degree. C. are obtained as a middle distillate conforming to
diesel fuel quality standard EN 590. Hydrocarbons distilling at
temperatures ranging from 150.degree. C. to 210.degree. C. are
useful as high quality gasoline fuel. They conform to the standard
EN 228. Hydrocarbons having a distillation temperature between
160.degree. C. and 300.degree. C. are useful as aviation
applications, generally referred to as jet fuel. The jet fuel
conforms to standard ASTM D-1655. Hydrocarbons having a
distillation temperature above 370.degree. C. is useful as heavy
fuel oil. The composition of the products obtained with the process
of the present invention depends on the feed material used as well
as on the operation conditions of the process.
[0055] The process of the invention provides high quality
hydrocarbon components that are useful as fuel or as a fuel
additive in the conventional fuel compositions. The invention thus
further provides a use of the hydrocarbon components prepared by
the process of the invention as a fuel composition or as an
additive in the fuel compositions. The fuel composition can be
gasoline, diesel, naphtha or jet fuel. The properties of fuel
composition conform to those of the desired standards, especially
to EN590, EN228 and ASTM D-1655. Preferably, the process of the
invention produces hydrocarbon components suitable as gasoline
fuel.
[0056] Another object of the invention is to provide an apparatus
for producing hydrocarbon components. The apparatus of the
invention is adapted to realize an embodiment of the process of the
invention. The apparatus comprising
[0057] at least one hydrogenation reactor 1, 1' comprising at least
one catalyst layer 3, 3' of a HDS catalyst
[0058] terpene inlet pipe 9
[0059] hydrogen feed pipe 5, 50, 50'
[0060] product outlet pipe 10, 15 for recovering a mixture of the
hydrocarbon components.
[0061] A further object of the invention is to provide a fuel
composition comprising hydrocarbon components produced by
subjecting a terpene feed and a hydrogen gas to a
hydrodesulphurization step in the presence of a
hydrodesulphurization catalyst.
[0062] A still further object of the invention is to provide an
additive to be used in a fuel composition comprising hydrocarbon
components produced by subjecting a terpene feed and a hydrogen gas
to a hydrodesulphurization step in the presence of a
hydrodesulphurization catalyst.
[0063] With reference to FIG. 1, crude sulphate turpentine and
H.sub.2 are fed to a hydrogenation reactor 1 including a catalyst
layer 3 for hydrodesulphurization of the CST. The hydrogenation
reactor is for example in a form of a separate tank or a tubular
reactor. CST and H.sub.2 are supplied via terpene feed pipe 4 and
hydrogen feed pipe 5, respectively. In the FIG. 1, CST and H.sub.2
feeds are combined and fed together via terpene inlet pipe 9 to the
reactor 1. In an embodiment of the invention, inlet pipe 9 is
omitted and the feed pipes 4 and 5 enter separately the reactor
1.
[0064] The catalyst bed comprising a HDS catalyst can be packed in
one or more layers 3, 3' in the reactor 1. Also, one or more of the
catalyst layers can be diluted with an appropriate medium. The
diluting material can be for example the passive material used in
passive layers described below, or another catalyst suitable for
hydrogenation. In an embodiment, where several catalyst layers are
used in the reactor, the first layer downstream of the turpentine
feed is diluted while the remaining layers are undiluted. If the
first layer downstream of the turpentine feed is diluted, it acts
as a pre-hydrogenation catalyst. In FIG. 1, the HDS catalyst is
packed in one layer 3. Preferably, the catalyst layer 3 is
undiluted in the embodiment illustrated in FIG. 1.
[0065] H.sub.2 feed can be supplied to reactor 1 downstream to the
turpentine feed. H.sub.2 feed can also be supplied to reactor 1 via
H.sub.2 feed pipe 50 at one or more locations between the terpene
inlet pipe 9 and the product outlet pipe 10, preferably at one or
more locations in the catalyst layer 3, to control reaction
conditions of the exothermic hydrogenation reaction. These H.sub.2
feed inlets are denoted by reference numbers 6,7 and 8.
[0066] H.sub.2 can also be fed upstream to the turpentine feed,
i.e. the H.sub.2 and turpentine feeds are countercurrent to each
other (not shown in FIG. 1).
[0067] Catalytic hydrodesulphurization reaction and other
reactions, i.e. ring opening and saturation of olefinic bonds, are
carried out in a catalyst layer 3 packed in the reactor 1. Product
is recovered from the reactor 1 via product outlet pipe 10. At
least a portion of the product, i.e. a mixture of the hydrocarbon
components, can be circulated back to the reactor 1 through
recirculation pipe 100 as shown by the dotted line in the Figure.
In the recirculation, the product can be combined with the initial
CST and H.sub.2 feeds into a single feed flow and supplied to the
reactor 1 through the terpene inlet pipe 9 as shown in the Figure.
The recirculation pipe 100 can also be arranged to the reactor 1
separately from the terpene inlet pipe 9. The product can also be
supplied to the reactor 1 at one or more locations between the
terpene inlet pipe 9 and the product outlet pipe 10, preferably at
one or more locations in the catalyst layer 3 via inlets 6,7 and
8.
[0068] Moreover, at least a portion of the product can be supplied
via pipe 101 to a separating reactor 17 for separating one or more
hydrocarbon fractions from the mixture of the hydrocarbon
components. The reactor 17 is appropriately a distillation
apparatus in which the hydrocarbon fractions are separated based on
differences in boiling points. One or more of the isolated
fractions useful as various fuel grade components can be recovered
via pipe 18.
[0069] Also, passive layers 11 and 12 comprising suitable passive
or inert material, such as Al.sub.2O.sub.3, SiC or glass beads can
be arranged in the reactor 1. Their task is to act as guard beds
against harmful substances in the feed. When a passive layer is
arranged in the reactor as the first layer to receive the feed via
inlet pipe 9, upstream of the catalyst layer, it acts also as
preheating and cleaning layer for the feed. It also enhances the
even distribution of the feed to the catalyst. In FIG. 1, a first
passive layer 11 is arranged upstream of the catalyst layer 3, and
a second passive layer 12 is arranged downstream of the catalyst
layer 3.
[0070] If appropriate, supplementary sulphur from an outer source
is supplied via sulphur feed pipe 16 to the reactor 1 through
inlets 6, 7, 8, and/or 9. Supplementary sulphur can also be fed to
the turpentine feed. Supplementary sulphur fed via pipe 16 can be
any compound that produces hydrogen sulphide in the process, like
organic sulphur compounds, such as dimethyl disulphide.
[0071] The crude turpentine is pumped to the reactor 1 at a desired
speed. Feed rate
[0072] WHSV (weight hourly spatial velocity) of the turpentine feed
is proportional to an amount of the catalyst and is calculated
according to the following equation:
WHSV [ h - 1 ] = V feed [ g / h ] m catalyst [ g ] ##EQU00001##
[0073] wherein V.sub.feed[g/h] means a pumping velocity of the
crude turpentine feed, and m.sub.catalyst[g] means an amount of the
catalyst;
[0074] WHSV is typically in the range from about 0.5 to about 10,
preferably in the range of about 1 to about 5.5.
[0075] The proportions of the hydrocarbon components in the product
mixture produced by the process can be influenced by adjusting WHSV
to a desirable range. In an embodiment of the invention, WHSV is
adjusted to the range from about 2 to about 3.5 where a production
of p-cymene is increased.
[0076] The amount of hydrogen feed is proportional to the amount of
the turpentine feed. Typically, the relation H.sub.2
feed/turpentine feed is in the range of about 100 to about 1 500
Nl/l, for example about 100 to about 350 Nl/l (Nl=normal
litre).
[0077] FIG. 2 shows another embodiment of an apparatus of the
invention where a HDS catalyst is packed in two separate catalyst
layers, a first catalyst layer 3' and a second catalyst layer 3, in
a hydrogenation reactor 1. The first catalyst layer 3' is arranged
upstream of the second catalyst layer 3 and it comprises diluted
hydrogenation catalyst material. The second catalyst layer 3
comprises undiluted hydrogenation catalyst material. Further, an
intermediate insulating layer 13 is disposed between the two
catalyst layers to prevent the layers to mix with each other and to
facilitate the operating of the first and second catalyst layers in
different temperatures. As an intermediate layer the same material
can be used as in the passive layers. A passive layer 11 is
arranged upstream of the first catalyst layer 3'. The H.sub.2 feed
can be supplied to the reactor 1 either downstream to the
turpentine feed, or the H.sub.2 feed can be supplied to the reactor
1 via H.sub.2 feed pipe 50 at one or more locations denoted by
reference numbers 6,7 and 8. When appropriate, the H.sub.2 feed can
be divided so that a part of the H.sub.2 feed is supplied to the
first catalyst layer 3' and a part of it is supplied to the second
catalyst layer 3, as shown in FIG. 2.
[0078] As in an embodiment illustrated in FIG. 1, external sulphur
can be supplied via sulphur feed pipe 16 to the reactor 1, if
appropriate. Also, external sulphur feed can be divided so that a
part of the external sulphur feed is supplied to the first catalyst
layer 3' and a part of it is supplied to the second catalyst layer
3.
[0079] In an embodiment of the invention, when NiMo/Al.sub.2O.sub.3
or CoMo/Al.sub.2O.sub.3 catalysts are being used in the catalyst
layer 3 and/or 3' for accomplishing the hydrogenation step, the
catalyst has to be activated before it is effective in
hydrogenation. The activation comprises several steps, of which one
is treating the catalyst with activating sulphur compound, for
example dimethyl disulphide. The activation of such catalysts is
common knowledge in the art and will thus not be discussed here in
detail.
[0080] Product recovered via product outlet pipe 10 can be further
led to a separating reactor 17 in a similar manner as shown in FIG.
1 (not shown in FIG. 2).
[0081] FIG. 3 shows an embodiment of the invention, where a HDS
catalyst is packed in two separate catalyst layers, a first
catalyst layer 3' and a second catalyst layer 3, which layers 3'
and 3 are disposed in separate reactors, a first reactor 1' and a
second reactor 1, respectively. The first reactor 1' is arranged
upstream of the second reactor 1. In an embodiment of the
invention, the first catalyst layer 3' includes diluted HDS
catalyst, whereas the second catalyst layer 3 includes undiluted
HDS catalyst. Passive layers 11' and 12', and 11 and 12 are
arranged in the reactors 1' and 1, respectively.
[0082] Crude sulphate turpentine is fed to the first reactor 1'.
The product obtained from the first reactor 1' is recovered via
pipe 10' and further supplied to the second reactor 1. The product
is recovered via product outlet pipe 10 from the second reactor
1.
[0083] H.sub.2 feed is supplied to both reactors 1' and 1. H.sub.2
feed can be supplied either downstream to the turpentine feed, or
the H.sub.2 feed can be supplied to the reactors 1' and 1 via
H.sub.2 feed pipes 50' and 50, at one or more locations denoted by
reference numbers 6', 7' and 8', and 6,7 and 8, respectively.
[0084] In another embodiment of the invention, both first and
second catalyst layers 3' and 3 comprise diluted hydrogenation
catalyst material. The catalyst layers may be arranged in the same
reactor, as in the embodiment shown in FIG. 2, or they may be
arranged in separate reactors, as illustrated in the embodiment
shown in FIG. 3.
[0085] In an embodiment of the invention, both first and second
catalyst layers 3', 3 comprise the same catalyst material, either
NiMo/Al.sub.2O.sub.3 or CoMo/Al.sub.2O.sub.3. In another embodiment
of the invention, the catalyst layers comprise different catalyst
materials, preferably the first catalyst layer 3' comprises
NiMo/Al.sub.2O.sub.3 and the second catalyst layer 3 comprises
Co-Mo/Al.sub.2O.sub.3.
[0086] At least a portion of the product, i.e. a mixture of the
hydrocarbon components, can be circulated back to the first reactor
1' through recirculation pipe 100 as shown by the dotted line in
the FIG. 3. In the recirculation, the product can be combined with
the initial CST and H.sub.2 feeds into a single feed flow and
supplied to the reactor 1' through the terpene inlet pipe 9 as
shown in the Figure. The recirculation pipe 100 can also be
arranged to the reactor 1' separately from the terpene inlet pipe
9. The product can also be supplied to the reactor 1' at one or
more locations between the terpene inlet pipe 9 and the pipe 10',
preferably at one or more locations in the catalyst layer 3' via
inlets 6', 7' and 8'.
[0087] If appropriate, external sulphur is supplied via sulphur
feed pipe 16 to the reactor 1' through inlets 6', 7', 8' and/or 9,
and/or to the reactor 1 through inlets 6,7 and/or 8. Supplementary
sulphur can also be fed to the turpentine feed.
[0088] Product recovered via product outlet pipe 10 can be further
led to a separating reactor 17 in a similar manner as shown in FIG.
1 (not shown in FIG. 3).
[0089] FIG. 4 shows an embodiment of the apparatus of the
invention, where the product recovered from the catalytic
hydrodesulphurization reaction of the CST in a liquid form is fed
from the hydrogenation reactor 1 via pipe 10 to a H.sub.2S removal
reactor 2. In the H.sub.2S removal reactor 2, gaseous compounds
composing predominantly of hydrogen sulphide, hydrogen and methane
are removed from the product via pipe 14. This can be accomplished
for example by stripping, flashing or bubbling with inert gas, such
as nitrogen.
[0090] When supplementary sulphur supply is desired, at least part
of the gaseous compounds recovered from the reactor 2 can be
recirculated back to the reactor 1 via H.sub.2S re-circulation pipe
140 as shown in FIG. 4 by a dotted line. Supplementary sulphur can
also be supplied to the reactor 1 from an outer source via sulphur
feed pipe 16 through inlets 6, 7, 8, and/or 9. Supplementary
sulphur can also be fed to the turpentine feed. Supplementary
sulphur fed via pipe 16 can be any compound that produces hydrogen
sulphide in the process, like organic sulphur compounds, such as
dimethyl disulphide.
[0091] The fuel grade product that has been treated in the H.sub.2S
removal reactor 2 is recovered via product outlet pipe 15. As in
the embodiment illustrated in the FIG. 1, at least a portion of the
product can be supplied to a separating reactor 17 for separating
one or more hydrocarbon fractions from the mixture of the
hydrocarbon components. Also, recirculation of the product obtained
in the process of the invention via product recirculation pipe 100
can be accomplished in a similar manner as in FIG. 1 in an
embodiment illustrated in FIG. 4 (not shown).
[0092] Gaseous compounds can also be led to a gas treatment system
(not shown in FIG. 4). In the gas treatment system, gaseous
compounds recovered from the H.sub.2S reactor are treated.
Unreacted hydrogen is cleaned from hydrogen sulphide and methane by
means of membrane technique, for example. The cleaned hydrogen is
pressurized and can be recycled into the reactor 1 (not shown).
Hydrogen sulphide and methane are utilized e.g. as energy by
burning. Hydrogen sulphide can also be recycled to pulp mills
chemical recovery cycle and converted to elementary sulphur by
Claus process.
[0093] The following examples are presented for further
illustration of the invention without limiting the invention
thereto.
EXAMPLE 1
[0094] Crude turpentine obtained from kraft pulping process, i.e.
CST, was used as a crude turpentine feed. The crude turpentine
comprised 50-60% .alpha.-pinene, 20-30% of A-carene, the rest being
other terpenes. The sulphur content was about 1.5%.
TABLE-US-00001 TABLE 1 Feed CST Sulphur content (%) about 1.5
Pumping of feed (V.sub.feed) (g/h) 10 Catalyst NiMo/Al.sub.2O.sub.3
Amount of catalyst (g) 10 Reaction pressure (bar) 50 H.sub.2 (l/h)
15 WHSV (h.sup.-1) about 1 Temperature of bed (.degree. C.) 300
H.sub.2 feed/turpentine feed (Nl/l) 1250
[0095] The catalyst was packed into one layer in the reactor.
[0096] The composition of the product obtained was measured for two
samples. For the first sample, no hydrogen sulphide was removed
from the product sample. This is denoted by sample number 1 in
Table 2 below. For the second sample, hydrogen sulphide was removed
from the product sample by bubbling it with gas. This is denoted by
sample number 2. The results from the two analyses are summarized
in Table 2.
TABLE-US-00002 TABLE 2 Sample number 1 2 Sulphur (ppm) 60 10
Density at 15.degree. C. (g/mL) 0.8124 0.8124 Vapour pressure
(DVPE) <1 <1 MON 75 75 RON 75 75 Benzene content <0.1
<0.1 Oxidation stability >720 >720 Hydrocarbon type
content Olefins 3.2 3.2 Aromatics 13.6 13.6 Unsaturated
hydrocarbons (non terpenes) n.d. n.d. Terpenes (%) n.d. n.d.
Acyclic hydrocarbons (%) 14 14 Polycyclic hydrocarbons (%) 16 16
Monocyclic hydrocarbons (%) 52 52 Aromatic hydrocarbons (%) 15 15
Others (%) 3 3 n.d.: not detected MON = Motor Octane Number RON =
Research Octane Number
[0097] The results indicate that the terpene structure is
decomposed and the olefinic bonds are hydrogenated so as to provide
components that are suitable for use as gasoline components.
EXAMPLE 2
[0098] The same turpentine feed as in Example 1 was used in this
Example. The process parameters are summarized in Table 3 below.
The catalyst was packed in two layers in the reactor. The first
layer comprised of diluted catalyst and the second layer comprised
of undiluted catalyst. The diluted catalyst layer comprised of 40%
catalyst and 60% of SiC, calculated on volume basis.
TABLE-US-00003 TABLE 3 Feed CST Sulphur content (%) about 1.5
Pumping of feed (V.sub.feed) (g/h) 40 Catalyst NiMo/Al.sub.2O.sub.3
Amount of catalyst (g) 30 (10 g diluted + 20 g undiluted) Reaction
pressure (bar) 50 H.sub.2 (l/h) 30 WHSV (h.sup.-1) about 1.3
Temperature of bed (.degree. C.) 340 H.sub.2 feed/turpentine feed
(Nl/l) 640
[0099] As in Example 1, the composition of the product obtained was
measured for two samples. The sample numbers have the same meanings
as in Example 1.
TABLE-US-00004 TABLE 4 Sample number 1 2 Sulphur (ppm) 60 6 Density
at 15.degree. C. (g/mL) 0.8202 0.8202 Vapour pressure (DVPE) <1
<1 MON 87 87 RON 96 96 Benzene content <0.1 <0.1 Oxidation
stability >1576 >1576 Hydrocarbon type content Olefins 1.7
1.7 Aromatics 28.6 28.6 Unsaturated hydrocarbons (non terpenes)
n.d. n.d. Terpenes (%) n.d. n.d. Acyclic hydrocarbons (%) 10 10
Polycyclic hydrocarbons (%) 10 10 Monocyclic hydrocarbons (%) 40 40
Aromatic hydrocarbons (%) 30 30 Others (%) 10 10
[0100] The quantities in both of the examples were measured in
accordance with the following standards: [0101] Sulphur: EN ISO
20846 [0102] Density at 15.degree. C. (g/mL): EN ISO 12185 [0103]
Vapour pressure (DVPE): EN 13016-1 [0104] Benzene content: EN 238
[0105] Oxidation stability: EN ISO 7536 [0106] Hydrocarbon type
content: EN 15553
[0107] The test results clearly show that it is possible to
influence on the shares of product components. By increasing the
content of the aromatic compounds one can increase the octane
number of the gasoline components produced from CST.
EXAMPLE 3
[0108] The products obtained in Examples 1 and 2, from which
hydrogen sulphide was removed by bubbling with inert gas, were
blended with a standard 95E gasoline in various mixing ratios. The
mixing ratios were as follows: [0109] Sample 1: 95E gasoline
blended with 5% of sample number 2 of Example 1. [0110] Sample 2:
95E gasoline blended with 10% of sample number 2 of Example 1.
[0111] Sample 3: 95E gasoline blended with 5% of sample number 2 of
Example 2. [0112] Sample 4: 95E gasoline blended with 10% of sample
number 2 of Example 2.
TABLE-US-00005 [0112] TABLE 5 95E gasoline Sample 1 Sample 2 Sample
3 Sample 4 MON 85.4 85.3 84.9 85.2 85.0 RON 95.8 95.3 94.5 95.6
95.1
[0113] The test results show that when using the product obtained
by the process of the invention as an additive in a standard 95E
gasoline, no significant change in the octane numbers was
observed.
EXAMPLE 4
[0114] The same turpentine feed as in Example 1 was used in this
Example. The process parameters are summarized in Table 6 below.
The catalyst was packed in two layers in the reactor, as in Example
2.
TABLE-US-00006 TABLE 6 Feed CST Sulphur content (%) about 1.5
Pumping of feed (V.sub.feed) (g/h) 98 Catalyst NiMo/Al.sub.2O.sub.3
Amount of catalyst (g) 10 g (diluted) + 20 g (undiluted) Reaction
pressure (bar) 30 H.sub.2 (l/h) 25 WHSV (h.sup.-1) 4.9 Temperature
of bed (.degree. C.) 405 H.sub.2 feed/turpentine feed (Nl/l)
215
[0115] The composition of the product is shown in Table 7
below.
TABLE-US-00007 TABLE 7 Polycyclic hydrocarbons (%) 14.6 Monocyclic
hydrocarbons (%) 21.3 Acyclic hydrocarbons (%) 7.9 Aromatic
hydrocarbons (%) 48.0 Others (%) 8.2
* * * * *